Shrikant Athavale

Rubber&
Adhesive Technologist

0091 7498956621
psatechno@gmail.com

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on
Resin Dispersions

A reference book
for Adhesive Compounder’s
Research & Development
e Book
on Resin Dispersions
A reference book for the Compounders of Pressure Sensitive
Adhesives, Lamination or other Adhesives, specially Water
Borne. This is A FREE e book available on Demand, through
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The Contents Page No

1. Fundamentals of WB Resin Technology 03- 04
2. Basic Dispersion Theory Part 1 05- 23
3. Basic Dispersion Theory Part 2 24- 46
4. Resin Dispersions Find application 47- 56
5. Solutions Colloids and Suspensions 57- 60
6. What is Resin 61- 73
7. Predicting Ingredient Compatibility 74- 84
8. Resin Dispersion Essentials 85- 98
9. Resin Dispersions a Research Report 99- 106
10. Selecting Tackifiers 107- 137
11. Tackifier Properties Part 1 138- 154
12. Tackifier Properties Part 2 155- 182
13. The Nature and Action of Tackifier Resins 183- 184
14. Resin Dispersions now made in India 185- 199
15. Now Boost WB PSA Performance 200- 213
16. Using HC Resin Dispersions 214- 218
17. Resin dispersions and Their Role 219- 232
18. US Patents on Resin Dispersion 233- 277
Fundamentals of Waterborne Resin Technology
Waterborne coatings are the largest type of
coating technology used on a global basis
and are expected to continue to grow as a
percent of the total coatings market. By
2022, the global market size of waterborne
coatings is expected to be over $146 billion
USD. Growth in large part is due to
increased volume in the construction and
automotive markets with acrylics being the
largest single type of waterborne resin system representing over 80% of
the total waterborne market.

Driving forces for the increased use of waterborne coatings include:

 Lower VOC
 Ease of clean-up in most cases
 Decreased fire hazard
 Lower insurance cost
 Lower energy use for baked coatings due to the need for less
oven make up air
 The need for decreased levels of petroleum-based materials.

As the May, 2014 Prospector

article on Flow, Levelling and
Viscosity Control in Water-
Based Coatings indicates, the
two largest classes of waterborne
coatings include water-
reducible and latex, with the
majority of baked coatings
falling in the first category with
most of the architectural coatings
belonging to the second
category. The term water-
reducible is used for resins made
in solvent and reduced in water to form a dispersion of resin in
water. Latex resins on the other hand are prepared by emulsion
polymerization in water.

Disadvantages for the use of waterborne coatings include:

 High dependence of evaporation rate on relative humidity

 High heat of evaporation for water requires 2260 J/g for water
and for example only 373 J/g for 2-butoxyethanol, a commonly
used cosolvent
 Nonlinear viscosity reduction curve for coatings using water
reducible resins
 High dependence of flow and appearance on relative humidity
 High surface tension of water (poorer wetting) requires the
addition of surfactants which in many cases detracts from
humidity resistance
 Waterborne coatings are more corrosive than solvent born
coatings and thus require lined containers, plastic or stainless
steel to avoid rust
 Waterborne coatings are more prone to popping in baked
applications as film formation begins to occur before water
evaporates from the film (see Table I)

However the continued advancement in material science to include

innovations in resin chemistry, surfactants, wetting agents and flow
agents will help enable the continued growth of waterborne coatings.

Figure I represent the various stages in drying of a latex based paint

system. The first stage involves the evaporation of water. The second
stage includes the continued evaporation of water and cosolvent to the
point where the latex particles touch and begin to coalescence to form a
film that is partially dried.

The final stage involves the continued coalescence and cure (in a
crosslinked system) to form a cured, dry adherent paint film.
One of the key considerations in the use of waterborne coatings is the
increased role that humidity in addition to temperature plays in the
application and cure of these coatings. For example, to provide
acceptable application properties, both the temperature and humidity
must be carefully controlled as illustrated in Figure II. The effect of
humidity on coatings containing water-organic solvent cannot be
ignored.

For example, the relative evaporation rate (E) of water at 0 – 5% RH at

25°C is 0.31, but at 100% RH the E is 0. The E of 2-butoxyethanol, a
commonly used cosolvent, is 0.077. At low RH, water evaporates more
rapidly and thus the ratio of 2-butoxyethanol to water increases; the
reverse is true at high humidity.

When waterborne coatings are applied, if humidity is ignored, variation

in application properties and appearance will result. For example, if the
temperature at application year-round is 70° – 80° F, dry application
(loss of flow) will result in winter months due to low humidity
especially in colder climates and excessive flow will be observed in
summer months (high humidity). An example of the later situation is
that at about 65% Relative Humidity/25 °C, a waterborne coating
containing 10.6% 2-
butoxyethanol of
volatiles, the
evaporation rate of
water and 2-
butoxyethanol is
equal. This relative
humidity is called
the Critical Relative Humidity.

Figure II Application Dependence of Waterborne Coatings on Humidity

and Temperature.

Table I illustrates the increased dependence of waterborne coatings on

popping at various film thicknesses when compared to solvent born
coatings.
 Table I Critical Film
Thickness for Popping in
Microns, Organic
Coatings, Wiley-
Intercedence, 2007, Zeno
W. Wicks Jr., Frank N.
Jones, S. Peter Pappas,
Douglas A. Wicks

Waterborne coatings
include a wide variety of
resin types such

as acrylic, alkyd, urethane, polyester, epoxy, fluoropolymer, waterborne

powder as well as curing chemistries including UV cure, aminoplast,
urethane, epoxy-polyamide, oxidative and air dry thermoplastic types.
As Table II illustrates, particle size and particle architecture (e.g. core
shell) also contributes to the ultimate film properties of the coating. In
summary, once the unique issues associated with the use of waterborne
coatings are fully considered they offer excellent performance in a wide
variety of applications.

Table II – Characteristics of Various Water Based Resins

Prospector lists several suppliers of waterborne resins, surfactants,

wetting and flow agents to meet a variety of requirements.
The Basics of Dispersion and Stabilization of
Pigments and Fillers
Introduction
Dispersion and
stabilization of
solid particles (pigments and fillers) in a liquid is a challenging process,
taking place during the production of paints, colorants and inks. The
whole process consists of three steps, starting from a dry powdery
material that consists of agglomerates of the solid particles.

The three steps of the dispersion process.

Wetting of the particles
takes place when the
powdery solid is brought in
contact with liquid. The
solid particles are separated
from each other by applying mechanical force. The separated particles
must be stabilized to prevent flocculation.
In the following, the three steps are discussed separately even though
they mostly occur simultaneously.
1. Wetting
During wetting, the air that is present at the surface of the particles and
within the agglomerates is replaced by the liquid that is used in the
dispersion process.

Wetting: solid-air interface transforms into solid-liquid interface.

A pre-condition for wetting is that the surface tension of the liquid is
low enough compared to the surface energy of the solid
particles1. Wetting agents are additives used to facilitate wetting in
case the surface energy of the particles is too low2. The functionality of
a wetting agent is to lower the surface tension of a liquid. The use of
wetting agents can induce problems like foam, insufficient intercoat
adhesion, increased water sensitivity and reduced film hardness.
In many cases, wetting agent is not needed in the dispersion process.
Moreover, using wetting agent often retards wetting instead of
improving it. Wetting, as well as the release of air from the system,
 proceeds faster when the viscosity of the
liquid is lower. The importance of
wetting is often underestimated, thus
giving problems in the steps that follow
in the dispersion and stabilization
process.
2. Separation
Agglomerates — solid particles that are
glued together — are split in the
separation step. Because of the strong attractive forces between the
solid particles, separating them requires a high amount of mechanical
energy that is provided by suitable equipment.

Two

principles are used to split

agglomerates into smaller
pieces.

A disk disperser, often called dissolver, works by means of shear

forces. A disk, with teeth on the edge, rotates with high speed in a
liquid mill base of high viscosity, thus shearing the particles apart.
In a bead mill, often called pearl mill, the impact principle (combined
with crunching) is used to split agglomerates. Beads (pearls) collide
with each other and agglomerates that are between the beads are
hammered and crunched into smaller pieces.

Mill chamber of a bead mill and beads. (courtesy of WAB)

An axis with rotor blades rotates in the mill chamber that is partly filled
with beads. The input of a bead mill is a redispersion that is made by
using, for example, a disk
disperser. The output of a bead
mill is a dispersion of solid
particles, with the desired
particle size distribution, in
liquid.
 3.

Stabilization
Particles that have been separated from each other must be stabilized to
prevent flocculation, the spontaneous gluing together of solid particles
in a liquid.

Separation and flocculation of solid particles in a liquid.

Solid particles are stabilized against flocculation by means of a
polymeric additive called dispersant3,4,5. Dispersant molecules must
adsorb strongly at the surface of the particles. This adsorption
phenomenon is often referred to as anchoring. The groups that have a
strong affinity for the surface of the particles are called anchoring
groups.

The functionality of a dispersant is to provide colloidal stability. A

dispersion is said to be stable from colloidal point of view when
flocculation of separated particles is prevented because the particles
repel each other.
Two principles of stabilization against flocculation are used.
First, all particles can have the same electrostatic charge, thus making
them repel each other. This so-called electrostatic stabilization is
critical, and it depends upon key system properties like pH and the
amount of electrolyte that is present. In water-based paints and inks
mostly anionic stabilization is used, implying that all particles have a
negative charge6.
Secondly, the particles can be covered with a layer of polymeric tails
that dissolve in the liquid that surrounds the particles, thus giving steric
stabilization7. It turns out that steric stabilization is the most secure
principle to use, in both solvents based and water-based systems.
References
Surface Tension & Surface Energy, Jochum Beetsma, 27 September
2019.
Surface Active Agents (Surfactants), Marc Hirsch, 25 September 2015.
Understanding Dispersants, Marc Hirsch, 19 February 2016.
 Dispersant Technology, George Deckner, 25
July 2014.
Settle Down: Factors that Influence Pigment
Settling and Stability, Ron Lewarchik, 12
May 2017.
Dispersants for Electrostatic Stabilization,
Jochum Beetsma, 7 October 2016.
Dispersants for Steric Stabilization, Jochum Beetsma, 28 October 2016.
Surface Tension and Surface Energy
Posted on September 27, 2019 by Jochum Beetsma — 2 comments

Interfaces, boundaries between two phases, are important in coating

and ink technology. The behavior of a system during production,
storage, application and film formation is, to a large extend, governed
by the composition of the interfaces that are present and by the total
amount of interfacial area. A key property, associated with the
composition of an interface, is interfacial tension. There are two
categories of interfacial tension, represented by the Greek
symbol γ (‘gamma’), that are most important in paints and inks.
Surface tension
Surface tension is a property of liquids that is governed by
intermolecular interactions: it originates from the cohesive forces
between molecules in a liquid. Thermodynamics tells us that systems,
like paints and inks, strive to attain a state with a maximum amount of
favorable interactions. This implies that liquids will shape in such a way
that the number of bulk molecules is at a maximum and the amount
of surface molecules is at a minimum.
Increasing surface area: molecules are forced from the bulk to the
surface.
Molecules at the surface of a liquid are not fully surrounded by their
fellows; surface molecules are partly naked. This implies that molecules
at the liquid-air interface experience less favorable interactions and are
in a state of higher energy compared to molecules in the bulk of the
liquid.Therefore, energy is needed to move molecules from the bulk of
the liquid to the surface. The stronger the interactions between the
molecules are, the more energy is required to increase the surface area
of a liquid.
 The surface tension of a
liquid, γlg, is defined as the
energy (in Joule) needed to
create 1 m2 of new liquid-gas interfacial area. The dimension of γ is
J/m2. Often the dimension N/m (Newton per meter) is used. Two
subscripts are used to specify the interface to which an interfacial
tension refers. An interface is a boundary between two phases.
Therefore, the abbreviation of these phases should be included in the
symbol for the interfacial tension. Surface tension is the interfacial
tension of a liquid-gas interface. In paints and inks the ‘gas’ phase is
most often the air above the system.
Surface tension values of some pure liquids at room temperature.
n-Hexane has a low surface tension because the mutual interactions
between the molecules in the liquid are relatively weak. The surface
tension of a

liquid with high surface

tension, like water, can be
lowered by adding molecules
that have a surfactant structure,
like wetting agents.1,2 Such additives lower the surface tension of a
liquid because the molecules adsorb and orient at the liquid-air
interface in such a way that the hydrophobic tails point towards the air
and the hydrophilic parts stick into the liquid. Wetting can be improved,
and film defects can be prevented, by using suitable wetting agents.3
Behavior of wetting agent at a liquid-air interface.
Surface energy
Surface energy is a key property of solid materials, like substrates that
must be coated. Surface energy is the interfacial tension of a solid-gas
interface. The property is represented by the symbol γsg, with the
subscript ‘s’ standing for solid and ‘g’ for gas. The gas above the solid
surface is most often air.
Surface energy of a solid material.
Strong interactions are possible with a solid surface that has a high
surface energy. Unsurprisingly, a high surface energy is beneficial for
the wetting of,
and adhesion on, substrates.
Solids with a low surface
energy, like most plastics, are
difficult to coat.
The surface energy of plastic objects can be raised by using pre-
treatment techniques, such as corona treatment, plasma treatment or
flame treatment, thus improving wetting and adhesion.4
Surface energy values of some substrates.
References
Surface Active Agents (Surfactants), Marc Hirsch, 25 September 2015.
[https://www.ulprospector.com/en/eu/Coatings/Detail/30648/635175/Su
rface-Active-Agents-Surfactants]
Breaking the Tension with Surfactants, Angie Pedersen, 27 July 2018.
[https://knowledge.ulprospector.com/8516/pc-surfactant-infographic/]
Overcoming Paint Film Defects: Causes and Remedies, Ron
Lewarchik, 16 June 2017.
[https://knowledge.ulprospector.com/6636/pc-overcoming-paint-film-
defects-causes-remedies/]
Plasma Processing of Plastic Surfaces, 30 December 2016, Andy Pye.
[https://knowledge.ulprospector.com/5708/pe-plastic-surface-plasma-
processing/]
The views, opinions and technical analyses presented here are those of
the author or advertiser and are not necessarily those of UL’s
Prospector.com or UL LLC. All content is subject to copyright and may
not be reproduced without prior authorization from UL or the
advertiser. While the editors of this site may verify the accuracy of its
content from time to time, we assume no responsibility for errors made
by the author, editorial staff or any other contributor.

Breaking the Tension with Surfactants [INFOGRAPHIC]

In this busy world, it pays to be a multitasker. At any given time, you
may need to wear any of several hats, depending on the situation.
Surfactants are like that. Otherwise known as “surface active agents,”
they can serve as wetting agents, emulsifiers, foaming agents,
and dispersants, depending on the formulation needs. To better
illustrate, we’ve gathered some relevant facts and market trends about
surfactants, specifically their use in the paints and coatings industry.
For example, did you know that Europe is the largest consumer of
biosurfactants, because of consumer awareness of potential health
hazards? For additional insights into surfactants in coatings
formulation, be sure to also check out Marc Hirsch’s article, “Surface
Active Agents (Surfactants).”

Understanding Dispersants
Posted on February 19, 2016 by Marc Hirsch — Leave a Comment

The definition of dispersant, in terms of physical chemistry, is: a

material that, when incorporated in to an admixture, is capable of
homogeneously maintaining the dispersed particles in suspension.
Therefore, the goal is to distribute dry pigments into a liquid medium
and eliminate agglomerates.
Agglomerates are clumps of pigment, which, when not dispersed fully,
affect many properties including¹:
Flocculation
Flooding/floating
Bénard cells
Color shift/change
Gloss decrease
Several types of additives can be used in the dispersion process in
which solid particles, like pigments and fillers, are distributed and
stabilized in a liquid. It is not enough to separate the particles, since
they can re-agglomerate afterwards. This re-agglomeration is termed
flocculation.

In Figure 1, a light blue paint has been applied to a substrate. Due to

poor dispersion or flocculation, when the paint is partially dry, a test for
dispersion is the application of shear by a finger in a circular motion
(“rub-out test”). That energy in a semi-set paint film is enough to
redistribute the pigment in the medium, resulting in the dark blue area.
In addition to the dispersion of pigments, the surfactant displaces the air
at the interface of the pigment particle. One of the more difficult
materials to disperse has been single-walled carbon nanotubes, due to
 their morphology, and the strong
attraction between the spindle-like
particles which possess a high aspect
ratio.

Looking for dispersants for your

coating’s formulations?
Prospector has hundreds of listings for disperant materials with
technical data and the ability to request samples.

Search Dispersants

Dispersants absorb onto the pigment surface and therefore maintain

pigment spacing by electrostatic repulsion and/or steric hindrance.
Both stabilization mechanisms are described below.
Electrostatic Repulsion
The pigment particles in the liquid paint carry electrical charges on their
surfaces. Ideally, using additives, it is possible to make all pigment
particles equally charged. Counterions to the pigment-surface ions,
concentrate at the pigment surfaces (in the liquid phase) so that an
“electrical double layer” is formed (Figure 3). This is the ideal case and
never wholly occurs practically.
The additives used for dispersion in such systems are polyelectrolytes –
higher molecular weight moieties which contain a multitude of
electrical charges in the side chains. The combination of side chains
with a multitude of electrical charges, makes these chemicals useless
as wetting agents.
Steric Stabilization/Hindrance
Dispersing additives, which function by steric hindrance, display two
structural features. First, the products contain resin-compatible chains
(hydro-carbon units) which, after adsorption of the additive onto the
pigment surface, project into the surrounding resin solution. This layer
of adsorbed additive molecules with the protruding chains is referred to
as steric hindrance or “entropic stabilization” (Figure 4).
Second, these materials contain one or more groups that have a strong
affinity to attach to the pigment, also known as “anchor groups” – that
all together provide a strong, durable adsorption onto the pigment
surface.
Steric stabilization occurs in
solvent-borne systems and in
water-reducible systems which
contain solvated resins. Structural
features composed of pigment
affinic groups (polar) and resin-
compatible chains (non-polar),
these additives exhibit surface-
active properties. Therefore, they
not only stabilize the pigment
dispersion, but they also function
as wetting agents.
Author’s Note: In previous
articles, topics like “Surfactants,”
and “The Differences Between
Wetting Agents and Dispersants”
have been discussed. Here I solely present the subject of dispersants. If
there is any confusion between the roles of wetting agents and
dispersants, I suggest you read the latter article.

Coating Film Defects

During film formation a paint should transform from a liquid into a

closed, solid film called a coating. In order to give optimum protective
and aesthetical properties, most coatings should be smooth and
without craters, pinholes, cracks etcetera. Coating film defects can ruin
protective and aesthetical properties of coatings. A huge amount of time
and money is invested in preventing and resolving defects.
Substantial savings can be made when knowledge, both simple and
available, is used. Resolving a defect turns out to be logical as soon as
the governing phenomena of the defect are known and understood. A
wide variety of coating defects occur, and in the following only a few of
them are briefly discussed.
Crawling
Fig. 1. Crawling: liquid paint retracts from the solid substrate.
Crawling, also called retraction or pulling back, is a uniform de-
wetting effect: the surface energy of the solid substrate is lower than
the surface tension of the liquid paint. The resulting effect is that
the liquid paint does not fully wet the substrate: the liquid retracts and
forms droplets, leaving part of the substrate naked, Figure 1.
A general statement that can be made is that wetting becomes more
critical when the surface energy
of the substrate is low and/or
when the surface tension of the
liquid paint is high. A substrate
having low surface energy is
called hydrophobic, implying that
the surface of the substrate is not able to interact strongly with a
material put on top of it. Unmodified plastics, for example, are
materials having low surface energy. Crawling can be prevented in
several ways. A pre-condition that must be met, in order to obtain
complete wetting, is that the substrate is clean. In some cases, the
substrate must be modified in such a way that the surface energy of the
substrate is raised, implying that the substrate is changed from
hydrophobic to more hydrophilic. Substrate treatment is often applied to
plastics prior to coating. Another approach, being most often used in
order to prevent crawling, is to lower the surface tension of the liquid
paint by adding a wetting agent (EU). However, the use of wetting
agents can worsen key properties of the system, like hardness, recoat
ability and foam sensitivity.
Cratering
Fig. 2. Cratering: a hydrophobic contaminant induces flow of liquid
during film formation.
Cratering is an interfacial phenomenon that can start at the interface
paint ↔ air or at the interface substrate ↔ paint. Cratering is the result
of flow of liquid being caused by gradients in surface tension gamma
(g) and taking place during film formation. These gradients develop
when materials are present in the liquid paint both having a low surface
tension (implying that they are hydrophobic, see Figure 1) and having a
limited miscibility with the paint.
A system strives to attain a state of minimum energy. Therefore, a
liquid will flow from an area with low surface tension to cover an area
with higher surface tension, Figure 2.
Droplets of hydrophobic contamination, like lubrication oil
or defoamer (EU), are often the initiators of craters in coatings. The
formation of craters can be prevented when the presence of
incompatible hydrophobic contaminants is excluded. In cases where
problems with craters are experienced, one of the aspects to look at is
the defoamer possibly being
present in the system.
Another point of attention is
to check whether the
substrate is contaminated.
Flooding
Fig. 3. Flooding: a mobile
pigment is dragged to the
surface of the liquid paint
during film formation.
Flooding is a film defect
originating from the evaporation of solvents (EU) during film
formation. Strong gradients in temperature and composition develop
when the evaporation of solvents proceeds quickly. The phenomenon,
which is a direct result of the gradients formed, is that flow of liquid
from the bulk of the wet film to the paint air interface takes place during
film formation. The temperature of the paint is lowest near the paint air
interface because solvents evaporate at this interface.
Mobile pigments (EU) that are not well stabilised can be dragged along
in the liquid flow. The resulting flooding gives a non-
uniform distribution of pigment particles over the dried film. Pigment
separation, from the paint air interface of the film to the bulk of the
film, takes place when pigments differ in mobility and a gradient in
pigment composition is formed throughout the coating, Figure 3.
Flooding becomes visible when several pigments, differing in colour,
are used in a system. An approach that can be used to prevent flooding
is to use solvents having a lower speed of evaporation. Another option
is to improve the colloidal stability of the pigment particles by using
suitable dispersants, possibly in combination with adjustment of the
rheology of the paint.
Foam
Fig. 4. Foam: the holes, that were left in the film when air was released
during film formation, do not level out.
Foam bubbles can already be present in the paint before application
starts. Foam can also be
introduced during the application
process; especially during brushing and
spraying, air can be brought into
the paint. A coating formulator wants to
develop a paint that loses its foam as
soon as application has finished and film
formation proceeds.
Two aspects strongly dominate the
formation, stabilisation and release of
foam. First, foam bubbles can be stabilised by additives having
a surfactant (soap) (EU) structure. This problem is experienced
most strongly in water-based paints (EU). The second important aspect
is the rheology (EU) of the paint. Despite the high viscosity, the foam
bubbles might be able to move to the surface of the film where they
can break. However, the resulting hole possibly is not able to level out
when the viscosity of the film is too high, Figure 4.
The prevention of bubbles and pinholes in films, caused by foam, can
be arranged in several ways. First, the use of surfactants should be
minimised, especially in water-based systems. Secondly, the
introduction of air in the paint during production, handling and
application should be prevented as much as possible. Finally, the
rheology of the system should be such that the air, that was
introduced, can easily escape during the first stage of film formation.
Please be aware that the use of defoamer, an approach that cannot
always be prevented, increases the risk of cratering, see ‘2. Cratering’.
Cracking
Fig. 5. Cracking: a coating breaks because of internal stress.
A thin film on a substrate can break when the film suffers from stress.
In coating technology breakage of a coating is called cracking, Figure 5.
It will be clear that a coating loses its protective properties in the areas
where the film has broken; at those spots there is direct contact possible
between the substrate and the environment. This can result in corrosion
when the substrate is metal or in rot in case of wooden substrates. In
many cases cracking of a coating is accompanied by loss of adhesion.
For example, water can migrate through a coating at the cracks, getting
into contact with the substrate coating interface. When doing so, water
can induce loss of adhesion either directly, by interfering with
the intermolecular forces between
substrate and coating, or indirectly, as a
result of corrosion caused by the water
being present at the interface.
Most often stress builds up in films
because of shrinkage (EU) taking place
during film formation. Several effects and
phenomena can result in film shrinkage
taking place. First, the chemical reaction taking place during film
formation, called crosslinking (EU), can be very fast. UV-systems, for
example, cure via radical polymerisation being a fast crosslink
chemistry. During cure of a UV system a high crosslink density is
generated in a short period of time during film formation giving rise to
stresses being frozen in. Secondly, evaporation can proceed too fast. In
many cases, there is a competition between cure and evaporation during
film formation, causing stress.
A high loading of solid particles, or pigments and fillers, can also
cause stress in films. Finally, stresses can occur when the substrate is
not stable in its dimensions. An example is the dimensions of wood
changing because of variations in humidity. Specifically, water-based
systems can suffer from internal stress, thus giving cracking. Water-
based wall paints, for example, are often based on binder emulsions.
During film formation, the water evaporates from the film and the
binder droplets merge together. Stress can build-up in such a system
during film formation, especially when a high number of solid
particles is present. In such a loaded system, the merging of the binder
droplets can become critical and the film can crack because of the stress
build-up during film formation.
It will be clear that cracking is highly undesirable from both protective
and esthetical point of view. As with many defects several options are
available to tackle a cracking problem. What solution must be chosen
depends upon the main cause of cracking of the film.

Dispersing & Wetting Hydrophobic Pigments & Fillers in Water-Based

Paints to Avoid Pigment Flooding & Floating
Posted on December 5, 2014 by Ron Lewarchik

A critical part of any coating’s formulation is ensuring that the coating

will be free of inherent defects, including pigment flooding and
floating. Waterborne formulations represent some unique challenges
due to multiple factors, including the high surface tension and polarity
of water that does not contribute to the wetting of most pigment and
filler particles. In this article, I’ll define some important considerations
in formulating waterborne paints to avoid pigment flooding and
floating.
Flooding, Floating, Surface Tension, Bernard Cells, Flocculation
and Agglomeration
Floating describes a mottled, splotchy appearance on the surface of a
paint film. It is most apparent in coatings colored with two or more
pigments and is a result of the horizontal separation of different
pigments. Flooding is the phenomena observed when the surface color
of an applied film is uniform but is darker or lighter than it should be.
This is attributed to a vertical separation of different pigments in the
film.
Vertical Separation Horizontal Separation
 Surface Tension results when the force
that occurs in a liquid at the interface
differs from the forces within the liquid.
Thus, surface tension is caused from the
surface molecules having a higher free
energy than those molecules in the bulk
of the liquid.
Surface tension differential can cause a convection current resulting in a
regular hexagonal surface pattern called Benard Cells. A hexagonal
Benard Cell pattern results in smaller, more mobile pigment particles
(smaller, less dense) being deposited on the perimeter and the less
mobile particles (larger, denser) remaining away from the perimeter.
Figure 2 – Rub-up of Flocculated Blue Pigment
Flocculation is the recombination of dispersed pigment particles that
were not properly stabilized in the pigment dispersion. Flocculation is
undesirable at it detracts from
hiding and color development.
Flocculation is reversible by
applying a low degree of shear.
In figure 2,
the phthalocyanine (EU) blue
pigment is flocculated. Upon
rubbing with a finger, the
deeper blue color returns.
Stabilized pigment
dispersion —
Flocculated pigment
dispersion

Pigment agglomeration is defined as pigment particles that are clumped

together without enough vehicle or wetting agents present between
pigment particles. When agglomeration occurs, extensive shear and
attrition forces are usually necessary to reinstate a stabilized pigment
dispersion.
Remedial Actions to Overcome Floating and Flooding in
Waterborne Paints
 Pigment dispersion in aqueous media
uses the same principles as in organic
solvent media such as proper wetting,
pigment dispersion and stabilization.
However, the surface tension of water
and high polarity make it more problematic in wetting low polarity
pigments. In many cases, water interacts aggressively with the surface
of the pigment, destabilizing the dispersant on the pigment surface.
Overcoming flooding and floating starts with selecting pigments that
are free of fines. Also, many pigment manufacturers supply surface
treated pigments to avoid flooding and floating.
Secondly, ensure that the pigment dispersion is uniform and stabilized
(elimination of pigment flocculation of one pigment, with the exclusion
of other pigments).
Thirdly, the use of suitable wetting agents/surfactants help to ameliorate
differences in polarity and surface tension between pigments that
contribute to flooding and floating. Inorganic pigments such as iron
oxides (EU), titanium dioxide (EU), calcium carbonate (EU) and many
other filler pigments have a polar surface and are easily wet by water.
However, water alone normally does not stabilize the pigment
dispersion against flocculation, so they require a surfactant to wet and
stabilize the dispersion. Also, many pigment manufacturers supply
surface treated pigments to avoid flooding and floating. For some
organic pigments that have a surface with low polarity, many
manufacturers modify the surface with a layer of inorganic oxide to
provide increased polarity to improve wetting in aqueous-based
systems.
Fourthly, the use of an appropriate thixotrope (EU) helps to build
sufficient viscosity and a network structure that discourages pigment
separation. However, one must be sure that there is acceptable
compatibility between the thixatrope and dispersant (EU).
Click to view larger image.
Overcoming flooding and floating in solvent-borne paints primarily
involves utilizing a suitable pigment dispersant and the elimination of
Benard Cell formation with the addition of a surface control agent.
A final consideration affecting the stability of an aqueous paint pigment
is the pH of the pigments. For example, if a low pH carbon black
pigment is used in the pigment dispersion without the use of a suitable
wetting agent in an anodic aqueous based paint (pH normally > 8),
longer term instability can result as the neutralizing amine on the resin
backbone can migrate to the acidic pigment.
Click to view larger image.
Care must be taken while reducing a latex paint with water because
floating can occur (slow addition of water with proper mixing and
ensure against over reduction). This is due to a shift in the equilibrium
between the dispersed pigment particles and water, resulting in a
decrease in the amount of stabilizing dispersant on the pigment.
There are numerous suppliers listed in UL’s Prospector website with a
wide variety of wetting agents (EU), pigment
dispersants (EU), surfactants (EU), thixotropes (EU) and pigments to
meet your requirements in both solvent and waterborne coatings.
Basic Dispersion Theory part 2
High quality coatings of high brilliance and Color strength are
characterized by a perfect pigment dispersion, optimal pigment particle
size, and long-term stabilization of the dispersed particle in the
formulation.

The dispersion of a pigment in liquid coatings, paints or inks to produce

stable suspension, can be divided into the following three processes:

Mechanisms in the dispersion

process

Pigment wetting: All the air and

moisture is displaced from the
surface and between the particles of the pigment aggregates and
agglomerates (clusters) and is replaced by the resin solution. The
solid/gaseous interface (pigment/air) is transformed into a solid/liquid
interface (pigment/resin solution).
Grinding stage: Through mechanical energy (impact and shear forces),
the pigment agglomerates are broken up and disrupted into smaller units
and dispersed (uniformly distributed).
Stabilization of pigment suspension: The pigment dispersion is
stabilized by dispersing agents in order to prevent the formation of
uncontrolled flocculates. The resultant suspension is stabilized due to
the adsorption of binder species or molecules at the pigment surface.
The choice of the more efficient dispersing agents is strongly related to
the chemical nature of the pigment and the resin solution (for the paint
manufacturer, it is essential to distinguish between organic and
inorganic types). This topic is discussed further in Formulating an
optimum dispersion.

Pigment wetting
The wetting step consists of replacing the adsorbed materials on the
surface of the pigments and inside the agglomerates (water, oxygen, air,
and/or processing media) by the resin solution.
The complete wetting out of the primary sized pigments particle helps
to enhance the technical performance of a liquid coating that depends
very much on interaction between the pigment particles and the binder
system. Dispersing additives, which adsorb on the pigment surface,
facilitate liquid/solid interfacial interactions and help to replace the
air/solid interface by a liquid medium/solid interface.

Replacement of air and water by the resin

The efficiency of the wetting depends
primarily on the comparative surface
tension properties of the pigment and
the
vehicle, as well as the
viscosity of the resultant mix.
The adsorption mechanism
depends on the chemical
nature of the pigment and the types
of dispersing agents used. (visit dispersants families)
Thermodynamic consideration:

The spontaneous wetting process (on wetting solid surfaces) is driven

by minimization of the free surface energy. Forced wetting processes
(in non-wetting conditions) require the application of external force,
and spontaneous de-wetting will take place when the force is removed.

Thermodynamic condition for wetting requires the work of liquid/solid

adhesion (Wa) to be as high as possible and, for unlimited wetting, at
least more than a half of the work of cohesion (Wk) is required: Wa>
Wk.

Velocity of penetration of a liquid into a powder can be explained in

terms of the Washburn equation (19):

Washburn equation
where h is the depth (or height) of penetration during the time t, - is the
surface tension of the wetting liquid, - its viscosity, - the wetting
angle, r - mean radius of capillaries, C - structural coefficient,
associated with parameters of the porous structure, W - energy (heat) of
wetting.
The wetting step of dispersing processes can be intensified using
wetting agents and/or binders with lower viscosity and surface tension.
On the other hand, a resting of
pigment/binder premixes prior to
their dissolving or grinding helps to
accomplish the wetting stage and
always eases and accelerates
dispersing processes.

Grinding stage
After the wetting stage, it is necessary to de-aggregate and
deagglomerate the pigment particles. This is usually accomplished by
mechanical action provided by high impact mill equipment.

In the grinding stage, the cohesive forces inside the agglomerates must
be overcome. Energy is added to the system and therefore smaller
particles (with a larger interface to the resin solution) are formed. This
results in loosened inter-particle contact durability, that eases the
destruction of pigment clusters under the action of shear stresses,
applied in dissolvers, mills etc.

Pigment dispersing

As the pigment powder is broken down to individual particles by

mechanical shear, higher surface areas become exposed to the vehicle
and larger amounts of additives are required to wet out newly formed
surfaces.
Once dispersed, the primary particles tend to re-agglomerate. This
process is called flocculation. From a structural standpoint, the
flocculates are very similar to the agglomerates; nevertheless, the
interstitial spaces between the pigments are now filled with resin
solution rather than air.
The grinding process can be regarded as a de-flocculation process. In
the absence of stabilizing agents, effects such as reduced color strength,
decreased gloss, and altered rheology then may occur.

Stabilization of pigment suspension - Overview

1. overview
2. Colloidal stabilization
3. Electrostatic stabilization
4. Steric stabilization

The aim of stabilization is to keep the pigment particles separated as

achieved in the last step, and to control the degree of pigment particle
size through the let-down and filling phase, storage and later in coating
films during film formation.

Flocculated pigment suspensions are characterized by the non-uniform

spatial distribution of particles, which are allowed for immediate
interparticle contacts. This
results in worse rheology
(structural viscosity, blob-
flow), low storage stability (in
paints) and poor optical and
color properties (in coatings).
It is well known, that even well grinded but not stabilized, fine particle
size pigment suspension can easily be destroyed by the letting down
into a non-suitable paint base: flocculation typically breaks down when
shear is applied and will form again, when the shear is removed.
Therefore, immediately after grinding pigment suspensions must be
stabilized by the addition of additives, whether they are intended to be
used immediately in let-down or as pigment preparations (colorants).

Dispersing agents avoid flocculation

Stabilization is achieved through absorption of stabilizing molecules on

the pigment surface, so that repulsive forces prevent other particles
from approaching close enough for the attractive van der Waals forces
to cause agglomeration. To know more about the factors influencing the
stability, look at the colloidal stabilization.

There are two principal mechanisms for the stabilization of pigmented

dispersions:
Electrostatic stabilization: electrostatic stabilization occurs when
equally charged local sites on the pigment surface meet one another.
Two particles having the same charges give a repelling effect. The
resulting Coulomb-repulsion of the charged particles allows the system
to remain stable.
Steric stabilization A pigment is said to be sterically stabilized when the
surface of the solid particles is completely covered by polymers,
making particle-to-particle contact impossible. Strong interactions
between polymers and solvents (organic solvent or water) prevent the
polymers from coming too closely into contact with one another
(flocculation).

Stabilization of pigment suspension - Colloidal stabilization

Stability of dispersion is a result of interplay of the heat (kinetic) energy
of particles, attractive interparticle forces and repulsive forces, all act
persistently between any neighboring particles.

Possessing kinetic (thermal) energy and being subjected to Brownian

movement, colloid particles persistently approach one another and
collide. Without restricting factors their approachment may occur so
close that even relatively short-range van der Waals forces will be
capable to joint particles irreversible, thereby destroying the dispersion.
Alternatively, having a certain source for interparticle repulsion,
capable to prevent particles from immediate contacts, a dispersion can
persist indefinitely without significant changes in particle size and
properties.

Attraction/ repulsion between two particles

The existence of enough repulsive forces

between neighboring colloid-size particles
 is therefore a matter of life or death
for any dispersion. Those repulsive
forces arise when lyophilized near-
particle layers interfere: the
persistent exchange of the
molecules of water between the
near-surface layer and the non-
changed water outside the layer creates the repulsive force, like osmotic
pressure (Figure 1). The repulsive forces can be of different nature:
Compression of electrical double layers, which surround the particles,
Osmotic pressure in non-ionically stabilized system (Derjagin, Fischer),
Chain elasticity in the dispersions stabilized with polymer surfactants,
entropic repulsion (Mackor),
Barrier-type stabilization with polymeric dispersants.
Practically, three systems of coating stabilization can be used in
aqueous medium:
the use of ionic surfactants or chemical lyophilizers which produce
carboxy, ammonium etc. ions, see electrostatic stabilization
non-ionic stabilization, owed to the adsorption of non-ionic surfactants
or corresponding chemical modification of the polymer phase (or
surface only) with non-ionic lypophilic fragments, see steric
stabilization
combined ionic non-ionic stabilization, which is widely used in
technologies of latexes, emulsions and paints, allowing to achieve
prominently high disperse stability toward the action of various
destabilizing factors.
As we are able to calculate of interparticle forces, we can characterize
dispersion stability via "potential curves" (Figure), where potential
energies of attractive and repulsive forces and total interaction are
expressed as a function of distance between particles "Potential barrier"
is the energy particles shouldn't be able to overcome on expense of their
heat energy in order to maintain the dispersion steady.

Potential energy curves between two particles

Stabilization of pigment suspension - Electrostatic stabilization
The pigment particles in the liquid paint carry electrical charges on their
surfaces. Using additives, it is possible to increase the charges and,
furthermore, to make all pigment particles equally charged.

Classic colloidal science explains electrostatic stabilization in terms of

an electrical double-layer. A charge is generated on the pigment
surface, and a more diffuse cloud of oppositely charged ions develops
around it. As two particles approach each other the charge effectively
provides a barrier to closer particle interactions. Stabilization increases
along with the thickness of this layer.

Electrostatic stabilization
Chemically speaking, the additives used for dispersion in such systems
are polyelectrolytes - high molecular weight products which contain a
multitude of electrical charges in the side chains.
In addition to polyphosphates, many polycarboxylic acid derivatives are
utilized as polyelectrolytes in the coatings industry. The
polyelectrolytes adsorb onto the pigment surface and consequently
transfer their charge to the pigment particle. Through electrostatic
repulsion between equally charged pigments, the flocculation tendency
is dramatically reduced so that the deflocculated state is stabilized.
Electrostatic stabilization is effective in media of reasonably high
dielectric constant, principally water;
although even in water-based coatings
systems, steric stabilization, or a
combination of steric and charge
stabilization will often provide better
overall performance.

Stabilization of pigment suspension - Steric stabilization

Charge stabilization is not be effective in media of low dielectric
constant (most organic solvents and plasticisers), and steric stabilization
is required to maintain dispersed particles in a stable non-flocculated
state.
Steric stabilization relies on the adsorption of a layer of resin or
polymer chains on the surface of the pigment. As pigment particles
approach each other these adsorbed polymeric chains intermingle and in
so doing they lose a degree of freedom which they would otherwise
possess. This loss of freedom is expressed, in thermodynamic terms, as
a reduction in entropy, which is unfavorable and provides the necessary
barrier to prevent further attraction. Alternatively, one can consider that,
as the chains intermingle, solvent is forced out from between particles.
This leads to an imbalance in solvent concentration which is resisted by
osmotic pressure tending to force solvent back between the particles,
thus maintaining their separation.

Steric stabilization
One fundamental requirement of steric stabilization is that the chains
are fully solvated by the medium.
This is important because it means
the chains will be free to extend
into the medium and possess the
above-mentioned freedom. This
requirement is usually expressed
by saying that the medium needs
to be a better-than-theta solvent (i.e. a relatively good solvent) for the
polymer chain. In systems where the chains are not so well solvated,
they will prefer to lie next to each other on the surface of the pigment,
providing a very much smaller barrier to inter-particulate attraction.

The greater steric repulsion generated by

the addition of polymeric dispersants
moves the minimum in the Potential
Energy Curve, and thus reduces the
overall viscosity.

This stabilization mechanism occurs in

solvent- based systems and in water-reducible systems which contain
solvated resins. Through specific structural elements composed of
pigment affinic groups (polar) and resin-compatible chains (nonpolar),
these dispersing agents exhibit definitive surface-active properties. In
other words, they not only stabilize the pigment dispersion, but they
also function as wetting additives.

Formulating an optimum dispersion

Dispersing agents are not just additives to conventional millbases. The
choice of the most suitable dispersing agents is sometimes difficult, and
their usage require sometimes specific guidelines.

In this part of the Dispersion Center we will discuss the main items that
have to be considered when formulating a pigment solution. To learn
more about how to formulate an optimum dispersion, click on the links
below:
Dispersant Choice
Grinding medium
Pigments**/Fillers
Order of addition
Surface Area

Dispersant Choice
With any effective polymeric dispersant, the two-component structure
is made up from a polymeric chain and a pigment affinic anchor group.
The nature of the polymeric chain is critical to the performance of the
dispersant. If the chains are not sufficiently solvated, then they will
collapse on to the pigment surface, allowing the particles to aggregate
or flocculate. This need for compatibility with the medium extends
throughout the final drying stages of any applied coating. If it ceases to
be compatible, flocculation may occur leading to reduced gloss and
tinctorial strength.
In order to meet the need for good compatibility, several different
polymer chains can be utilised effectively covering the variety of
solvents encountered. The structure of some dispersing additives can be
described as one or more spatially close anchor groups with several
polymer chains. Other dispersing additives are designed to improve the
flocculation resistance of pigments (particularly non-polar, organic
pigments) and have higher molecular weights through the attainment of
more complex polymer like structures.
The molecular weight of the dispersant is enough to provide polymer
chains of optimum length to overcome Van der Waals forces of
attraction between pigment particles. If the chains are too short, then
they will not provide an enough thick barrier to prevent flocculation.
This will lead to an increase in viscosity and a loss of tinctorial
properties.

Dispersant choice involves several criteria, and the nature of the

pigment, the resin involved, and the solvent can all affect the
performance of the polymeric additive.

Grinding Medium
Anchoring of the polymeric dispersant to the pigment surface can be
affected by competition between the resin and dispersant for the surface
of the particle. Once the anchor group of the dispersant is attached to
the pigment surface it will remain firmly attached. Molecules of resin,
however, are transiently adsorbed on the surface of the pigment, and
even though not firmly anchored they can hinder the dispersant
anchoring process.
Minimal-resin solids (or resin-free systems) can be used in the
dispersion, if good let-down stability is sufficiently available.
Dispersant technology is now more advanced, and in some systems
dispersing without resin is possible.

As an example, Avecia SOLSPERSE 43000 polymeric dispersant

would be recommended for dispersing various pigments in resin-free
dispersions for general industrial and decorative water-based paints. A
key benefit of using this kind of product is the wide resin compatibility
it offers in various resin systems, including polyester, acrylic,
polyurethane, alkyd and epoxy.

Pigments / Fillers

P11The choice of dispersant is also related to the surface nature of the

pigment. The polarity of the surface of the pigment differs from organic
(non-polar) to inorganic (more polar), and this means that the nature of
 the
C.I. Pigment Solsperse Solsperse Solsperse
Pigment Talc Antifoam Water
No. % 6100 6200 6300
Iron
Oxide - PB7 30.0 - - 16.5 5.5 0.3 35.7
Yellow
Carbon
PB7 30.0 - - 16.5 5.5 0.3 35.7
Black
Bismuth
PY184 50.0 10.0 8.0 - 8.0 - 24.0
Vanidate
Titanium
PW6 58.0 5.0 4.0 - 4.0 - 29.0
Dioxide
dispersant anchor group is critical for optimum adsorbtion. The choice
of anionic anchor group should allow for better performance with
inorganic pigments and a cationic anchor group should be more
appropriate for organic pigments.

The surface area of the pigment also affects the level of dispersant used,
and in general, if too little is used then the full benefits will not be
realized. If too much is used, it can be shown that the thickness of the
protective barrier is reduced as a result of overcrowding on the pigment
surface. Therefore, the use of an excess level of dispersant leads to final
coating properties which are inferior to those obtained with an
optimized dosage. Furthermore, film properties such as adhesion or
hardness can be adversely affected using an excess of dispersant
because of the free molecules in the drying film.

The Table below show a range of typical starting point formulations for
inorganic and carbon black based decorative universal tinters using
polymeric dispersant (Avecia Solsperse).

Order of Addition
The usual way of incorporation of dispersant in a coating formulation
would be in three stages:
1. Mix the dispersant in the millbase solvent or in the resin/solvent
mixture,
2. Add any other additives,
3. Add the pigment, in stages, and disperse in the normal manner.
In case you want to optimize a Polymeric dispersant millbase, 4 stages
are involved. The following example explaining using Avecia Solsperse
products (referred to as a ladder series).
Stage 1 - Calculation of % AOWP of Polymeric hyperdispersant

The theoretical number of Polymeric dispersants (e.g. Avecia

Solsperse) agent required in a millbase is 2mg Polymeric agent per sq.
meter pigment surface area.

Example:
Pigment surface area - 70m2/g
Therefore, 140mg Polymeric agent/1g pigment
are required = 14g agent/100g pigment i.e. 14%
AOWP
Synergists (if required) are used with the
Polymeric in ratios between 4:1 and 9:1 [Polymeric: synergist].
Stage 2 - Determines the higher pigment content required
(Can be performed on lab. shaker e.g. Red Devil)

Using the % AOWP of Polymeric agent

(calculated above) + synergist (if
required) prepare a series of millbases
with increasing pigment contents in a
GRINDING MEDIUM containing
APPROXIMATELY 10% SOLID
RESIN. Note: the ratio of
[hyperdispersant: pigment] must be
maintained.

The pigment concentration giving the same viscosity as the control

should now be used in Stage 3.
Stage 3 - Determines optimum amount of Solsperse Hyperdispersant
(Can be performed on lab. shaker e.g. Red Devil)

Using the higher pigment content established in Stage 2: Carry out a

series of Polymeric agent dosages around the theoretical % AOWP (+
 any synergist required) to optimize the required
agent dosage. Determine the best
hyperdispersant dosage by measuring desired
property.
Stage 4 - Optimizes final pigment
concentration
(Should be done in equipment representative of bulk production)

Using the % agent on weight of pigment established in Stage 3: Prepare

final ladder series of pigment contents – maintaining [agent: pigment]
ratio determined in Stage 3 to determine optimum amount which gives
best final product.

Surface Area
As a rule, 2-2.5mg
of polymeric dispersant, per square meter of pigment surface area will
be close to the optimum amount required.

A ladder series of polymeric dosage levels should be evaluated based

around this 2-2.5mg/m2 level. Measurement of dispersion viscosity will
show a minimum at the optimum dosage; although it is also possible to
measure gloss or color strength of the coating which will show a
maximum at the same optimum dosage.
Typically, the surface area of phthalocyanine blue pigment is 50 m2/g:

So, a typical dosage would be:

• Phtalocyanine blue pigment 30.0 (i.e: 10% active dispersant on
the weight of pigment)
• Polymeric dispersing agents 3.0

Dispersants families - Introduction

The choice of the dispersing agents is a key issue in the coating and ink
industry. Formulators must find the most suitable products for their
formulation considering the final application of their coating, the
coating system (water based, solvent based, etc.) and the other
additives.

The role of the dispersing agents is to enhance the dispersion process

and ensure a fine particle size in order to stabilize pigments in the resin
solution. As explained earlier, an efficient dispersant must perform the
three main functions: pigment wetting, dispersing, and stabilizing.
Dispersing agents generally differ for aqueous and solvent-based
coatings.

In term of chemical structure one can divide dispersing agents into the
two following classes:
Polymeric dispersants
Surfactants
The main differences of those two types of dispersants being the
molecular weight, the stabilization mechanism and the resulting let
down stability.

Polymeric disperants - Description

1. General description
2. Anchor groups
3. Polymeric chains

Polymeric dispersants stabilize paints, coatings and ink systems via a

steric stabilization mechanism previously described. They have a two-
component structure which combines the following two very different
requirements:
It must be capable of being strongly adsorbed into the particle surface
and thereby possess specific anchoring groups
The molecule must contain polymeric chains that give steric
stabilization in the required solvent or resin solution system.
There are many copolymer/functional polymer configurations that
might be expected to give effective polymeric dispersants. Six possible
arrangements are illustrated in Figure 1:
 Figure 1: These anchor onto the
particle surface either through
functional groups (b and c) or
through polymeric- blocks (a and
d-f). The steric stabilization
polymer chain is either anchored to
the particle surface at one end (b,
d, and f) or at both ends (a, c, and
e).
Polymeric dispersants differentiate themselves from the other types of
dispersing agents through considerably higher molecular weights.
Because of its structural features, a polymeric dispersant is bound to
numerous sites at the same time, forming durable adsorption layers
upon many pigment particles. Optimal steric stabilization is achieved
when the polymer chains are well solvated and properly unfurled,
therefore they must be highly compatible with the surrounding resin
solution. If this compatibility is obstructed, the polymer chains collapse
causing the steric hindrance and the resulting stabilization to be lost.
For additives to be effective, the adsorption into the pigment surface
must be durable and permanent. The surface properties of the pigment
particles are therefore crucial to the additive's effectiveness:
With pigments possessing high surface polarities, such as inorganic
pigments that are ionically constructed, the adsorption of any dispersing
additive is relatively easy.
However, for pigments with nonpolar surfaces, such as organic
pigments whose crystals are composed of nonpolar individual
molecules, a proper adsorption is rather difficult to obtain with
conventional additives. The wide range of anchor groups that polymeric
dispersants provide make them very efficient to anchor on pigments
with nonpolar surfaces.
In the traditional method of stabilizing pigments in water, the
stabilizing charges used are often disturbed by impurities, such as other
ions, or the presence of other pigments with different zeta-potentials.
This leads to a destabilizing effect, caused by the reduction of the
repulsive forces. Steric stabilization can avoid this issue, making
polymeric dispersants very useful for dispersing all types of pigments,
 even the organic ones, that are very
difficult to be deflocculated by
traditional wetting and dispersing
additives.

The level of the polymeric dispersant

used is very important, since
performance depends on the optimum amount of saturation by the
dispersant of the pigment surface.

Polymeric disperants -
Anchor groups
It does not matter whether the
previously discussed
polymer chains are provided by
polymeric dispersants
containing either single chains or up to many hundreds of chains. The
essential requirement is that the chains are successfully anchored to the
pigment surface, and that the surface of the particles are covered with
an enough density of chains to ensure minimum particle-particle
interaction.
As shown in the picture below the anchoring function of a polymeric
dispersant may be a single functional group, or an oligomeric or
polymeric chain:
Schematic molecular structure of dispersants

Studies have shown that steric stabilization chains anchored at only one
end are most efficient. Given that steric stabilization is entropically
driven in non-aqueous media, this conclusion is not surprising.
Anchoring both ends of the polymer chain will clearly inhibit its
freedom of movement, even before it starts to intermingle with the
steric stabilization chains of an adjacent particle.

Anchoring Mechanisms

As the nature of the surface of pigments differ, according to their

chemical type, many different chemical groups can be found as anchor
groups for polymeric dispersants. This wide range of anchoring
possibility enables polymeric dispersants to disperse inorganic pigments
as well as pigments with polar surfaces. The actual anchoring can then
take place through a variety of mechanisms:

Anchoring Through Ionic or Acidic/Basic Groups.

When a pigment particle has a relatively reactive surface (eg: inorganic
pigments) it is possible to form an ion-pair bond between a charged site
on the particle surface and an oppositely charged atom or functional
group on the dispersant.
This situation is illustrated
in Figure 1a and is effective
because organic solvents
normally have a relatively
low dielectric constant, so
charge separation is not favored.

Figure 1: Anchoring through Ionic or Acidic/Basic Groups

In fact, many inorganic pigment particle surfaces are quite

heterogeneous, with both positive and negative sites. It is therefore
quite common to find that a pigment can be dispersed by using
polymeric dispersants with either negatively or positively charged
anchor groups, as illustrated in Figures 1b and 1c.
Examples of functional groups that can be used to anchor polymeric
chains to charged or acidic/basic surfaces include amines; ammonium
and quaternary ammonium groups; carboxylic, sulfonic, and
phosphoric, acid groups and their salts; and acid sulfate and phosphate
ester groups.

Anchoring Through Hydrogen-Bonding Groups.

Although most organic pigment particles and some relatively inert
inorganic particles such as quartz do not have charged sites on their
surface, they may have hydrogen-bond donor or acceptor groups, such
as esters, ketones, and ethers It is therefore possible for a hydrogen
bond between the particle and an anchor group on the polymeric
dispersant to form. Even individual hydrogen bonds will be weak. A
strong interaction may be developed between the pigment particle and a
polymeric dispersant containing many hydrogen-bond donors and
acceptors in its anchor chain, see figure 2

Figure 2: Anchoring by hydrogen bonding to a polymeric group.

Polyamines and polyols are used to anchor

via hydrogen bonding, either donor or
acceptor. Polyethers can be used to anchor
via hydrogen-bond acceptance.

Anchoring Through Polarizing Groups.

An interaction can also take place between polarized or polarizable

groups on an organic pigment particle surface, and similarly polarized
or polarizable groups on the anchoring function of the polymeric
dispersant. Again, these interactions will often be relatively weak, but
strong interaction may be developed with a polymeric dispersant
possessing an anchor chain composed of several of these groups.

Figure 3: Anchoring through polarizing groups

Polyurethanes are commonly used as polarizable anchor groups.

Anchoring Through Solvent-Insoluble

Polymer Blocks.

It is possible to anchor a polymeric

dispersant onto a pigment particle surface
simply via van der Waals interactions and
without recourse to ionic, hydrogen-
bonding, or polarizing effects. The polymeric block within the
dispersant must simply be insoluble in the medium, see figure 4.
It is possible, for example, to disperse a pigment in an aliphatic
hydrocarbon using a polymeric dispersant based on poly(tert-
butylstyrene) chains, which are solvent-soluble, and polystyrene chains,
which are not solvent-soluble.
Figure 4: Anchoring through solvent insoluble polymer blocks.

Polyurethane anchor groups are said to operate via this mechanism. In

fact, it is very difficult in practice to distinguish between this and the
previous two adsorption mechanisms. Most polymeric anchor chains
probably anchor via a mixture of electrostatic forces (hydrogen bonding
and/or polarization) and van der Waals forces. One of the mechanisms
may be dominant, but the most effective polymeric dispersants probably
maximize the effect from all three mechanisms.

Derivatives of the Dispersed Particle.

Some organic pigments (phthalocyanine blues and

dioxazine violet are good examples) are not very
responsive to any of the anchoring mechanisms just
described. In such systems it can be very difficult to
obtain anything other than dispersions of relatively
low pigment concentration, and these dispersions are prone to
flocculation on letdown. Then the only way to solve the issue is by
modifying the chemical structure of the particle itself in order to make it
act as the anchor group. This system works most effectively on higher
molecular weight pigments with large planar structures, because the
anchor group can pack very closely onto the pigment particle surface
and maximize the van der Waals attractive forces between particle and
anchor groups.
The copper phthalocyanine molecule has been modified by the addition
of polymeric chains to give a particularly effective dispersing agent for
copper phthalocyanine pigments. Alternatively, derivatives with
substituted ionic groups can be used to activate the surface of a pigment
and make it receptive to the charged anchor group of a polymeric
dispersant. This mechanism is illustrated in the figure 5 below.

Figure 5: synergists
Polymeric disperants – Polymeric chains
The nature of the polymeric
chain is critical to the
performance of polymeric
dispersants. If the chains are
not sufficiently solvated, then
they will collapse on to the
pigment surface allowing the
particles to aggregate or
flocculate. The need for compatibility with the medium extends
throughout the final drying stages of any applied coating. If it ceases to
be compatible, flocculation may occur leading to a decrease of surface
properties such as losses in gloss and tinctorial strength, etc.
The molecular weight of the polymeric dispersants must be enough to
provide polymer chains of optimum length to overcome Van der Waals
forces of attraction between
pigment particles:
If the chains are too short, then
they will not provide a
sufficiently thick barrier to
prevent flocculation. It means
that too low a molecular weight
will cause dispersion instability
and will lead to an increase in viscosity and a loss of tinctorial
properties.
When the chains are too long, they tend to “fold back” on to
themselves. Too high a molecular weight will also give reduced
performance.
Ideally the chains should be free to move in the dispersing medium. As
previously said: chains with anchor groups at one end only, have shown
to be the most effective in providing steric stabilization.
Finally, for good surface coating properties and performances, the
polymer must be fully compatible with the coating resin after the
solvent has evaporated off and the resin has been cross-linked.
Chemistry of the Steric Stabilization Chain
In order to meet the need for good compatibility, several different
polymer chain types are utilized in the polymeric dispersant range,
effectively covering the variety of solvents encountered.
Examples, spanning the range of solvent from nonpolar aliphatic
hydrocarbons to alcohol/water includes:
Polyisobutylene
Polyesters
Poly methyl methacrylate
Polyethylene oxides
The amount of polymeric dispersant used is also an important parameter
to consider. Many surface coating systems will tolerate a polymeric
dispersant at low levels of addition, but problems will be caused at
higher loading. Some systems are particularly tolerant to the presence
of polymeric dispersants. Long-oil alkyd resins for air-drying paints and
resins used in publication gravure inks and offset lithography inks are
all good in this respect. Similarly, paper or wooden substrates tend not
to give major adhesion problems. Higher quality stoving or two-pack
paint systems and many packaging ink systems pose much more severe
requirements.

It is therefore vital that after an initial screening of polymeric

dispersants for rheological and color/gloss changes, their effect on the
performance of the surface coating be checked by the appropriate tests.

Surfactants
Surfactants are conventional low molecular weight dispersing agents.
Surfactant molecules can modify the properties and they lower the
interfacial tension between the pigment and the resin solution.

This surface activity arises because the surfactants’ structure consists of

two groups of contrasting solubility or polarity. In aqueous systems, the
polar group is known as a hydrophilic group and the non-polar group as
hydrophobic or lipophilic. In non-aqueous systems, the polar group is
known as the oleophobic group and the non-polar group as oleophilic.
Surfactants are classified according to their chemical structure and,
more specifically, their polar group: anionic, cationic, electroneutral and
non-ionic (see figure 1).
 As with the polymeric dispersing
agents, their effectiveness is
determined by:
The absorption of the polar group
onto the pigment surface. The
anchoring groups can be amino,
carboxylic, sulfonic, phosphoric
acids or their salts.
The behaviour of the nonpolar chain in the medium surrounding the
particle. This part of the molecule (aliphatic or aliphatic-aromatic
segments) must be highly compatible with the binder system.
The stabilization mechanism of surfactant-like dispersing agents is
electrostatic: the polar groups forming an electrical double layer around
the pigment’s particles. Due to the Brownian movement the pigment
particles frequently encounter each other in the liquid medium thus
having a strong tendency to re-flocculate on the let-down stage.

Because of their chemical structure (eg: low molecular weight) and the
electrostatic method of stabilization, surfactants may cause the
following defects:
_ Water sensitivity: Surfactants generally tend to provide water
sensitivity to the final coating, thus making them inappropriate for use
in outdoor applications.
_ Foam formation: Many surfactants generate foams which lead to
surface defects (e.g. fisheyes, craters) on the final coating. If foaming
occurs at the milling stage it can also cause a loss of production
capacity.
_ Interference with intercoat adhesion.
Over the past years specific surfactants have been developed to
minimize these defects, and some provide other advantages to the final
paints such as defoaming/dearation or difficult substrate wetting.
The most widely used surfactants for pigment dispersion in coating
formulations are:
Fatty acid derivatives
Phosphate esters
Sodium polyacrylates / polyacrylic acid
Acetylene diols
Soya lecithin
For more information, click on the links above.

Fatty Acid Derivatives

Nonionic fatty acid derivatives such as the alkyl phenol ethoxylates
(APEs) and fatty alcohol ethoxylates (FAEs) are one of the main types
of surfactant used in coating applications as wetting and dispersing
agents for pigment particles, particularly in decorative emulsion paints
and water-based inks.

Typical structures of fatty alcohol ethoxylates (FAE) and alkyl phenol

athoxylates
These types of surfactants help stabilizes the aqueous dispersions of
organic pigment particles by the steric stabilization mechanism. Most of
the time, they are used in combination with an anionic surfactant which
provides stabilization of the dispersion by the electrostatic stabilization
mechanism but concerns over the APEs nonionic surfactants has led to
the recent apparition of new product blends advertised as APE free.

Coating formulated with these types of nonionic dispersing agents are

sometimes subjected to foaming, water sensitivity, intercoat adhesion
and blistering
Resin Dispersions applications in Water based
Pressure Sensitive Adhesives , formulating (
Compounding ) with Resin Dispersions, to optimize
overall , Peel Adhesion, Shear Strength and Tack.
Especially for Improving the Bond strength with , Foams, Rubber
sheets and Low Surface energy ( Low Surface Tension ) substrates.
The role of Resin Dispersions in Compounding Adhesives
Due to stiff competitive market , Adhesive Formulators are under
constant pressure to find cost-effective solutions that meet both
performance and environmental requirements for applications including
pressure-sensitive adhesive (PSA) tapes and labels, protective tapes and
films, contact adhesives, and sealants and coatings.
Resin dispersions are used with emulsion polymers to optimize peel,
tack and shear performance in such applications.
The fundamentals of resin dispersions & detail factors to consider
when formulating an adhesive using resin dispersions to balance peel
and tack with shear performance for PSA applications.
Resin Dispersion Basics
A resin dispersion contains a
 low-molecular-weight tackifier resin dispersed in water
 with the aid of a surfactant.
These tackifier resins include
 hydrocarbon resins or
 rosin ester resins.
Hydrocarbon resins used to make dispersions include
• C5 resins based on piperylene,
• C5/C9 resins based on piperylene & aromatic feedstocks, or
• pure monomer resins (PMRs) based on styrene and styrene
derivatives.
Rosin esters are the product of a reaction between rosin acid and a
multifunctional alcohol.
Rosin esters may be used alone or in a blend with hydrocarbon resins to
make rosin ester dispersions.
The materials required to synthesize resin dispersions include the
precursor resin, surfactant and water.
Generally, the percent solids level of resin dispersions
is between 50% and 58%.
Optional additives include materials such as
 plasticizers,
 ion tolerance agents,
 antioxidants and
 biocides.

Particle Size is a key factor in the overall performance of resin

dispersions.
Small particle size
 enhances dispersion performance by providing increased shelf
life,
 improved mechanical stability,
 improved pumpability and easy filtration.
Small particle size is also important in applications
o where clarity is crucial, such as in filmic labels.
o Particle size can be affected by the surfactant level.
o The resin particle size decreases with increasing surfactant level.
Selecting the Right Resin Dispersion
Compatibility and Physical Properties
When selecting resin dispersions, formulators need to consider
compatibility with emulsion polymers.
When formulating with resin dispersions, the "like-dissolves-like"
principle applies.
For example,
rosin ester dispersions, which are based on polar tackifier resins, are
compatible with polar polymers such as acrylic emulsions.
Physical properties include
the softening point, or
glass-transition temperature (Tg), of the tackifier resin.
In addition,
low color and UV stability are critical physical properties
for certain applications, such as clear filmic labels.
Finally, depending on the adhesive application,
other factors might include FDA compliance and environmental
requirements.

Specific Applications
Depending on the application,
there are specific types of resin dispersions to address nearly every need
(see Table 1).
For example, rosin ester dispersions provide a cost-effective solution
for high-volume paper label applications.
Aliphatic resin dispersions are ideal for applications using natural
rubber latex because of their compatibility.
For applications where clarity is critical, hydrogenated rosin esters and
pure monomer aromatic resins are a good choice, due to their UV
resistance.
Hybrid resin dispersions improve peel and tack and provide good
cohesive strength. And aromatic modified hydrocarbon resin
dispersions offer outstanding cohesive strength and UV resistance.

Resin Dispersions
When an adhesive is being compounded and applied either in solution
or at 100% solids, it is simply a matter of mixing to bring the various
components of the system into the homogeneous state required for use.
Today, however, the use of adhesives based on water dispersions of
polymers is an indispensable part of the industry. When the base
polymer for the adhesive is dispersed in water, the tackifiers and other
components of the system must either disperse readily in the latex or be
supplied in dispersed form for easy combination with the base latex.
Early resin dispersions were used to liquefy hard resins to permit their
dispersion. This solvent cut technique worked well but produced a
material with a significant content of volatile organic solvent in the
system. With the increasing demand to protect the environment, solvent
cut-based dispersions are no longer acceptable and solvent free resin
dispersions are now required.
The production of resin dispersion is usually done by emulsifying the
resin at high temperature (the resin becomes liquid) into the aqueous
phase. Once the system has cooled down, the resin becomes hard again
and remains finely dispersed in the aqueous phase. For some
specialized applications, room temperature liquid resins are dispersed as
well. The resin dispersion can be mixed into the polymer dispersion
easily. The adhesive film formed upon drying is an intimate mixture of
elastomer and tackifier resin.

In combination with a given polymer, the type and concentration of

dispersed resin drives the properties of the final formulation. In order to
be useful, the resin dispersion must not cause undue changes such as
coagulation or grit formation in the elastomer dispersion. The solid
resin must also be compatible with the dry elastomer. The amount and
type of emulsifier used to form the dispersion are the main factors
determining the storage stability, inter compatibility between the resin
dispersion and the elastomer latex, and processability on coating
equipment. Because many variables must be considered, a broad range
of resin dispersions targeted for specific applications are available:
Rosin acid-based dispersions - The dispersed phase is based on aging
resistant stabilized rosin acids. They provide good compatibility with all
polymer dispersions commonly used to produce pressure sensitive
adhesives. Good adhesion to many substrates can be expected. The low
molecular weight of the base resin may be a disadvantage due to the
reduced cohesion that results from their use.

Rosin ester-based dispersions - The dispersed phase is based on aging

resistant stabilized rosin esters. Rosin esters have a higher molecular
weight than rosin acids and therefore provide good cohesion. Ester type
resin dispersions provide good compatibility and improved adhesion in
all polymer dispersions commonly used to produce pressure sensitive
adhesives.

Rosin acid-based dispersions - The dispersed phase is based on aging

resistant stabilized rosin acids. They provide good compatibility with all
polymer dispersions commonly used to produce pressure sensitive
adhesives. Good adhesion to many substrates can be expected. The low
molecular weight of the base resin may be a disadvantage due to the
reduced cohesion that results from their use.

Rosin ester-based dispersions - The dispersed phase is based on aging

resistant stabilized rosin esters. Rosin esters have a higher molecular
weight than rosin acids and therefore provide good cohesion. Ester type
resin dispersions provide good compatibility and improved adhesion in
all polymer dispersions commonly used to produce pressure sensitive
adhesives.

Hydrocarbon resin-based dispersions - While not compatible with as

wide a range of elastomers as the rosin resin-based dispersions, they can
impart specific adhesion properties to polyolefin substrates that are
superior to rosin resin. Hydrocarbon resin dispersions generally have a
cost advantage over other types.

Resin dispersions based on hybrid feedstock - The dispersed phase is

based on a combination of a hydrocarbon resin and stabilized rosin
acids or esters. Compared to the ester- and acid-based types, these resin
dispersions provide similar or superior properties in the final
formulation and generally have a better cost structure. Apart from the
acrylic latex polymers, traditionally well evaluated in pressure sensitive
label formulations, many polymer dispersions are available. Sometimes,
the compatibility of the hybrid resin dispersions may be limited. Proper
testing and evaluation of each resin dispersion is recommended.

Recommended Resination Levels

For label applications, the acrylic latex may be based on either butyl
acrylate or 2-ethyl hexyl acrylate. For paper label applications, 15-30%
resin dispersion on a dry weight basis is recommended, while 10-15%
dispersion is recommended for filmic label applications (see Table 2).
Waterborne tape formulations generally consist of either acrylic latex or
natural rubber latex. For acrylic PSA tapes, 10-20% resin dispersion is
recommended, while 20-50% dispersion is recommended for natural
rubber formulations.
When formulating pressure-sensitive adhesives, raw materials must be
added in the specific order shown in Table 2 to avoid grit formulation
or coagulation. Depending on the performance requirements, it may
also be necessary to post-add materials such as a surfactant, thickener,
defoamer or biocide to optimize the adhesive formulation.

Specialty Dispersion Applications

Resin dispersions are ideal for specialty adhesive applications such as
waterborne contact adhesives, specialty tapes and protective films, and
filmic labels. Eastman offers a family of Tacolyn resin dispersions to
meet the specific requirements of these applications.

Waterborne Contact Adhesives

Waterborne contact adhesives are environmentally friendly, solvent-free
and clean up easily with water. Contact adhesives are used for
applications such as laminate bonding and foam bonding. Contact
adhesive formulations generally contain either polychloroprene latex or
styrene-butadiene latex (see Table 3).

Adhesives consisted of 100 parts tackifier resin (dry weight) and

100 parts natural rubber latex.
Labels consisted of 25 g/m2 dry adhesive coated onto Mylar (PET)
film.
Dimensions for 178° shear test were 1" x 1" contact area with a 1kg
weight.
Shear adhesion was determined in accordance with test method PSTC-
7.
Test data was reported as an average five specimens.

Adhesives consisted of 100 parts tackifier resin (dry weight) and

100 parts natural rubber latex.
Labels consisted of 25 g/m2 dry adhesive coated onto Mylar (PET) film.
Dimensions for 178° shear test were 1" x 1" contact area with a 1kg
weight.
Shear adhesion was determined in accordance with test method PSTC-
7.
Test data was reported as an average five specimens.

Filmic Labels
The need for environmentally friendly, waterborne PSAs continues to
grow. Filmic label applications have shown significant growth. These
demanding applications require PSAs that are non-water-whitening
because clarity is crucial in filmic labels. Excellent adhesion to low-
and high-energy substrates is also important in filmic label applications.
A resin dispersion is generally added to a filmic latex at the 15%
resination level, on a dry weight basis (see Table 4).

Adhesives consisted of 100

parts tackifier resin (dry
weight) and
100 parts natural rubber
latex.
Test laminates consisted of
25 g/m2 dry adhesive coated
onto Mylar (PET) film.
180° peel adhesion was
determined in accordance with test method PSTC-1 with a five-minute
dwell time.
All tests were performed @ 23°C, 50% relative humidity. Test data was
reported as an average five specimen.

Figure 7. Loop Tack Test Results

Note:
Adhesives consisted of 100
parts tackifier resin (dry
weight) and 100 parts natural
rubber latex.
Test laminates consisted of 25
g/m2 dry adhesive between
Mylar (PET) film and
siliconized release liner. Loop
tack was determined in
accordance with test method PSTC-16.
All tests were performed at 23°C, 50% relative humidity. Test data was
reported as an average five specimens.
 Figure 8. Peel Strength versus
Resination Level on Stainless
Steel

Note: Adhesives consisted of

100 parts tackifier resin (dry
weight) and 100 parts natural
rubber latex. Test laminates
consisted of 25 g/m2 dry
adhesive between Mylar (PET)
film and siliconized release liner. 180° peel adhesion was determined in
accordance with test
method PSTC-1 with a five-
minute dwell time. All tests
were performed at
23°C, 50% relative
humidity. Test data was
reported as an average five
specimens.

Figure 8 also
demonstrates that peel strength of natural rubber-based adhesives is
increased in small increments relative to the resination level. Thus, it is
possible to use a single resin dispersion in a natural rubber latex system
at different loadings to produce several adhesives with low, medium or
high peel performance (see Figure 8).

Figure 9. 180 Peel Test Results

Note:
Labels consisted of 21 g/m2 dry adhesive between 100-gauge corona
treated oriented polypropylene and siliconized release liner.
180° peel adhesion was determined in accordance with test method
PSTC-1 with a five-minute dwell time.
All tests were performed at 23°C, 50% relative humidity. Test data was
reported as an average five specimens.
 Figure 10. Loop Tack Test
Results
Note:
Labels consisted of 21 g/m2 dry
adhesive between 100-gauge
corona treated oriented
polypropylene and siliconized
release liner.
Loop tack was determined in
accordance with test method PSTC-16.
All tests were performed at 23°C, 50% relative humidity.
Test data was reported as an
average five specimens.
Figure 11. 1" x 1' Shear Results
Note:
Dimensions for 178° shear test
were 1" x 1" contact area with a
1kg weight.
Shear adhesion was determined
in accordance with test method
PSTC-7 with a 30-minute dwell time.
All tests were performed at 23°C, 50% relative humidity. Test data was
reported as an average five specimens.

Figure 12. Water Resistance

Testing.
180° Peel Testing After 24 Hour
Water Soak.
Note: Panels were placed in
room temperature deionized
water and soaked for 24 hours.
Labels were observed for whitening.

Panels were removed from the water bath, gently wiped dry and
immediately subjected to 180° peel test.
180° peel adhesion was determined in accordance with test method
PSTC-1 with a five-minute dwell time.
Test data was reported as an average five specimens.

Conclusion

PSA manufacturers are being challenged to reduce costs without

sacrificing performance or the environment.
Resin dispersions help to meet these challenges by offering many
advantages when formulated with emulsion polymers.
Performance advantages include optimized peel and tack and enhanced
specific adhesion to low- and high-energy substrates, such as
polyethylene and glass.
Resin dispersions also improve high- and low-temperature performance
and have excellent compatibility with many types of emulsion
polymers.
Finally, resin dispersions are environmentally friendly, FDA-compliant
and can improve the overall cost efficiency of an adhesive formulation.
Solutions, Colloids and Suspensions
Mixture of other substances in water cab ne classified as Solutions,
Colloids and Suspensions
A solution consists of particles of matter called as solute mixed
with a more abundant substance (usually water) called the solvent. The
solute can be gas, solid or liquid, as in a solution pf oxygen, sodium
chloride, or alcohol in water, respectively. Solutions are defined by the
following properties.
o The solute particles are under 1 nanometer (nm) in size, the
solute and the solvent therefore cannot be visulaly distinguished
from each other, even with a microscope
o such small particles do not scatter light niticeably, so solutions
are usually transparent (pl see the Firure)
o The solute particles will pass through most selectively
permeable membranes, such as dialysis tubing and cell
membranes.
o The solute does not seperate from the solvent when the solution
can stand.

The most common Colloids in the body are mixtures of

Protein and water, such as the albumin in blood plasma. many Colloids
can change from liquid to gel states - gelatin desarts, agar culture
media, and the fluids within and between our cells for example.
Colloids are defined by the following physical properties.
o The colloids particles range from 1 to 100 nm in size.
o Particles this large scatter light, so colloids are usually cloudy
(see fig)
o The particles are too large to pass through most selectively
permeable membranes.
o The particles are still small enough, however, to retain
permanently mixed with the solvent when the mixture stands

Suspensions are defined by the following properties

The suspended particles exceed 100nm in size
Such large Particles render suspensions cloudy or opaque
 The particles are too large to
penetrate selectively
permeable membranes
The particles are too heavy to
remain permanently
suspended so suspensions
seperate on standing. Blood
cells, for example, from a
suspension in the blood
plasma and settle to the
bottom of a tube when blood
can stand without mixing (see
Figure)

An emulsion is a suspension of one liquid in another, such as oil

and vinegar salad dressing. The fat in breast milk ia an emulsion, as are
medications such as Kaopectate and milk of magnesia

What are the differences

between solutions,
suspensions, and emulsions
in chemistry?

What is the major

difference between
emulsion and suspension?
emulsions are two liquids that are insoluble to EACH other. That is
key! The two chemicals liquids repel each other due to surfactants. The
do not like to be mixed hence they form droplets or separate identities
when mixed-applied together as an emulsion. An example of this would
be oil and vinegar would you apply on salad and they collect
vinaigrette.

A solution is we are two chemical elements or liquids are mixed and

form a fine particle missed or spray. They do not resist each other hence
they are in solution with each other. Solutions are usually represented in
in percentages. For example, milk would be 2% solution with fat. Verse
it is low fat milk or reduced fat milk. You don’t see separate droplets of
fat floating around in your milk because it’s in solution and it’s mixed
because there’s no surfactant or resistance causing them to repel each
other. I hope this gives you a better understanding of how chemistry is
applied daily in our life by giving you two examples of food which
there are many! There are so many more! Take some time the next
opportunity you must look at the different salad dressings for emulsions
and then you can go into the drinks sections and see the different
solutions that drinks are proportioned out at.

What is an emulsion?
In the Organic Coating industry, there are two groups of materials. One
group is the water loving (Hydrophilic) group of substances. The other
is the Oil loving (Lyophilic) substances. These two-separate group of
substances arise due to their polar or non-polar nature.

Usually a water loving, or polar substances contain oxygen. They

contain a shorter hydrocarbon entity in them and oxygen carrying
groups like Acids, Alcohols, Aldehydes, Ketones, Esters and so on.
Their molecules need not be smaller, and they could even be polymers
like Starch, Carbohydrates, Carboxy Methyl Cellulose. (Examples of
Polar Substances: Acetic Acid, Methyl Ethyl Ketone, Acetaldehyde,
Ethyl Alcohol, Oxalic Acid, Formaldehyde, Starch, Glucose, Sucrose
etc).

In wide contrast, the Non-Polar substances may or may not contain

oxygen and have larger Hydrocarbon chains. The examples are petrol
(n-Octanes), Kerosene, Diesel, Coconut oil, Palm Oil etc.)
WATER LOVING = HYDROPHILIC
WATER HATING = HYDROPHOBIC

Depending on which has a higher density, they separate into two layers,
so that the lighter layer goes to the top and with the higher density
material settling at the bottom. If you stir and mix them thoroughly,
they shall form small spherical droplets of one surrounded by the other
material. If water is more in volume, the small droplets shall be oils
which are surrounded by water and are called oil in water suspension. If
oil is in excess then the droplets shall be water, suspended in oil and
this mixture is called as water in oil suspension.

In the example shown above, both oil and water are in same proportion
with the oil denser than water settling to the bottom. Let us consider a
case of water in excess than the oil or in other words a suspension of oil
in water. When you mix these and stir continuously, they form droplets
but over a period separate again. If you add some soap solution to this
mixture of suspension of oil in water, it stabilizes this suspension.
Why?

A soap is unique in that it has both Hydrophilic and Hydrophobic parts

or two different moieties in one molecule. The example shown below is
that of Sodium Stearate the sodium salt of stearic acid
 What is a Resin
From Wikipedia, the free
encyclopaedia
Cedar of Lebanon cone showing flecks of resin as
used in the mummification of Egyptian Pharaohs.

Insect trapped in resin

In polymer chemistry and materials
science, resin is a solid or highly viscous substance of
plant or synthetic origin that is typically convertible
into polymers. Resins are usually mixtures of organic
compounds. This article focuses on naturally occurring
resins.
Plants secrete resins for their protective benefits in
response to injury. The resin protects the plant from
insects and pathogens. Resins confound a wide range
of herbivores, insects, and pathogens, while the
volatile phenolic compounds may attract benefactors such
as parasitoids or predators of the herbivores that attack the plant.

Rosin

Extremely viscous resin extruding from the

trunk of a mature Araucaria columnar is.
Solidified resin from which
the volatile terpenes have been removed by
distillation is known as rosin. Typical rosin is a
transparent or translucent mass, with a vitreous
fracture and a faintly yellow or brown colour,
non-odorous or having only a slight turpentine odour and taste. Rosin is
insoluble in water, mostly soluble in alcohol, essential oils, ether, and
hot fatty oils. Rosin softens and melts when heated and burns with a
bright but smoky flame.
Rosin consists of a complex mixture of different substances including
organic acids named the resin acids. Related to the terpenes, resin acid
is oxidized terpenes. Resin acids dissolve in alkalis to form resin soaps,
from which the resin acids are regenerated upon treatment with acids.
Examples of resin acids are abietic acid (silvic acid), C20H30O2, plicatic
acid contained in cedar, and pimaricin, C20H30O2, a constituent
of galipot resin. Abietic acid can also be extracted from rosin by means
of hot alcohol. Pimaric acid closely
resembles abietic acid into which it
passes when distilled in a vacuum; it
has been supposed to consist of three
isomers.
Rosin is obtained from pines and
some other plants, mostly conifers.
Plant resins are generally produced as
stem secretions, but in some Central
and South American species such
as Euphorbia dalechampia and Clusia species they are produced as
pollination rewards, and used by some stingless bee species to construct
their nests.[6][7] Propolis, consisting largely of resins collected from
plants such as poplars and conifers, is used by honey bees to seal small
gaps in their hives, while larger gaps are filled with beeswax.
Petroleum- and insect-derived resins
Shellac and lacquer are examples of insect-derived resins.
Asphaltite and Utah resin are petroleum bitumens, not a product
secreted by plants, although it was ultimately derived from plants.
History and etymology

The material dripping from an almond tree looks confusingly like resin,
but actually is a gum or mucilage, and chemically very different.
Human use of plant resins has a very long history that was documented
in ancient Greece by Theophrastus, in ancient Rome by Pliny the Elder,
and especially in the resins known as frankincense and myrrh, prized
in ancient Egypt. These were highly prized substances, and required
as incense in some religious rites.
The word resin comes from French resine, from Latin resina "resin",
which either derives from or is a cognate of the
Greek ῥητίνη rhētinē "resin of the pine", of unknown earlier origin,
though probably non-Indo-European
The word "resin" has been applied in the modern world to nearly any
component of a liquid that will set into a hard lacquer or enamel-like
finish. An example is nail polish. Certain "casting resins" and synthetic
resins (such as epoxy resin) have also been given the name "resin."
Some resins when soft are known as 'oleoresins', and when
containing benzoic acid or cinnamic acid they are called balsams.
Oleoresins are naturally occurring mixtures of an oil and a resin; they
can be extracted from various plants. Other resinous products in their
natural condition are a mix with gum or mucilaginous substances and
known as gum resins. Several natural resins are used as ingredients in
perfumes, e.g., balsams of Peru and tolu, elemi, styrax, and certain
turpentines.[5]
Resin, any natural or synthetic organic compound consisting of a
nanocrystalline or viscous liquid substance. Natural resins are typically
fusible and flammable organic substances that are transparent or
translucent and are yellowish to brown in colour. They are formed in
plant secretions and are soluble in various organic liquids but not in
water. Synthetic resins comprise a large class of synthetic products that
have some of the physical properties of natural resins but are different
chemically. Synthetic resins are not clearly differentiated from plastics.
Most natural resins are exuded from trees, especially pines and firs.
Resin formation occurs as a result of injury to the bark from wind, fire,
lightning, or other cause. The fluid secretion ordinarily loses some of its
more volatile components by evaporation, leaving a soft residue at first
readily soluble but becoming insoluble as its ages. The ancient Chinese,
Japanese, Egyptians, and others used resins in preparation of lacquers
and varnishes.

Natural resins may be classified as spirit-soluble and oil-soluble.

Among the former are balsams, long popular as a healing agent;
turpentines used as solvents; and mastics, dragon’s blood, dammar,
sandarac, and the lacs, all used as components of varnishes. The oil-
soluble resins include rosin, derived along with turpentine from the
long-leaf pine and long used for a variety of applications, including
soapmaking; copal’s, used in varnishes; amber, the hardest natural
resin, fabricated into jewellery; Oriental lacquer, derived from a tree
native to China; and cashew-nutshell oil, derived from cashew nuts.

In modern industry natural resins have been almost entirely replaced by

synthetic resins, which are divided into two classes, thermoplastic
resins, which remain plastic after heat treatment, and thermosetting
resins, which become insoluble and infusible on heating.

Description
All resins can harden under certain conditions - by mixing with a setting
agent, heated, or exposed to light. The latter method is used for resin 3D
printing. Such materials are highly viscous liquids before solidifying.
The range of synthetic resins is huge and includes resins created from
thermoplastics like ABS, Nylon, and Polypropylene. Some of these are
referred to as resins only in their liquid form – after curing, they are
simply called plastics or elastomers. Some resins after hardening can’t
be melted or re-used. Different types of resins exist depending on their
chemical compounds which define its properties: silicones, epoxies,
acrylics, alkyds, and more.

What is resin material made of?

There is a huge variety of different resin materials, both natural and
synthetic. Resins consist of long chains of monomers, which form
cross-link bonds during the curing process.

What are the different types of resin?

Typically, resins are divided into thermosets and thermoplastics based
on whether the hardening reaction can be reversed. Widely used
thermoplastic resins include ABS, polyethylene, polystyrene, and
polycarbonate. Most common thermoset resins are polyester, vinyl
ester, epoxy, and polyurethane.

Thermoplastic resins are basically the ones that can be melted and then
hardened once cooled. Within the molecule chain of such resins, there
are extremely strong bonds between molecules. Thermosets, on the
contrary, undergo a non-reversible reaction resulting in a hard product.
It is determined by the process called polymerization or cross-linking
which takes place in such materials caused using a catalyst, heat or a
combination of the two.

How is resin produced?

Production of artificial resins starts from a so-called cracking process,
which means that different types of hydrocarbons are heated up to
separate molecules. Then polymer compounds are built in order to
create a specific resin.

Resin material properties

Properties can be improved to certain levels depending on the resin's
composition. But we included several quite popular resins into a list to
demonstrate how different can these materials be once hardened.

Resin material properties

Resin Properties Max. Temperature (ºC)
ABS Glossy finishing, good shock resistance. 100
Epoxy Great physical and chemical properties.
Easy to cast with. 200
Nylon Great wear resistance. 140
Polycarbonate
(PC) Transparent. Withstands acid and shock. 130
Polypropylene
(PP) Great mechanical strength 140

3D printing with Resin

In 3D printing, resins are a family of photopolymers that consist of a
photo initiator and different monomers. These materials react under
UV-light, daylight or laser beam energy that changes their state from a
liquid to a solid structure. 3D printers direct light sources to certain
areas that need to be solidified and create a part, layer-by-layer, or in
the case of MJP technology, resin drops are applied all together and
cured after each layer.

Resin Casting
Resins are used in casting for low-volume production, props, in the
medical industry, and more. It requires molds, which are filled with
liquid resin and hardens inside polymerizing. Some resins are easy to
use and compatible with silicone or DIY molds, so even hobbyists can
use them without special tooling to produce parts. The liquid nature of
resin material also allows mixing it with additives for improving its
properties and easier removal of molds.

Resin casting guide

Resin casting is a manufacturing method widely used for low volume
production by professionals and hobbyists. The general idea is to fill in
a mold with a liquid resin, leave it until the material hardens and then
release a product from its mold.

Commonly flexible molds are used, which can be made from latex or
silicone rubber, to make releasing the cast easier. Such molds can be
used multiple times depending on their condition but they tend to have
their own limits that don’t allow to use resins casting for big batches.
Some simple molds for one-time use can also be made from available
materials like plastic folders, wood pieces and more.
For mechanical and automotive parts, when all the details should be
transferred to the casted part perfectly, special resin grades and mold
materials are used to cut down shrinkage and inaccuracy.

Typically resin casting procedure starts from making a master model. It

can be hand carved, CNC milled, 3D printed, sculpted or manufactured
in any other way. The material of the master model should be sturdy
enough to allow making a precise mold, so popular choices include
rigid plastics such as polyurethane, epoxy, polyester, ABS, Nylon or
Delrin. Stretchy or fragile materials would deliver a poor surface of the
piece and imprecise details.
The next step would be creating a negative mold with an imprint of the
master model. Many makers prefer silicone rubbers for molds due to
them providing an easy working process, good accuracy and
mechanical properties, non-sticky surface for casting and little to no
shrinkage. The mold itself should be made so that the resin would easily
fill in the imprint of a master model without gaps or extras. Therefore,
sometimes the mold is made in two or more pieces to allow resin
spreading inside evenly.
After a mold is prepared, it comes to the actual resin mixing and
pouring. Here the process varies based on the type of the resin used for
casting.
After pouring the material some additional work (like vacuum chamber,
heat treatment) may be required to remove the air bubbles and help
resin cure well.
If all steps were processed correctly, the final product would be a nearly
identical copy of the master model made from resin.

CNC Machining Resins

Resins aren’t commonly used in CNC machining since they require a
solid material to work with. Hardened resins like ABS, epoxy, Nylons
and others can be machined as they are already plastics. However, on
the market, there are some rare CNC machines that can combine paste
extrusion of resins with milling operations. Resins, in this case, are
typically used as a coating for other materials and they can be placed
and then machined with the same CNC machine in one go.
What is resin used for?
Resins have numerous applications starting from jewellery making to
manufacturing parts for sports cars. Different resins can be used by
themselves as a base or as a gluing agent for materials like carbon fibre,
fiberglass and more.

Resin construction material

Resins are widely used in building as adhesives, coatings or as a
construction material when a strong bond is required. For example, for
laminated wood construction. Resins are also popular in the decoration
of self-levelling floors and architectural surfaces enabling to use of
recycled materials.

Common Uses
1. Adhesives, paints and coatings
2. Decoration
3. Electronic components and replacements for metal parts
4. Gears, pipes and tubes
5. Intricate models and parts
6. Jewellery
7. Medical devices
8. Consumer goods
9. Boat, car and parts repairing

Advantages:
1. Precision
2. Large variety of resins with different properties
3. A wide range of applications
4. Can be food-safe
5. Can be easily colored, dyed, mixed with metal powders or
fluorescent pigments
6. Easy to work with
7. Hardened resins can be machined
8. Disadvantages:
9. Some resins are toxic
10. Fast polymerization reaction requires being quick
 11. Requires special storing (some resins are sensitive to moisture,
temperature and light)
12. Casting Resins need components accuracy
13. Low volume casting may require much handwork, which makes
its net cost high

Tackifier Resins
Tackifiers are low-molecular weight compounds (oligomers) that are
added to adhesive formulations to improve tack and peel adhesion.
Their glass transition temperature (Tg) is typically higher than that of
the base polymer but their molecular weight is much lower.

Tackifiers are chemical compounds used in formulating adhesives to

increase the tack, the stickiness of the surface of the adhesive.[1] They
are usually low-molecular weight compounds with high glass transition
temperature. At low strain rate, they provide higher stress compliance
[clarification needed], and become stiffer at higher strain rates.

Tackifiers tend to have low molecular weight, and glass transition and
softening temperature above room temperature, providing them with
suitable viscoelastic properties. Tackifiers frequently represent most of
both weight percentage and cost of hot melt adhesives and pressure-
sensitive adhesives. In hot melt adhesives they can comprise up to about
40% of total mass.

Tackifiers are usually resins (e.g. rosins and their derivates, terpenes
and modified terpenes, aliphatic, cycloaliphatic and aromatic resins (C5
aliphatic resins, C9 aromatic resins, and C5/C9 aliphatic/aromatic
resins), hydrogenated hydrocarbon resins, and their mixtures, terpene-
phenol resins (TPR, used often with ethylene-vinyl acetate adhesives)),
novolacs.

Many pressure-sensitive adhesives are a blend of rubbers (natural or

synthetic) and a tackifying resin. Some acrylic adhesives also include
an additional tackifier. Silicone rubber–based pressure-sensitive
adhesives require special tackifiers based on "MQ" silicate resins,
composed of a monofunctional trimethyl silane ("M") reacted with
Quadra functional silicon tetrachloride ("Q").

Tackifiers are also used in tyres.

How do tackifiers work?

How do Tackifiers Work. Tackifiers work by reducing the modulus and
increasing the glass transition temperature (Tg) of the resulting
adhesive formulations. Both these factors are critically important to
achieve the necessary tack and peel strength.

What is tackifier adhesive?

Tackifiers are chemical compounds used in formulating adhesives to
increase the tack, the stickiness of the surface of the adhesive. They are
usually low-molecular weight compounds with high glass transition
temperature.

What are hydrocarbon resins?

Hydrocarbon resin is a C5/C9 aromatic hydrocarbon used in industrial
applications. ... It is a kind of thermal plasticizing hydrocarbon resin
produced by C5, C9 fraction, by-products of petroleum cracking,
through pre-treatment, polymerization and distillation.

What is Hydroseed tackifier?

HYDROBOND™ Hydroseeding Tackifier Amendment. Hydro Bond is
a safe, non-toxic linear anionic polymer that can be used with any paper
or fibre mulch products. The anionic high molecular weight polymer
binds the hydroseeding media to the soil particles.
Predicting Ingredient
Compatibility Using HSP
in Adhesive Formulations
Steven Abbott – Mar 29, 2018
When an adhesive needs a new solvent
blend, or you have to find ways that
the components in an adhesive can be
optimized to be “happy” together, or
you need to find how to match the
properties of the adhesive to those of a
substrate, what should the adhesives formulator do?

To approach these issues from a science-based formulation method, we

can use a powerful solubility and compatibility technique that
uses Hansen Solubility Parameters. Via HSP values for all our
components we can rapidly identify which components like, or don’t
like to be with each other.

Learn from Professor Steven Abbott what Hansen Solubility Parameters

are and how they should become a
go-to tool for science-based
formulation.

Let's get started...

Better Adhesives via Science-based

Formulation using Hansen
Solubility Parameters

You have been asked to find a new

solvent blend, or there is a
requirement to incorporate some
new ingredients into a formulation,
or the compatibility between
adhesive and substrate must be
maximized. How can you manage these requirements using the least
amount of effort and expensive lab time?

If we try to use vague terms such

as hydrophilic/hydrophobic or polar/non-polar we quickly hit the
problem that they are inadequate for describing the complexities of the
molecules we use. We need something better. And “better” means “with
numbers” so we can formulate scientifically.

Focusing Specific Areas of Adhesives

We need a good measure of whether two molecules (or formulations)

are “like” or “unlike” each other, via a “distance” between them. To do
this, we must start with three numbers - The HSP, that describe each
component within in our adhesive formulation. We need three numbers
because we can’t capture chemistry in two numbers, and with four
numbers things are too complex to handle. Note, however, that the size
of the molecule (via molecular weight or molar volume) plays an
important role and is an implicit extra parameter.

We start by describing:

What those three numbers are

How you go about estimating or measuring them
How you can use them in three specific areas of adhesion

The three specific areas of adhesion are:

o Coating an adhesive layer
o Ensuring compatibility between additives and the adhesive
polymer
o Ensuring compatibility between adhesive and adherend

Hansen Solubility Parameters – The Three Numbers

A solvent like hexane or a polymer like polyethylene is held together by
general van der Waals or Dispersive forces. Aromatics still only have
Dispersion, but they have a broader electron cloud so have a larger
amount of it. So, already we can see that one of the parameters must
describe Dispersion, labeled δD.
Obviously, many solvents and polymers contain polar groups, so we
need a number, δP, to describe them.
Finally, there is a difference between being Polar and having Hydrogen
Bonds, so we need a Hydrogen Bonding parameter, δH.

These three factors are the Hansen Solubility Parameters.

The table below lists the HSP of some common solvents:

Solvent δD δP δH
Acetonitrile 15.3 18 6.1
Acetone 15.5 10.4 7
Benzene 18.4 0 2
Diethyl Ether 14.5 2.9 4.6
Dimethyl Sulfoxide 18.4 16.4 10.2
Hexane 14.9 0 0
Ethyl Acetate 15.8 5.3 7.2
Ethanol 15.8 8.8 19.4
Methylene Dichloride 17 7.3 7.1
N-Methyl-2-
18 12.3 7.2
Pyrrolidone
Tetrahydrofuran 16.8 5.7 8
Water 15.5 16 42.3

Looking at the list above, there is no problem making sense of the broad
trend of the numbers.

Acetonitrile, for example, is very polar, so its δP value is high, whereas

its δH value is not so big as its ability to hydrogen-bond is modest.
Ethanol is medium in terms of δP value, with a large δH value, as we
would expect from such a hydrogen-bonded solvent. Each of them has a
relatively small δD value.
Benzene and DMSO both have higher δD values. Thanks to the large
electron clouds around them!
Hexane is a simple, relatively low δD solvent; acetone and ethyl acetate
are just middle-of-the-road in their three parameters.

Determining How "Like" Molecules are

Now we are ready to find how “like” two molecules are. We just
calculate the “distance”, D, in 3D space between any pair using the
famous HSP formula (including a factor of 4 for the δD values)

D² = 4(δD1-δD2) ²+ (δP1-δP2) ²+ (δH1-δH2) ²

If the D value is less than ~ 4, then this is a reasonable match. If the

value is greater than ~ 8, then this is a poor match.
Given a target molecule plus a list of potentially interesting molecules,
you simply calculate D between the target and each molecule, and after
sorting them from low (good) to high (bad); you can choose which of
the low D molecules meet your other requirements, such as volatility or
greenness.

Typical examples involve a polymer as a target with the molecules

being solvents. Equally, the target could be a specific portion of a resin
and the molecules could be tackifiers. HSP also works well when the
target is a filler or nanoparticle and the aim is to ensure maximum
compatibility.
What if no molecule matches all your adhesive formulation
requirements?

There is another key feature of HSP; when no single molecule meets all
the requirements, you can work out a successful blend between two
molecules which have high D values but which, for other reasons, you
would like to use.

Suppose each molecule is reasonably matched to your target in terms of

δD and δP but one has a high δH and the other has a low δH. The HSP
of a blend is the weighted average of the respective parameters, so in
this case, the δH can be tuned for a smaller distance to your target.

Therefore, you can blend two unusable molecules (D too large) into a
usable formulation. This ability to turn poor starting materials into great
blends is the reasons for HSP’s success over the past 50 years.

Given that to do these calculations you need the HSP values, where can
you find them?

Finding the Parameters

Fortunately, the HSP are known (and in the public domain) for all
the common solvents, the newer green solvents and for many polymers
and additives.

What about your own special chemical, polymer, additive, filler?

The answer is that there are two techniques for measuring HSP values,
each of which you can do in-house or contract out to those set up to
offer such a service.
The first technique requires you to judge whether your material is
“happy” (soluble, swellable, dispersible …) or “unhappy” in a set of
solvents that span HSP space. The set of “good” solvents defines a
sphere with the HSP at its centre and the radius of which defines the
usable range of solvents.
The second technique is based on Inverse Gas Chromatography
(IGC) and measures the strength or weakness of the interactions of
probe solvent molecules with your sample, which forms the stationary
phase of the IGC column. The standard technique is the more widely
used. The IGC technique is especially useful for oligomers, surfactants,
and excipients that are so fluid at room temperature that the standard
test gives too many “good” solvents and too few “bad” ones.

We can now discuss how to use HSP in three specific areas of adhesive
formulation: finding the right solvent blend; using compatible additives;
and ensuring good compatibility across the adhesive interface.

Finding the Right Solvent (blend)

Given a known HSP for an adhesive polymer it is very easy to find an
effective solvent for it. Get a list of solvent HSP values, calculate the
Distance from the material and choose the solvent with the shortest
Distance.

But real life is not like that!

We don’t want just an effective solvent; we want a usable solvent. So

cost, odor, VOC level, hazard rating etc. all become significant factors
in our choice. Almost always the best solvent in terms of HSP is
unsatisfactory for other reasons and as we go down our list in terms of
increasing Distance, we might fail to find a satisfactory compromise.
This is when the power of HSP is fully revealed.

Imagine that our adhesive has an HSP represented by the green dot
inside the green sphere, and that we have two bad solvents which, by
definition, are outside the sphere. In the diagram, those bad solvents
happen to be exactly opposite each other. Now make a blend with
50:50. The HSP of a blend is the volume weighted average of the two
components which, in this case, would make this blend a perfect solvent
for the solute.
 If you try this in practice, you find
that you really can make a good
solvent from two bad solvents or
take two OK solvents and create a
really good blend. All it needs is the
HSP of your target. An optimum
blend can readily be found with a
list of suitable solvents via:

Human judgment, or
Computer algorithm with
weightings for factors such as cost,
greenness etc.

Fine-tuning the Evaporation Rate

If we know the relative evaporation rates of the individual solvents and

their individual distances; we can even tune what happens to a coating
during evaporation. When the solution is relatively dilute, we can get a
cheap, but not very good solvent. As the coating dries, we often want
the polymer to stay in solution for as long as possible to be relaxed and
glossy. This means that the less volatile solvent should be a closer
match.

The app below shows an

example where the Distance
(called Ra) goes from 5.2 at the
start (not great, but Ok) to 3 as
the ethyl acetate evaporates
faster than the cyclohexanone

HSP Distance Transition in Solvent Blends

If you want the coating (or a component in it) to crash out quickly, you
tune the blend so that the better solvent is more volatile.

Producing a Rational Blend of "Greener" Solvents

One area where solvent blends are especially important is, in

the replacement of a toxic or environmentally unfriendly solvent
with a greener alternative. Using your current solvent as the target,
you can take any convenient list of green solvents and find the closest
match.

It is usually the case that no single solvent is good enough, so you have
to produce a rational blend of the greener solvents. This HSP method
for creating greener blends has been proven to work many times – in
the lab and in the real world of cleaning. For example: creating safer
solvents for cleaning up after a printing or coating run. Once, some of
my operators complained about one cleaning solvent blend and they
asked me to use it myself. It was terrible in two senses:

It was smelly and unhealthy

It was so volatile that the polymer would re-deposit before it had been
properly removed

Using HSP and being limited to the nicer solvents we happened to have
in-house, I could quickly create a pleasant, low odor, low volatile blend.
When we tried it; it was useless if the previous cleaning regime was
followed. But, by putting it onto the equipment as soon as it needed
clearing, attending to other jobs and returning, we found that the solvent
blend was still, and had time to dissolve the polymer. A simple wipe
removed most of the polymer and a quick clean with the old blend
finished the process. Far less work for far better results – and much
safer.

Polymer Compatibility with Other Ingredients of Adhesive Formulation

#1. Polymer-Polymer Compatibility

From the formal theory behind HSP, it is possible to prove a rather

shocking fact that has been validated experimentally. That is, most
polymers are insoluble in most other polymers. For instance, PMMA is
not soluble in PEMA. It turns out that for mutual compatibility, the HSP
Distance between two polymers must be less than 0.1, which is
impossible.

Our real-world experience is that there are plenty of reasonable polymer

blends between related polymers. Here we have a difference between
“reasonable” and “thermodynamics”.

Moderate molecular weight PMMA and PEMA are easily mixed and
under normal circumstances will not phase separate.
The thermodynamic limit applies to high molecular weights and long
times at high temperatures allowing the polymers to reach equilibrium.

So if you want practical polymer blending with a low risk of long-term

phase separation, a low HSP Distance is a good starting point.

If you use a more elaborate version of HSP which splits δH into

donor/acceptor, you can find that polymers with relatively large
distances, such as polyvinyl phenol and polyvinyl acetate can form
stable blends via donor/acceptor interactions.

#2. Polymer-Other Additive Compatibility

When it comes to additives in adhesives, such as plasticizers,

antioxidants or fillers etc. - low HSP Distance is the first criterion for
long-term stability. By knowing the HSP of your additives from your
suppliers or by measuring the values for your own special ingredients, it
becomes much easier to create “happy” formulations where everything
likes to be with everything else.
Many long-term adhesive problems are caused by incompatibilities that
could easily have been identified early on via HSP Distance.

Polymer-polymer Adhesion
The best way to get adhesion across a polymer-polymer interface is to
have polymer chains crossing from both sides and becoming entangled.
How can we calculate the chances of two polymers being able to
intermingle and entangle
to the required amount?

A rather simple formula

from Helfand relates the
intermingling distance to the χ parameter and, therefore, to HSP
Distance.

Relation Between χ Parameter and HSP Distance

In this example, a polymer with a Kuhn length (a virtual, effective,

monomer length) of 1.5nm could intermingle by 3.2nm when the HSP
Distance = 3.9 (at χ = 0.15).

Because the mythology that adhesion depends on surface energies is so

widespread (even though surface energies are 1000x too small to be
relevant) this powerful way to understand adhesion across interfaces is
far too little known. But those who know it can attest to its power in
being able to formulate correctly.

And it’s not just polymer-polymer. We often have a non-polymer

surface and need to attach a primer molecule to aid adhesion. The
primer needs to be long enough to tangle and compatible enough to be
happy to associate with the polymer. So, finding the HSP of the primer
is vital for success.

But however much the Helfand formula tells us we might get

intermingling; the polymers are not going to cross the interface unaided.
For heat sealing, we have temperature and time
For coating we have solvents

If one polymer is being delivered from the solvent then, of course, there
must be good polymer-solvent compatibility as discussed earlier. But
we also need the solvent to attack the polymer onto which we are
coating. Attack, yes, but not too much or we destroy the surface.

Tuning the solvent to have enough “bite” into the surface to enable
entanglement to take place (i.e. over a few nm) without destroying the
surface (defects on the µm) scale is another job for HSP.

Conclusion

For more than 50 years, HSP has proven themselves in the world of
formulations. Common tasks such as finding good solvents (or blends)
or ensuring compatibility between components in a formulation become
much more rational and efficient when the HSP of all the key
ingredients are known, either from your suppliers or internally, and
HSP Distance calculations are used routinely to find the best
combinations.
Adhesives Essentials: Formulating with Resin
Dispersions
Editor's note: This is the fifth in a series of articles designed to address
the fundamentals of adhesive and sealant formulation.

In an increasingly competitive marketplace, adhesive formulators are

under constant pressure to find cost-effective solutions that meet both
performance and environmental requirements for applications including
pressure-sensitive adhesive (PSA) tapes and labels, protective tapes and
films, contact adhesives, and sealants and coatings.
Resin dispersions are used with emulsion polymers to optimize peel,
tack and shear performance in such applications.
This article will touch on the fundamentals of resin dispersions and
detail what factors to consider when formulating an adhesive using
resin dispersions to balance peel and tack with shear performance for
PSA applications.

Resin Dispersion Basics

A resin dispersion contains a low-molecular-weight tackifier resin
dispersed in water with the aid of a surfactant. These tackifier resins
include hydrocarbon resins or rosin ester resins. Hydrocarbon resins
used to make dispersions include C5 resins based on piperylene, C5/C9
resins based on piperylene and aromatic feedstocks, or pure monomer
resins (PMRs) based on styrene and styrene derivatives. Rosin esters
are the product of a reaction between rosin acid and a multifunctional
alcohol. Rosin esters may be used alone or in a blend with hydrocarbon
resins to make rosin ester dispersions.
The materials required to synthesize resin dispersions include the
precursor resin, surfactant and water. Generally, the percent solids level
of resin dispersions is between 50% and 58%. Optional additives
include materials such as plasticizers, ion tolerance agents, antioxidants
and biocides.
Particle size is a key factor in the overall performance of resin
dispersions. Small particle size enhances dispersion performance by
providing increased shelf life, improved mechanical stability, improved
pumpability and easy filtration. Small particle size is also important in
applications where clarity is crucial, such as in filmic labels. Particle
size can be affected by the surfactant level. The resin particle size
decreases with increasing surfactant level. Eastman Tacolyn resin
dispersions feature an optimized balance between particle size and
surfactant level.
In addition to optimizing peel and tack, resin dispersions can provide
other key performance benefits. These include enhanced adhesion to
low-energy and high-energy surfaces (i.e. polyolefin and glass
surfaces), and increased performance at low or at higher temperatures.
Waterborne resin dispersions have broad compatibility with latex
polymers and are also environmentally friendly and FDA compliant for
either indirect or direct food contact. These combined performance
properties result in versatile and cost-effective adhesive formulations.

Table 1. Selecting Resin Dispersions for Specific Applications

SELECTING THE RIGHT RESIN DISPERSION
Compatibility and Physical Properties
When selecting resin dispersions, formulators need to consider
compatibility with emulsion polymers. When formulating with resin
dispersions, the "like-dissolves-like" principle applies. For example,
rosin ester dispersions, which are based on polar tackifier resins, are
compatible with polar polymers such as acrylic emulsions.
Physical properties include the softening point, or glass-transition
temperature (Tg), of the tackifier resin. In addition, low color and UV
stability are critical physical properties for certain applications, such as
clear filmic labels. Finally, depending on the adhesive application, other
factors might include FDA compliance and environmental
requirements.

Specific Applications
Depending on the application, there are specific types of resin
dispersions to address nearly every need (see Table 1). For example,
rosin ester dispersions provide a cost-effective solution for high-volume
paper label applications. Aliphatic resin dispersions are ideal for
applications using natural rubber latex because of their compatibility.
For applications where clarity is critical, hydrogenated rosin esters and
pure monomer aromatic resins are a good choice, due to their UV
resistance. Hybrid resin dispersions improve peel and tack and provide
good cohesive strength. And aromatic modified hydrocarbon resin
dispersions offer outstanding cohesive strength and UV resistance.

Table 2. Recommended Resination Levels

RECOMMENDED RESINATION LEVELS
For label applications, the acrylic latex may be based on either butyl
acrylate or 2-ethyl hexyl acrylate. For paper label applications, 15-30%
resin dispersion on a dry weight basis is recommended, while 10-15%
dispersion is recommended for filmic label applications (see Table 2).
Waterborne tape formulations generally consist of either acrylic latex or
natural rubber latex. For acrylic PSA tapes, 10-20% resin dispersion is
recommended, while 20-50% dispersion is recommended for natural
rubber formulations.
When formulating pressure-sensitive adhesives, raw materials must be
added in the specific order shown in Table 2 to avoid grit formulation
or coagulation. Depending on the performance requirements, it may
also be necessary to post-add materials such as a surfactant, thickener,
defoamer or biocide to optimize the adhesive formulation.
Table 3. Contact Adhesive Formulations
SPECIALTY DISPERSION APPLICATIONS
Resin dispersions are ideal for specialty adhesive applications such as
waterborne contact adhesives, specialty tapes and protective films, and
filmic labels. Eastman offers a family of Tacolyn resin dispersions to
meet the specific requirements of these applications.

Waterborne Contact Adhesives

Waterborne contact adhesives are environmentally friendly, solvent-free
and clean up easily with water. Contact adhesives are used for
applications such as laminate bonding and foam bonding. Contact
adhesive formulations generally contain either polychloroprene latex or
styrene-butadiene latex (see Table 3).

Figure 1. Room Temperature Cleavage

Note: Substrates consisted of high-pressure laminate bonded to
particleboard. The adhesive was brush applied to both substrates.
Approximate coating weight was 0.10 grams dry total per 2"x 2"bond
area. Substrates were bonded using a laboratory laminator set at 30 psi
and a roll speed of 3 ft/minute. Room temperature cleavage samples
were tested in a 90° peel configuration using a tensile tester with a
20"min crosshead speed.

For high-pressure laminate/particleboard applications, Tacolyn 5003

offers excellent high-temperature performance and can be used as the
sole tackifier.

Figure 2. Shear Adhesion Failure Results (SAFT)

Note: Substrates consisted of high-pressure laminate bonded to
particleboard. The adhesive was brush applied to both substrates.
Approximate coating weight was 0.05 grams dry total per 1" x 1" bond
area. Substrates were bonded using a laboratory laminator set at 30 psi
and a 3 ft/minute roll speed. Shear adhesion was determined in
accordance with test method PSTC-7

Tacolyn 3400 offers good temperature performance and a balance of

peel and shear (see Figures 1-2). Maximum peel strength is achieved
with short or long open times, allowing for versatility in bond assembly.
Figure 3. Adhesive Fast Break

For foam bonding applications, the adhesive is spray-applied using a

coagulating agent such as citric acid.

Figure 4. Adhesive Quick Grab

Note: Substrates consisted of polyurethane foam. Adhesives were lightly
spray applied to both foam substrates.
Tacolyn 5002 gives especially fast break performance as well as
immediate contractibility (see Figures 3-4).

Figure 5. Shear Results

Note: Adhesives consisted of 100 parts tackifier resin (dry weight) and
100 parts natural rubber latex. Labels consisted of 25 g/m2 dry
adhesive coated onto Mylar (PET) film. Dimensions for 178° shear test
were 1" x 1" contact area with a 1kg weight. Shear adhesion was
determined in accordance with test method PSTC-7. Test data was
reported as an average five specimens.

Specialty Tapes and Protective Films

Aliphatic resin dispersions are ideal for applications that involve
pacification of natural rubber latex for specialty tape and protective film
applications. Aliphatic resin dispersions have excellent compatibility
and impart peel strength in small increments relative to resination level.
Thus, a single resin dispersion may be used at various loadings to
customize adhesives with various peel performance.
The use of Tacolyn 5070 in a natural rubber latex resulted in a residue-
free adhesive with low shear strength, a desirable property in protective
film applications (see Figure 5).
Figure 6. 180º Peel Test Results
Note: Adhesives consisted of 100 parts tackifier resin (dry weight) and
100 parts natural rubber latex. Test laminates consisted of 25 g/m2 dry
adhesive coated onto Mylar (PET) film. 180° peel adhesion was
determined in accordance with test method PSTC-1 with a five-minute
dwell time. All tests were performed @ 23°C, 50% relative humidity.
Test data was reported as an average five specimen.

Used in natural rubber tape applications, Tacolyn 5085 offers a good

balance of peel and tack coupled with high shear performance (see
Figures 6-7).
Figure 7. Loop Tack Test Results
Note: Adhesives consisted of 100 parts tackifier resin (dry weight) and
100 parts natural rubber latex. Test laminates consisted of 25 g/m2 dry
adhesive between Mylar (PET) film and siliconized release liner. Loop
tack was determined in accordance with test method PSTC-16. All tests
were performed at 23°C, 50% relative humidity. Test data was reported
as an average five specimens.

As illustrated in Figure 8, there is a direct correlation between peel

strength and resination level.
Figure 8. Peel Strength versus Resination Level on Stainless Steel
Note: Adhesives consisted of 100 parts tackifier resin (dry weight) and
100 parts natural rubber latex. Test laminates consisted of 25 g/m2 dry
adhesive between Mylar (PET) film and siliconized release liner. 180°
peel adhesion was determined in accordance with test method PSTC-1
with a five-minute dwell time. All tests were performed at 23°C, 50%
relative humidity. Test data was reported as an average five specimens.

Figure 8 also demonstrates that peel strength of natural rubber-based

adhesives is increased in small increments relative to the resination
level. Thus, it is possible to use a single resin dispersion in a natural
rubber latex system at different loadings to produce several adhesives
with low, medium or high peel performance (see Figure 8).

Table 4. Adhesive Formulations

Filmic Labels
The need for environmentally friendly, waterborne PSAs continues to
grow. Filmic label applications have shown significant growth. These
demanding applications require PSAs that are non-water-whitening
because clarity is crucial in filmic labels. Excellent adhesion to low-
and high-energy substrates is also important in filmic label applications.
A resin dispersion is generally added to a filmic latex at the 15%
resination level, on a dry weight basis (see Table 4).

Figure 9. 180 Peel Test Results

Note: Labels consisted of 21 g/m2 dry adhesive between 100-gauge
corona treated oriented polypropylene and siliconized release liner.
180° peel adhesion was determined in accordance with test method
PSTC-1 with a five-minute dwell time. All tests were performed at 23°C,
50% relative humidity. Test data was reported as an average five
specimens.

The incorporation of Tacolyn resin dispersions to a filmic latex

improves peel adhesion to low- and high-energy substrates, while shear
performance is maintained (see Figures 9-11).
Figure 10. Loop Tack Test Results
Note: Labels consisted of 21 g/m2 dry adhesive between 100-gauge
corona treated oriented polypropylene and siliconized release liner.
Loop tack was determined in accordance with test method PSTC-16. All
tests were performed at 23°C, 50% relative humidity. Test data was
reported as an average five specimens.

The non-water-whitening performance of PSAs containing Tacolyn

resin dispersions is comparable to the control filmic latex (see Figure
12).
Figure 11. 1" x 1' Shear Results Note: Dimensions for 178° shear test
were 1" x 1" contact area with a 1kg weight. Shear adhesion was
determined in accordance with test method PSTC-7 with a 30-minute
dwell time. All tests were performed at 23°C, 50% relative humidity.
Test data was reported as an average five specimens.

Tacolyn 1070 and Tacolyn 3280 are recommended when non-whitening

performance and UV resistance are critical.
Figure 12. Water Resistance Testing. 180° Peel Testing After 24 Hour
Water Soak.
Note: Panels were placed in room temperature deionized water and
soaked for 24 hours. Labels were observed for whitening. Panels were
removed from the water bath, gently wiped dry and immediately
subjected to 180° peel test. 180° peel adhesion was determined in
accordance with test method PSTC-1 with a five-minute dwell time. Test
data was reported as an average five specimens.
CONCLUSION
PSA manufacturers are being challenged to reduce costs without
sacrificing performance or the environment. Resin dispersions help to
meet these challenges by offering many advantages when formulated
with emulsion polymers. Performance advantages include optimized
peel and tack and enhanced specific adhesion to low- and high-energy
substrates, such as polyethylene and glass. Resin dispersions also
improve high- and low-temperature performance and have excellent
compatibility with many types of emulsion polymers. Finally, resin
dispersions are environmentally friendly, FDA-compliant and can
improve the overall cost efficiency of an adhesive formulation.
Resin Dispersions: A Research Report

What is the use of butylated hydroxytoluene?

BHT (butylated hydroxytoluene) is a lab-made chemical that is added to
foods as a preservative. People also use it as medicine. BHT is used to
treat genital herpes and acquired immunodeficiency syndrome (AIDS).
Some people apply BHT directly to the skin for cold sores.

Butylated hydroxytoluene (BHT) is a chemical cousin to BHA that is

also listed as “generally recognized as safe.” It, too, is added to food as
a preservative. The two compounds act synergistically and are often
used together. BHT is not a listed carcinogen, but some data have
shown that it does cause cancer in animals.
Here's a hint: It's a preservative, and you can find it in (drum roll,
please): potato chips, lard, butter, cereal, instant mashed potatoes,
preserved meat, beer, baked goods, dry beverage and dessert mixes,
chewing gum, and other foods. Oh, also: rubber, petroleum products,
and, of course, wax food packaging.

This report researches the worldwide Tackifier Resin Dispersions

market size (value, capacity, production and consumption) in key
regions like United States, Europe, Asia Pacific (China, Japan) and
other regions.
This study categorizes the global Tackifier Resin Dispersions
breakdown data by manufacturers, region, type and application, also
analyses the market status, market share, growth rate, future trends,
market drivers, opportunities and challenges, risks and entry barriers,
sales channels, distributors and Porter’s Five Forces Analysis.
The following manufacturers are covered in this report:

1. Eastman Chemical
2. Lawter
3. Harima Chemicals
4. Dyna-Tech Adhesives
5. RESPOL RESINAS
6. BAOLIN
7. DANQUINSA
 8. Kraton
9. Schill + Seilacher
Tackifier Resin Dispersions Breakdown Data by Type
1. Rosin Ester Series
2. Terpene Phenolic Resin Series
3. Polymeric Rosin
Tackifier Resin Dispersions Breakdown Data by Application
1.Packaging
2.Building & Construction
3.Automotive
4. Nonwovens
Tackifier Resin Dispersions Production Breakdown Data by Region
United States
Europe
China
Japan
Other Regions
Tackifier Resin Dispersions Consumption Breakdown Data by
Region
North America
United States
Canada
Mexico
Asia-Pacific
China
India
Japan
South Korea
Australia
Indonesia
Malaysia
Philippines
Thailand
Vietnam
Europe
Germany
France
UK
Italy
Russia
Rest of Europe
Central & South America
Brazil
Rest of South America
Middle East & Africa
GCC Countries
Turkey
Egypt
South Africa
Rest of Middle East & Africa

Table of Contents
Global Tackifier Resin Dispersions Market Insights, Forecast 2019
to 2026
1 Study Coverage
1.1 Tackifier Resin Dispersions Product
1.2 Key Market Segments in This Study
1.3 Key Manufacturers Covered
1.4 Market by Type
1.4.1 Global Tackifier Resin Dispersions Market Size Growth Rate by
Type
1.4.2 Rosin Ester Series
1.4.3 Terpene Phenolic Resin Series
1.4.4 Polymeric Rosin
1.5 Market by Application
1.5.1 Global Tackifier Resin Dispersions Market Size Growth Rate by
Application
1.5.2 Packaging
1.5.3 Building & Construction
1.5.4 Automotive
1.5.5 Nonwovens
1.6 Study Objectives
1.7 Years Considered
2 Executive Summary
2.1 Global Tackifier Resin Dispersions Production
2.1.1 Global Tackifier Resin Dispersions Revenue 2014-2025
2.1.2 Global Tackifier Resin Dispersions Production 2014-2025
2.1.3 Global Tackifier Resin Dispersions Capacity 2014-2025
2.1.4 Global Tackifier Resin Dispersions Marketing Pricing and Trends
2.2 Tackifier Resin Dispersions Growth Rate (CAGR) 2019-2025
2.3 Analysis of Competitive Landscape
2.3.1 Manufacturers Market Concentration Ratio (CR5 and HHI)
2.3.2 Key Tackifier Resin Dispersions Manufacturers
2.4 Market Drivers, Trends and Issues
2.5 Macroscopic Indicator
2.5.1 GDP for Major Regions
2.5.2 Price of Raw Materials in Dollars: Evolution
3 Market Size by Manufacturers
3.1 Tackifier Resin Dispersions Production by Manufacturers
3.1.1 Tackifier Resin Dispersions Production by Manufacturers
3.1.2 Tackifier Resin Dispersions Production Market Share by
Manufacturers
3.2 Tackifier Resin Dispersions Revenue by Manufacturers
3.2.1 Tackifier Resin Dispersions Revenue by Manufacturers (2014-
2019)
3.2.2 Tackifier Resin Dispersions Revenue Share by Manufacturers
(2014-2019)
3.3 Tackifier Resin Dispersions Price by Manufacturers
3.4 Mergers & Acquisitions, Expansion Plans
4 Tackifier Resin Dispersions Production by Regions
4.1 Global Tackifier Resin Dispersions Production by Regions
4.1.1 Global Tackifier Resin Dispersions Production Market Share by
Regions
4.1.2 Global Tackifier Resin Dispersions Revenue Market Share by
Regions
4.2 United States
4.2.1 United States Tackifier Resin Dispersions Production
4.2.2 United States Tackifier Resin Dispersions Revenue
4.2.3 Key Players in United States
4.2.4 United States Tackifier Resin Dispersions Import & Export
4.3 Europe
4.3.1 Europe Tackifier Resin Dispersions Production
4.3.2 Europe Tackifier Resin Dispersions Revenue
4.3.3 Key Players in Europe
4.3.4 Europe Tackifier Resin Dispersions Import & Export
4.4 China
4.4.1 China Tackifier Resin Dispersions Production
4.4.2 China Tackifier Resin Dispersions Revenue
4.4.3 Key Players in China
4.4.4 China Tackifier Resin Dispersions Import & Export
4.5 Japan
4.5.1 Japan Tackifier Resin Dispersions Production
4.5.2 Japan Tackifier Resin Dispersions Revenue
4.5.3 Key Players in Japan
4.5.4 Japan Tackifier Resin Dispersions Import & Export
4.6 Other Regions
4.6.1 South Korea
4.6.2 India
4.6.3 Southeast Asia
5 Tackifier Resin Dispersions Consumption by Regions
5.1 Global Tackifier Resin Dispersions Consumption by Regions
5.1.1 Global Tackifier Resin Dispersions Consumption by Regions
5.1.2 Global Tackifier Resin Dispersions Consumption Market Share by
Regions
5.2 North America
5.2.1 North America Tackifier Resin Dispersions Consumption by
Application
5.2.2 North America Tackifier Resin Dispersions Consumption by
Countries
5.2.3 United States
5.2.4 Canada
5.2.5 Mexico
5.3 Europe
5.3.1 Europe Tackifier Resin Dispersions Consumption by Application
5.3.2 Europe Tackifier Resin Dispersions Consumption by Countries
5.3.3 Germany
5.3.4 France
5.3.5 UK
5.3.6 Italy
5.3.7 Russia
5.4 Asia Pacific
5.4.1 Asia Pacific Tackifier Resin Dispersions Consumption by
Application
5.4.2 Asia Pacific Tackifier Resin Dispersions Consumption by
Countries
5.4.3 China
5.4.4 Japan
5.4.5 South Korea
5.4.6 India
5.4.7 Australia
5.4.8 Indonesia
5.4.9 Thailand
5.4.10 Malaysia
5.4.11 Philippines
5.4.12 Vietnam
5.5 Central & South America
5.5.1 Central & South America Tackifier Resin Dispersions
Consumption by Application
5.5.2 Central & South America Tackifier Resin Dispersions
Consumption by Countries
5.5.3 Brazil
5.6 Middle East and Africa
5.6.1 Middle East and Africa Tackifier Resin Dispersions Consumption
by Application
5.6.2 Middle East and Africa Tackifier Resin Dispersions Consumption
by Countries
5.6.3 Turkey
5.6.4 GCC Countries
5.6.5 Egypt
5.6.6 South Africa
6 Market Size by Type
6.1 Global Tackifier Resin Dispersions Breakdown Dada by Type
6.2 Global Tackifier Resin Dispersions Revenue by Type
6.3 Tackifier Resin Dispersions Price by Type
7 Market Size by Application
7.1 Overview
7.2 Global Tackifier Resin Dispersions Breakdown Dada by
Application
7.2.1 Global Tackifier Resin Dispersions Consumption by Application
7.2.2 Global Tackifier Resin Dispersions Consumption Market Share by
Application (2014-2019)
8 Manufacturers Profiles
8.1 Eastman Chemical
8.1.1 Eastman Chemical Company Details
8.1.2 Company Description
8.1.3 Capacity, Production and Value of Tackifier Resin Dispersions
8.1.4 Tackifier Resin Dispersions Product Description
8.1.5 SWOT Analysis
8.2 Lawter
8.2.1 Lawter Company Details
8.2.2 Company Description
8.2.3 Capacity, Production and Value of Tackifier Resin Dispersions
8.2.4 Tackifier Resin Dispersions Product Description
8.2.5 SWOT Analysis
8.3 Harima Chemicals
8.3.1 Harima Chemicals Company Details
8.3.2 Company Description
8.3.3 Capacity, Production and Value of Tackifier Resin Dispersions
8.3.4 Tackifier Resin Dispersions Product Description
8.3.5 SWOT Analysis
8.4 Dyna-Tech Adhesives
8.4.1 Dyna-Tech Adhesives Company Details
8.4.2 Company Description
8.4.3 Capacity, Production and Value of Tackifier Resin Dispersions
8.4.4 Tackifier Resin Dispersions Product Description
8.4.5 SWOT Analysis
8.5 RESPOL RESINAS
8.5.1 RESPOL RESINAS Company Details
8.5.2 Company Description
8.5.3 Capacity, Production and Value of Tackifier Resin Dispersions
8.5.4 Tackifier Resin Dispersions Product Description
8.5.5 SWOT Analysis
8.6 BAOLIN
8.6.1 BAOLIN Company Details
8.6.2 Company Description
8.6.3 Capacity, Production and Value of Tackifier Resin Dispersions
8.6.4 Tackifier Resin Dispersions Product Description
8.6.5 SWOT Analysis
8.7 DANQUINSA
8.7.1 DANQUINSA Company Details
8.7.2 Company Description
8.7.3 Capacity, Production and Value of Tackifier Resin Dispersions
8.7.4 Tackifier Resin Dispersions Product Description
8.7.5 SWOT Analysis
8.8 Kraton
8.8.1 Kraton Company Details
8.8.2 Company Description
8.8.3 Capacity, Production and Value of Tackifier Resin Dispersions
8.8.4 Tackifier Resin Dispersions Product Description
8.8.5 SWOT Analysis
8.9 Schill + Seilacher
8.9.1 Schill + Seilacher Company Details
8.9.2 Company Description
8.9.3 Capacity, Production and Value of Tackifier Resin Dispersions
8.9.4 Tackifier Resin Dispersions Product Description
8.9.5 SWOT Analysis
Selecting Tackifiers for Adhesives and Sealants
Tackifiers are important constituents in adhesives formulations in order
to maintain the correct balance between adhesion and cohesion. They
must be considered with regard to the end-used properties, adhesive
processing as well as compatibility with base polymer to achieve
desired performance requirements.

Since, there is no specific set of rules for tackifier selection due to

the significant number of potential applications and property variables
that can be achieved, finding an optimal tackifier therefore requires a
disciplined approach.

Get an in-depth understanding of the various classes of tackifiers and

their mechanism, applications as well as benefits and limitations. Also,
get tips to select the right tackifier for different polymers. Review:

1. How Do Tackifiers Work

2. Functions of Tackifiers
3. Types of Tackifiers
4. Tackifiers — Advantages and Disadvantages
5. Selecting Tackifiers for Polymers
6. Other Key Points in Tackifier Selection
7. Tackifiers Selection Checklist
8. Applications of Tackifiers

(Continue reading or click to go on specific section of the page)

We would like to acknowledge Edward M. Petrie for providing

technical information needed to develop this guide.

What are Tackifiers?

 Tackifiers are important low
molecular weight constituents in hot-
melt and pressure-sensitive adhesives
in terms of their effect on both cost
and performance properties. They
frequently represent most of the
weight percentage (up to 40 percent of
total mass) and cost of the adhesive
formulation. They are used to increase
the tack or "stickiness" of the adhesive.

In practice, formulators use tackifiers to make the correct balance

between adhesion and cohesion which is dependent on the end-use
application. They do this by lowering the modulus and increasing the
glass transition temperature of the final adhesive.

Tackifiers must be considered with regard to:

 The end-properties that the formulator is trying to achieve

 The type of processing that the adhesive will be subject to, and
 The chemical nature of the base polymer

Basic Requirements for Tackifiers

While formulating an elastic adhesive, a rubbery polymer provides the

elastic component where as, a low molecular weight tackifying resin
constitutes the viscous component. The resin ultimately determines the
viscoelastic behavior and the final properties of the adhesive.

Tackifiers tend to have relatively low molecular weight with glass

transition and softening temperatures that are above room temperature.
They are most often used in an adhesive formulation containing a base
polymer that has a Tg below room temperature. Therefore, the tackifier
addition raises the Tg of the final adhesive.

Tackifiers operate opposite to plasticizers which lower the Tg of the

adhesive formulation.

The tackifying agent must be compatible with the base polymer. With
hot-melt adhesives, consideration must also be given to the heat
stability of the tackifier in the melt. Tackifiers with unsaturation could
potentially gel while the adhesive is in the melt phase. They should also
have a relatively low surface tension so as to readily wet the substrate.

» View All the Commercially Available Tackifiers Here!

This adhesives database is available to all, free of charge. You can

filter down your options by suitable resin, system or application
(adhesives, sealants...), supplier and regional availability.

Let's understand what happens when tackifiers reduce the modulus and
increase the glass transition temperature.

How do Tackifiers Work

Tackifiers work by reducing the modulus and increasing the glass

transition temperature (Tg) of the resulting adhesive formulations. Both
these factors are critically important to achieve the necessary tack and
peel strength. In order to effectively provide these modifications,
tackifiers must be compatible or partially compatible with the base
polymer.

Reducing the Modulus

In the 1960s, Dahlquist observed a minimum level of compliance that a

pressure-sensitive adhesive must have in order for it to exhibit tack.
 This can be broadly described as a need for the material to be
pliable in order to absorb energy inputs rather than allowing it to
propagate through cracks.

The lower the modulus, the easier the PSA adhesive will be to deform,
flow, and make good contact with the substrate to which it is bonding.
Observations concluded that for pressure sensitivity the adhesive's
storage modulus (G') must be below 3.3 x 105 Pa. This is now known as
the Dahlquist criterion.

Tackifiers must have a low to moderate molecular weight (generally

between 300 and 2000), which imparts some cohesive strength and
prevents the formation of weak boundary layers at the interface - a
problem that happens often with low molecular weight plasticizers.

Because tackifiers have lower molecular weight than the base polymer,
they dilute the polymeric network and reduce the modulus. A plasticizer
by itself could also reduce the modulus, but this is generally an
ineffective approach because the Tg of the entire formulation is
significantly reduced.

Increasing the Glass Transition Temperature

The glass transition temperature also plays an important role in tack,

and tackifiers generally increase the Tg of the adhesive.

At temperatures near the glass transition region, the adhesive is very

effective at dissipating energy and providing good adhesive strength.
Most base polymers that go into pressure-sensitive adhesives have
relatively low Tg – some significantly below room temperature.
However, adhesives that are applied and operate near room temperature
require a Tg that is nearer to those temperatures. In these
cases, tackifiers with Tg from about room temperature to 100°C are
used to increase the Tg of the adhesive.
To be an effective pressure-sensitive adhesive, the formulation must
have a modulus
below 3.3 x 105 Pa and a Tg near to the application & end-use
temperatures.

The image below illustrates the optimum modulus and Tg for various
adhesives that are applied and operate at different temperatures.

Optimum Storage Modulus and Glass Transition Temperatures for

Different Pressure-sensitive Adhesives

Functions of
Tackifiers

In adhesive
and sealant
formulations,
tackifiers are
used
to generate
tack and
improve specific adhesion (peel strength). They are incorporated into
base polymers which mainly lack tackiness and pressure-sensitive
properties but provide cohesion. In this way, tackifiers provide the
formulator with a tool to balance adhesion and cohesion in line with the
end-use requirements.

The image below shows the dependence of tack, peel, and shear on the
base polymer / tackifier ratio. Note that the properties are highly
dependent on the concentration of tackifier in the adhesive formulation
and that an optimal concentration must be identified as well as a
favorable tackifier chemistry.

Dependence of Tack, Peel, and Shear on Resin / Tackifier Ratio1

 Tackifiers have been found to be especially useful in improving

adhesion to hard-to-bond substrates such as low surface energy
plastics and coated paper.
 They have also been found to promote high temperature adhesive
performance in certain adhesive systems.
 Two examples that illustrate the additional benefits of tackifiers are:
o Thermoplastic elastomer systems (e.g., styrene butadiene
copolymers) in which hydrocarbon resins are used to increase
heat resistance, and
o Neoprene contact adhesives, in which phenolic resins are used
to improve processing and heat resistance.

In addition to modify tack, adhesion, and cohesion, tackifiers will affect

other properties. These may be advantageous or disadvantageous to the
formulator. Properties such as viscosity, color, color change on aging,
thermal stability, and odor are also dependent on the tackifier chosen
and its concentration. As a result, tackifiers in every formulation need
to be tested against an extended list of criteria.
Types of Tackifiers

Tackifiers can be divided into three main groups:

 Hydrocarbon resins
 Rosin resins, and
 Terpene resins

These are derived from natural or petroleum feedstocks.

Although the natural tackifying resins represent the oldest technology, a

recent increase in interest has occurred in these products due to the
emphasis on bio-based, green additives. Important characteristics of the
various types of tackifying resins are summarized below.
Main Types of Tackifier Resins and Their Feedstocks
#1. Hydrocarbon Resin Tackifiers
Hydrocarbon resin tackifiers are manufactured from petroleum-
based feedstock, and therefore, they have the disadvantage of being
linked to the price of oil. These resins have a somewhat lower
compatibility range with base polymers than tackifiers produced from
natural feedstock.

Hydrocarbon resins tackifiers are either aliphatic, aromatic, or mixtures

of the two. Hydrocarbon resin tackifiers are polymerized to raise their
softening points to a level that is useful in adhesives. They are low
molecular weight amorphous synthetic polymers.

Table below summarizes the most common types of hydrocarbon resin

tackifiers. Hydrocarbon resins tackifiers can be hydrogenated for the
same advantages that hydrogenation provides rosin resins as was shown
in the image above.

Hydrocarbon Resins for Tackifying Adhesives

Pure monomer hydrocarbon resins are used to modify the styrene end-
blocks of styrene block copolymer. This increases the temperature
range and adhesion. Their high polarity has been shown to significantly
elevate the performance of EVA-based adhesives.

The major types of hydrocarbon resins are:

 C5 aliphatic resins
 C9 aromatic resins
 DCPD cycloaliphatic resins (dicyclopentadiene)
 Hydrogenated hydrocarbon resins (A sub-category based on the
above major types)

The
feedstocks to
produce C5
and C9
hydrocarbon
resins are
fractions from
a naphtha
cracker. The
feed streams
to produce hydrocarbon resins can be divided into two groups — C5
piperylene feedstock and C9 resin oil.

a. C5 Aliphatic Hydrocarbon Resins

C5 piperylene contains various monomers. (See figure below)

The liquid C5
feedstock can be
polymerized to a
hard resin using
a Lewis acid
catalyst and
carefully
selecting
temperature and pressure to obtain the desired softening point and
molecular weight.
 C5 resins are in essence
aliphatic materials. They are
available in a wide range of
softening points and
molecular weights.

b. C9 Aromatic Hydrocarbon
Resins

C9 resin oil contains various

monomers. (See figure below)

A cationic
polymerization
reaction converts
the liquid feed to
a hard resin.

C9 resins are
aromatic
molecules. They are also available in a wide variety of softening
points and molecular weight.

C5 and C9 resins can be modified by mixing the two feed streams

together in certain ratios. (Piccotac™ 9095, Piccotac™ 6095-E) This
ratio determines the aliphatic/aromatic balance of the resin, which is
essential to formulators. The aliphatic C5 feed can be replaced with a
terpene feedstock and modified with styrene to form styrenated terpenes
which have excellent color and stability and are very good tackifiers for
block copolymers.

There are various physical and chemical parameters that are important
 to characterize tackifier
resins. For hydrocarbon
tackifier resins the
aromatic/aliphatic balance
of the resin is of special
interest to adhesive
formulators since it largely
determines compatibility
and ultimately, adhesive
performance. The
following criteria to
characterize these resins:

 Color, Gardner and Hunter Lab scales

 Softening point, Ring & Ball
 Molecular Weight
 Melt Viscosity
 Thermal stability
 Compatibility, Polarity and Cloud points

c. Dicyclopentadiene Hydrocarbon Resins

Dicyclopentadiene (DCPD) feedstock contains various structures such

as those shown in figure below, but is primarily made up of
dicyclopentadiene. The feed stock also contains co-dimers with dienes
such as isoprene, butadiene and methylcyclopentadiene. At elevated
temperature (170-190°), dicyclopentadiene will crack into
cyclopentadiene.

Although the exact

structure of DCPD
 resins is not
known, early steps
of the thermal
polymerization
most likely
involve the
addition of
cyclopentadiene to
the norbornene
olefin followed by continued additions of this type by additional
cyclopentadiene to propagate the growing chain.

Dicyclopentadiene is polymerized either thermally or with a catalyst to

form relatively dark and unstable resins with a characteristic odor. They
are normally used for construction adhesives and inks. They are more
commonly used as a base resin for subsequent hydrogenation to form
water white resins with excellent stability and low odor.

d. Hydrogenated Hydrocarbon Resins

Hydrogenation is primarily used to improve color and stability of the
resin by removing vulnerable double bonds. Partial and selective
hydrogenation are methods used to produce resins with broad
compatibility and good stability. The most common base resins used for
hydrogenation are as follows:
 C9 resins
 C5 resins
 DCPD and modified DCPD resins

The first hydrogenated hydrocarbon resins were fully hydrogenated,

producing aliphatic resins with excellent initial color and stability.
These are:
 C9 resins (e.g. Regalite™ R1125)
 DCPD resins (e.g. Regalite™ T1140)
 C5 resins (e.g. Eastotac™ H-100W Resin)
 Pure monomer styrene-based resins (e.g. Regalrez™ 1094)
These resins are ideal for tackifying SIS and SEBS block copolymers.

» Find Suitable Hydrogenated Hydrocarbon Tackifier Resin in

Our Database!
To produce light colored and stable resins with the correct compatibility
to tackify SBS block copolymers and to adjust properties in high
styrene SIS block copolymers, two methods were introduced:
 Partial hydrogenation of C9 aromatic resins
 Selective hydrogenation of mixed feedstocks

Hydrogenated C9 Hydrocarbon Resins

C9 resins contain double bonds, which are relatively unstable. A useful
way to stabilize these resins is to hydrogenate them. C9 resins have
predominantly aromatic ring structures with an overall aromaticity of
around 40%, measured by proton NMR. Resins are hydrogenated in a
solution with very specific operating parameters like:
 Temperature
 Pressure
 Hydrogen concentration, and
 Catalyst level
Changing any of these operating parameters will bring a change in
the degree of hydrogenation of the final resin. During hydrogenation,
the aromatic ring structures gradually lose their aromatic nature and
become cycloaliphatic.

When the process is allowed to go to completion, the result is a fully

hydrogenated hydrocarbon resin with full aliphatic character. The
process can also be adjusted so that partially hydrogenated resins are the
end result.

This is very necessary in order to prepare resins for wide use in

adhesive formulations and is achieved through sequential, but not total
hydrogenation of the rings. This means that partially hydrogenated
resins still have some aromatic rings.
 The ability to be
hydrogenated to
varying degrees,
resulting in
various
aliphatic/aromatic
balances, gives
these resins their
unique properties.
In theory any
degree of
hydrogenation can be manufactured. Hercules resins carry a range of
hydrogenation levels, varying from 50% to 100%. Example: Regalite™
S5100, Regalite™ 6108

Selective Hydrogenation of Mixed Feedstocks

To obtain resins with comparable compatibility to partially
hydrogenated C9 resins, aromatic modification of DCPD (and other
cycloaliphatic structures) and C5 resins is necessary.
This is usually achieved by the addition of styrene-based monomers
to the aliphatic monomers and subsequently polymerized.
Thereafter selective hydrogenation needs to be performed, in order to
reduce unsaturation and improve color of the cycloaliphatic and
aliphatic structures without significantly affecting the aromatic content.
Example: Regalite™ V6100

#2. Rosin Acids and Esters

Rosin is one of the oldest raw materials for the adhesives industry,
either as such or converted to rosin ester. These resins (rosin acids and
rosin esters) are derived from pine tree by-products such as:
 Gum rosin
o It is the oleo resin (pine gum) of the living pine tree.
o The harvesting of the oleo resin is simple, involving only periodic
wounding of the tree and collecting of the exudate into cups.
 Wood rosin
o After harvesting pine trees, the stump is allowed to remain in the
ground for about ten years so that its bark and sapwood may
decay and slough off to leave the heartwood rich in resin.
o Resinous material is extracted from the stump.

 Tall oil rosin

o It is obtained by distillation of crude tall oil (CTO), a by-product
of the kraft sulfate pulping process.
o CTO contains 70-90% acidic material, which is composed
essentially of fatty acid and tall oil rosin. It has the tendency to
crystallize and usually contains 200-600 ppm sulfur.
o Highly distilled TOR can produce esters which are competitive
with gum and wood rosin derivatives. PAMITE® 79 is an
example of tall oil resin.

They provide tack to almost all polymer types but are most often used
to tackify natural rubber, ethylene vinyl acetate (both high and low
vinyl acetate content), acrylic, styrene butadiene rubber, styrene
butadiene copolymers, and polyurethanes.
The main types of rosin acids and esters that are used as tackifiers are
given in the table that follows.
Main Types of Rosin Tackifiers
These rosin tackifiers are manufactured in a wide range of molecular
weight and
softening
points, which
significantly
affects their
compatibility
with base
polymers and
their
tackifying
efficiency. Within these various types, differences in softening point
mainly affect compatibility and therefore performance.

Hydrogenation & Esterification of Rosin Resins

Early rosin resin tackifiers had developed a reputation for poor stability
caused by unsaturation of the molecule. However, stability can be
improved by various methods such as hydrogenation and esterification
through rearrangements of the double bonds.

The table below lists other advantages achieved by esterification or

hydrogenation of rosin resin

Advantages of Esterification or Hydrogenation of Tackifiers

Chemistry of Rosins
Rosin resins are not polymers, but they are a blend of different
molecules. The figure below displays some of structures of rosin
molecules.
Structure of Different Rosin Molecules

Rosin molecules
have poor stability
caused by
unsaturation.
Stability can be
improved by various
methods such as disproportionation, hydrogenation and
esterification2. Rearrangement of the double bonds by
disproportionation leads to improved stability.

Another method to improve stability is to hydrogenate the rosin

molecules. Example: Staybelite™ Resin-E, Foral™ AX-E

Disproportionation of Rosin Acids

Hydrogenation of Rosin Acids

The carboxylic acid can be converted to an ester using various alcohols.
The molecular weight of the alcohol determines the softening point of
the subsequent ester.

 Glycerol (Permalyn™ 5095, Permalyn™ 2085) and pentaerythritol

(Permalyn™ 3100, Permalyn™ 5110) are the most commonly
used alcohols.
 Methanol (Abalyn™ E) and tri-ethylene-glycol (Staybelite™ Ester
3-E) are used to produce lower softening point esters.

 Reaction of
Rosin Acid with
Glycerol

In the above
figure glycerol is
used as alcohol.
The reaction is an
equilibrium
reaction, which is
driven to near
completion.
However, there
will always be
some unreacted
acidic and
hydroxyl groups.

A typical acid number for a pure rosin acid is around 170. A glycerol
ester typically has an acid value below 20. The type of alcohol chosen is
the key to the molecular weight of the rosin ester and its softening
point. A typical softening point for glycerol esters is 85°C, and 105°C
for pentaerythritol esters. The difference in softening point affects their
compatibility and hence adhesive performance.

Rosin resins have a wide span of compatibility with almost all

polymers. They are well known for their peel and tack contribution
to the adhesive, but generally decrease cohesive strength.

In addition to improved oxidative stability and color, rosin esters impart

excellent adhesion to a wide range of substrates due to their polarity and
compatibility.
#3. Terpene Resin Tackifiers
Another natural tackifier known as the terpenes are sometimes referred
to as "universal" tackifiers due to their compatibility with a great
many polymers including EVA, amorphous polyolefin, polyethylene,
natural rubber, acrylic, styrene butadiene rubber and styrene butadiene
copolymers. Terpene resins are especially compatible with polyolefins
and the mid-block of styrene-isoprene-styrene resins.

Terpene tackifiers are usually polymerized, and a broad range of

softening temperatures is available which depend strongly on molecular
weight. The softening point is generally higher than for other tackifiers.
The high softening point grades provide excellent heat resistance.
Terpene tackifiers provide improved adhesion for almost all polymer
types as well as excellent initial color. These resins can also meet direct
food contact requirements. As a result of their properties and natural
source, terpene tackifiers have a relatively high use but limited supply.
This combination leads to somewhat higher price.
Terpene resins are based on three feed streams:
 Alpha-pinene and beta-pinene are derived primarily from two
processes: stump extraction leading to the isolation of steam distilled
wood turpentine and the kraft sulfate pulping process leading to the
isolation of sulfate turpentine. The individual terpene compounds are
isolated by distillation from these two streams.
 d-Limonene is obtained from citrus sources and a similar
compound, dipentene, is obtained by distillation from petroleum
sources.
Different Structures of Terpenes
The main difference for the formulator between these resins is that the
d-limonene (and dipentene based) resins are not compatible with SBR
polymers.

These resins are

formed by a
cationic
polymerization
reaction using a
Lewis acid catalyst.
These resins have excellent initial color and have a broad range of
softening points and have been produced for many years.

There are several terpene resins that are used as tackifiers (see table
below).

Terpene Resins for Tackifying Adhesives

#4. Tackifier Resin Dispersion

Incorporation of tackifiers into water-borne adhesive systems has been
made easy with the development of tackifier resin dispersions. These
are usually manufactured by emulsifying the resin as a melt into the
aqueous phase.
Once the system has been cooled down, the resin becomes hard again
and remains finely dispersed in the aqueous phase. In certain cases,
resins that are liquid at room temperature are dispersed as well.
Tackifier resin dispersion can be mixed into the polymer dispersion
easily.
The amount and type of emulsifiers used are the main factors for
storage stability, compatibility, and coatability. As a result, a broad
range of resin dispersions have been manufactured from rosin and
hydrocarbon resin based tackifiers.

Tackifiers Advantages and Disadvantages

Every additive that is added to a formulation either strengthens it or
carries some drawbacks. Apprise yourself with the advantages and
disadvantages of different types of tackifiers used with adhesive and
sealants.
The table below consists of the technical and commercial benefits and
limitations of adding a typical tackifier to your adhesive/sealant
formulation. Have a look and easily select the tackifier that suits your
needs.
Selecting Tackifiers for Polymers
The first and most important criterion in the selection process is the
compatibility between the tackifier and the base polymer in the
adhesive formulation. The higher the compatibility, the more efficient
will be the tackification.
If a tackifier is chosen that is incompatible with the base polymer, then
it acts like filler. In this case the modulus is increased and there is little
change in Tg – circumstances that fail to produce an effective pressure
sensitive adhesive.

The tackifying ability of various base polymers strongly differs.

For solvent-based adhesives, the versatility range can be listed as
follows:

Acrylic > NR >> CR > APO > BR > SIS >> SBS > SBR

For water-borne adhesives the versatility range is given as follows:

Acrylic > NR > CR < BR > EVA > SBR

Certain classes of tackifiers work best with certain types of

polymers. Unless the tackifier is compatible with the base polymer
there is no need to extend the selection process. Solubility parameters,
molecular weight, and molecular weight distribution determine
compatibility.

Hydrocarbon resins can be selected for compatibility based on their

cloud points. Cloud point measurements reveal aromatics. Cloud point
tests determine polarity and aromaticity by heating the tackifier in two
solvents and recording the temperature at which the resin begins to
form a separate phase. In such tests, low temperature values indicate
high levels of polarity and aromaticity, and tackifiers should be used
with polymers demonstrating similar properties.

The tables below provide a general guide to the selection of tackifiers

with various common polymers used in hot-melt and pressure-
sensitive adhesives. This grouping is based primarily on compatibility
and it is a good starting point in the selection of a tackifier.

Care must be taken in the formulation of block copolymer adhesives

because they generally have a high temperature thermoplastic end-
phase and an elastomeric mid-phase. The tackifier can be directed to
either or both phases depending on its compatibility. For example, in
styrene block copolymers the formulator may want the polystyrene
phase to remain glassy for optimum cohesive properties.

The aliphatic C5 resins, which are more compatible in the non-styrene

phase, therefore are more likely to be used. However, in certain
applications it may be desirable to increase or decrease the Tg of the
end-phase and for this an end-phase compatible tackifier such as
aromatic hydrocarbon resin may be used.

Select Tackifiers for Rubbers

 Select
Tackifiers
for Vinyl
Polymers

Other Key
Points in
Tackifier
Selection

Click Here
to Learn
About the
Different
Parameters
to Select
the Right
Tackifiers:

 Solubility
 Softening Point
 Resin Level
 Stability
 Applications

Solubility
One can either employ solubility parameters or other parameters to
estimate the compatibility of a tackifier with a certain polymer.
However, usually trial and error testing is required. Materials that
possess similar solubility parameters are generally assumed to be
compatible with each other.

The image below illustrates solubility parameters for various base

polymers and tackifiers.

Solubility
parameters for
base polymers
and tackifiers

Softening Point
In systems having
good tackifier /
polymer
compatibility,
softening point is
an important
parameter relative to the selection of a tackifier.

In general, soft resins impart aggressive tack, while harder resins

help retain good cohesive strength and creep resistance.
A higher softening point resin is less miscible with the base polymer.
Softening temperatures of commercial tackifiers range between room
temperature to about 115°C, and all types of tackifiers can be
manufactured within this softening point range.

Some Tackifying Resins with Different Glass Transition

Temperatures and Softening Points3

Resin Level Required

It is difficult to predict the resin level required to achieve a certain tack
or peel value because of the dependence on the nature of the base
polymer and the tackifier. The type of substrate that is being bonded
should be taken into account as well.
A level of up to 30-40% by weight of tackifying resin is used in
formulating many acrylic-PSAs for bonding to polyolefin film.
A modulus increase will usually begin in the range of 40-60% resin
loading. However, more than 20% tackifier resin generally results in
lowering of cohesive strength. For natural rubber-based PSAs tackified
with hydrocarbon resins, maximum tack is obtained at about 50-65%
tackifying resin, and optimum peel strength is obtained at a
concentration of about 50% by weight.

Stability
After determining the compatibility, stability is the next most important
tackifier characteristic to consider. The stability of the plasticizer will
depend on the compounding and application processes that the adhesive
will need to go through as well as the environment (heat, oxygen,
chemicals, etc.) once the adhesive is placed in service.
Additives may be used in the adhesive formulation to prevent stability
problems associated with the tackifiers. These include antioxidants and
other stabilizers.
With hot-melt adhesives, consideration must also be given to the heat
stability of the tackifier in the melt. Tackifiers with unsaturation could
potentially gel while the adhesive is in the melt phase. Heat stability can
often be approximated by the:
 Chemical composition (aromatic > aliphatic) and
 Glass transition or softening temperature of the tackifier

When using dispersions of tackifying resins in water-borne adhesives,

stability testing will ensure that there are no undesirable reactions
between the emulsifier systems in the tackifier and base polymer
dispersions.

Applications
Tackifiers are sold either as 100% non-volatile forms (mainly solids and
some liquids), as solution cutbacks, or as water-borne resin dispersions.
The choice of form will depend on the processes required to formulate
the adhesive and specific logistic or regulatory requirements.
High viscosity tackifying resins are usually pre-warmed for easier
handling. Resins that have a high melting point should be added early in
the mixing cycle in order to guarantee melting and sufficient dispersion.
Soft resins can be added together with filler and other additives to make
use of their wetting and dispersing properties, and relatively late
addition can be useful for building maximum tack.
The type of tackifier used can significantly affect the viscosity of the
adhesive system. For a given temperature, the viscosity can vary up to 5
times or more depending on the type of plasticizer used. Image below
illustrates the variety of viscosities that can be achieved by a given SIS
polymer system depending on the choice of tackifier. As a result,
tackifiers are sometimes used to fine-tune viscosity requirements.

Influence of tackifier choice on the viscosity of an SIS hot-melt

adhesive system

Tackifiers Selection Checklist

 There is no specific set
of rules for tackifier
selection due to the
significant number of
potential applications
and property variables
that can be achieved
with tackifiers.

Selecting an optimal tackifier requires a disciplined

approach. Tackifiers are costly to qualify and it is very difficult to
qualify a secondary supplier as a "drop-in" replacement for an original
tackifier source.

Expensive and lengthy trial and error experimentation is generally

required, and formulation adjustments are usually necessary.

 The most important criteria for selecting a tackifier is compatibility

with the base polymer. However, once compatibility is provided,
other parameters such as softening point or Tg, concentration,
stability, and compounding / application properties become
important selection factors.
 Once compatibility and stability have been determined, other criteria
can be
considered.
These
additional
criteria are
related to the
specific
application;
whereas,
compatibility
and stability
requirements
are universal.
These additional selection criteria will depend on the requirements of
the adhesive and its application.
Applications of Tackifiers

The primary application for tackifiers is in pressure sensitive, contact,

and assembly adhesives and in sealants. They can be used in water-
borne, solvent-borne, hot-melt, or reactive adhesive formulations.
The primary adhesive and sealant applications for tackifiers are:
 Tapes and labels
 Disposables and non-wovens
 Paper and packaging, and
 Building and construction
 Other minor applications of tackifiers include tires, textiles, paper
sizing, and road marking
 Applications Hot-Melt Solvent Water Reactive

Tapes and SBC, Acrylic, UV acrylic

SBC Acrylic, NR
labels EVA and SBC
SBC, APO,
Disposables SBC Acrylic, VAE
EVA
SBC, APO, UV acrylic
PSAs Graphic arts
PE, EVA and SBC
SBC, Acrylic Acrylic
General
EVA, SBC
assembly
EVA, SBC, PVA, VAE,
Packaging SBC
APO NR
Heat seal
NR
labeling SBC, EVA,
SBC
APO
Non-wovens Acrylic, VAE

EVA, PVAc,
General UV acrylic
Packaging SBC, APO,
Assembly Acrylic, VAE, and SBC
PE SBC, Acrylic
PVAc
Product SBC, EVA,
Assembly APO

Bookbinding EVA, SBC SBC

Insulated glass Butyl, SBC Urethane

Ceramic tiles
Sealants
and fixtures
Acrylic, VAE
SBC, Butyl,
General SBC, Butyl Urethane
Acrylic
Urethane,
Shoemaking Urethane
neoprene
Contact Neoprene,
Construction / SBC, Urethane
Adhesives urethane
product SBC neoprene,
assembly urethane
Tackifiers and Properties 01
AKROCHEM® HR-100
Akrochem
Hydrophilic thermoplastic hydrocarbon tackifier resin. Designed for use
in rubber goods, especially those loaded with non-black fillers. Used as
a thixotropic resinous tackifier, plasticizer and...

AKROCHEM® HR-100
Technical Datasheet | Supplied by Akrochem
Hydrophilic thermoplastic hydrocarbon tackifying resin. Designed for
use in rubber goods, especially those loaded with non-black fillers.
Used as a thixotropic resinous tackifier, plasticizer and process aid for
synthetic and natural rubbers and plastics. Possesses very good color,
helps build tack and binds together and disperses mineral fillers in a
rubber compound. Improves flex-crack and cut-growth resistance.
Increases elongation and tensile.
Product Type Tackifiers > Hydrocarbon Resins > Mixed Aliphatic /
Aromatics
Chemical Composition : Thermoplastic hydrocarbon resin
Physical Form : Flakes
Product Status COMMERCIAL
Applications/ Recommended for : Polymers > Synthetic
Rubbers
Bio Based : No
AKROCHEM® HR-100 Properties
Property : Value & Unit
Test Condition Test Method
Gardner color: (50% toluene) :8
Specific gravity @ 25°C :1.06
Softening point (B&R) :100 °C
Ash content :< 0.1 %

AKROCHEM® HR-801
Akrochem
Low cost, aliphatic hydrocarbon tackifier resin. Designed as an
economical alternative to conventional aromatic resins. Can be used in a
variety of rubber compounding applications. Builds tack...

AKROCHEM® HR-801
Technical Datasheet | Supplied by Akrochem
Low cost, aliphatic hydrocarbon tackifier resin. Designed as an
economical alternative to conventional aromatic resins. Can be used in a
variety of rubber compounding applications. Builds tack. Increases
tensile and elongation. Reduces flex cracking and cut growth and aids
processing of mineral filled elastomers.
Product Type Tackifiers > Hydrocarbon Resins > Aliphatic
Chemical Composition : Aliphatic hydrocarbon resin
Physical Form : Flakes
Product Status COMMERCIAL
Applications/ Recommended for : Polymers > Synthetic
Rubbers
Bio Based : No
AKROCHEM® HR-801 Properties
Property Value & Unit
Test Condition Test Method
Color (70% mineral spirits): 12
Specific gravity 1.08
Melt Point (Ball & Ring) 105 °C

AKROCHEM® P-03
Akrochem
Thermoplastic, oil soluble, high melting terpene phenolic resin. Used to
increase the open time of neoprene solvent cements. Provides good tack
and is often used in combination with a heat reactive...

AKROCHEM® P-03
Technical Datasheet | Supplied by Akrochem
Thermoplastic, oil soluble, high melting terpene phenolic resin. Used to
increase the open time of neoprene solvent cements. Provides good tack
and is often used in combination with a heat reactive resin to give a
balance of properties. Shows some reactivity with magnesium oxide.
Use level: 10 to 150 parts per 100 parts of neoprene.
Product Type Tackifiers > Terpenes > Terpene phenol
Chemical Composition : Thermoplastic terpene phenolic resin
Physical Form : Flakes
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives > : Solvent based
Polymers > : Synthetic Rubbers > Chlorinated Rubbers /
Chloroprene’s (CR)
Bio Based : Yes
AKROCHEM® P-03 Properties
Property Value & Unit
Test Condition Test Method
Specific gravity 1.10
Melting point 150 °C
Acid number 65

AKROCHEM® P-101
Akrochem
Heat reactive, phenolic resin. Used in the resin curing of butyl rubbers,
adhesive systems and sealants. Possesses very good compatibility with
chloroprene, nitrile and natural rubbers. Provides...

AKROCHEM® P-101
Technical Datasheet | Supplied by Akrochem
Heat reactive, phenolic resin. Used in the resin curing of butyl rubbers,
adhesive systems and sealants. Possesses very good compatibility with
chloroprene, nitrile and natural rubbers. Provides good contact cement
with long open time and good dry tack properties with chloroprene
rubber. Gives good chemical, abrasion and heat resistance in butyl
rubber sealants.
Product Type Tackifiers > : Alkyl phenolics
Chemical Composition : Phenolic resin
CAS Number : 9003-35-4
Physical Form ; Flakes
Product Status COMMERCIAL
Bio Based: No
AKROCHEM® P-101 Properties
Property Value & Unit
Test Condition Test Method
Melting point (Cap. Tube) 140 - 150 °C
Specific gravity 1.04
Methylol content 9.5 - 11 %
Softening Point, Ball & Ring 80 - 95 °C

AKROCHEM® P-105
Akrochem
Oil soluble, heat reactive phenolic resin. Used in neoprene solvent type
contact cements. Provides high heat resistance, high cohesive strength,
shorter open time, and light color. Possesses...

AKROCHEM® P-105
Technical Datasheet | Supplied by Akrochem
Oil soluble, heat reactive phenolic resin. Used in neoprene solvent type
contact cements. Provides high heat resistance, high cohesive strength,
shorter open time, and light color. Possesses superior phase resistance.
Can react with an active magnesium oxide in solvent solution, forming
a salt which greatly increases the heat resistance of the adhesive.
Product Type : Tackifiers > Alkyl phenolics
Chemical Composition : Phenolic resin
CAS Number 9003-35-4
Physical Form: Flakes
Product Status COMMERCIAL
Bio Based: No
AKROCHEM® P-105 Properties
Property Value & Unit
Test Condition Test Method
Specific gravity 1.10
Melting point 160 - 190 °C
Methylol content 8 - 12 %
Color, Gardner, 60% in Toluene 1-7
Solubility Properties Element
Test ConditionTest Method
Soluble in aromatic hydrocarbons and ketone
solvents
Soluble in acetone, benzene, MEK, MIBK,
toluene and xylene
Slightly soluble in aliphatic solvents

Biofene®
Amyris
Biofene® is a renewable, long-chain, branched hydrocarbon molecule
called farnesene (trans-ß-farnesene). Acts as a tackifier. With its unique
backbone and structure, Biofene® can provide superior...

Biofene®
Technical Datasheet | Supplied by Amyris
Biofene® is a renewable, long-chain, branched hydrocarbon molecule
called farnesene (trans-ß-farnesene). Acts as a tackifier. With its unique
backbone and structure, Biofene® can provide superior qualities in
various polymer applications. It replaces petroleum-derived feedstock
in the production of specified classes of high-performing polymers.
Used in adhesives application.
Product Type Tackifiers
CAS Number 502-61-4
Product Status COMMERCIAL
Applications/ Recommended for Adhesives
Bio Based Yes

AQUARES T 10B
Aquaspersions
Emulsion of a low molecular weight polybutene. It is a wet-tack
enhancer which is miscible in water and exhibits negligible evaporation
rate. Recommended for acrylic PSA and SBR. Can also be used in...

AQUARES T 10B
Technical Datasheet | Supplied by Aquaspersions
Emulsion of a low molecular weight polybutene. It is a wet-tack
enhancer which is miscible in water and exhibits negligible evaporation
rate. Recommended for acrylic PSA and SBR. Can also be used in latex
formulations. It should not be used with strong acids, strong bases and
strong oxidizing agents.
Product Type Tackifiers
Chemical Composition Emulsion of a low molecular
weight polybutene
CAS Number 9003-28-5
Physical Form Liquid
Appearance White
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives
Adhesives>> Pressure sensitive (PSA)
Polymers > Acrylics & Acrylic Copolymers
Styrene-butadiene rubber (SBR)
AQUARES T 10B Properties
Property Value & Unit
Test Condition Test Method
Boiling point/range 100 °C
Melting point/range 0 °C
Relative density 0.90 - 1.05
pH 5.0 - 9.0
Solubility Properties Element
Test Condition Test Method
Miscible in water

AQUARES T 600 B
Aquaspersions
Emulsion of a low molecular weight polybutene. It is a wet-tack
enhancer which is miscible in water and exhibits negligible evaporation
rate. Recommended for acrylic PSA and SBR. Can also be used in...

AQUARES T 600 B
Technical Datasheet | Supplied by Aquaspersions
Emulsion of a low molecular weight polybutene. It is a wet-tack
enhancer which is miscible in water and exhibits negligible evaporation
rate. Recommended for acrylic PSA and SBR. Can also be used in latex
formulations. It should not be used with strong acids, strong bases and
strong oxidizing agents.
Product Type Tackifiers
Chemical Composition Emulsion of a low molecular weight
polybutene
CAS Number 9003-28-5
Physical Form Liquid
Appearance White
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives
Adhesives>> Pressure sensitive (PSA)
Polymers > Acrylics & Acrylic Copolymers
Styrene-butadiene rubber (SBR)
AQUARES T 600 B Properties
Property Value & Unit
Test Condition Test Method
Boiling point/range 100 °C
Melting point/range 0 °C
Relative density 0.90 - 1.05
pH 5.0 - 9.0
Solubility Properties Element
Test Condition Test Method
Miscible in water

AQUARES T100H
Aquaspersions
Emulsion of an aliphatic hydrocarbon resin. It is a non-viscous cream
colored liquid which exhibits negligible evaporation rate.
Recommended for acrylic PSA. Can also be used in latex
formulations...

AQUARES T100H
Technical Datasheet | Supplied by Aquaspersions
Emulsion of an aliphatic hydrocarbon resin. It is a non-viscous cream
colored liquid which exhibits negligible evaporation rate.
Recommended for acrylic PSA. Can also be used in latex formulations.
It should not be used with strong acids and strong bases.
Product Type Tackifiers > Hydrocarbon Resins > Aliphatic
Chemical Composition Emulsion of an aliphatic
hydrocarbon resin
Physical Form Liquid
Appearance Cream
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives
Sealants
Adhesives>> Pressure sensitive (PSA)
Polymers > Acrylics & Acrylic Copolymers
AQUARES T100H Properties
Property Value & Unit
Test Condition Test Method
Boiling point/range 100 °C
Melting point/range 0 °C
Relative density 0.90 - 1.00
Solubility Properties Element
Test Condition Test Method
Miscible in water

AQUARES T20H
Aquaspersions
Emulsion of a liquid aromatic hydrocarbon resin. It is miscible in water
and exhibits negligible evaporation rate. Recommended for acrylic
PSA. Can also be used in latex formulations. It should not...

AQUARES T20H
Technical Datasheet | Supplied by Aquaspersions
Emulsion of a liquid aromatic hydrocarbon resin. It is miscible in water
and exhibits negligible evaporation rate. Recommended for acrylic
PSA. Can also be used in latex formulations. It should not be used with
strong acids and strong bases.
Product Type Tackifiers > Hydrocarbon Resins > Aromatics
Chemical Composition Emulsion of a liquid aromatic
hydrocarbon resin
Physical Form Liquid
Appearance Off-white
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives
Sealants
Adhesives>> Pressure sensitive (PSA)
Polymers > Acrylics & Acrylic Copolymers
AQUARES T20H Properties
Property Value & Unit
Test Condition Test Method
Boiling point/range 100 °C
Melting point/range 0 °C
Relative density 0.90 - 1.00
pH 8.5 - 10.5
Solubility Properties Element
Test Condition Test Method
Miscible in water

AQUARES T85E
Aquaspersions
Emulsion of a blend of rosin ester resin. It is a wet-tack enhancer which
is miscible in water and exhibits negligible evaporation rate.
Recommended for acrylic PSA and SBR. Can also be used in...

AQUARES T85E
Technical Datasheet | Supplied by Aquaspersions
Emulsion of a blend of rosin ester resin. It is a wet-tack enhancer which
is miscible in water and exhibits negligible evaporation rate.
Recommended for acrylic PSA and SBR. Can also be used in latex
formulations. It should not be used with strong acids and strong bases.
Product Type Tackifiers > Rosin Esters
Chemical Composition Emulsion of a blend of rosin ester
resin
Physical Form Liquid
Appearance Cream
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives
Adhesives>> Pressure sensitive (PSA)
Polymers > Acrylics & Acrylic Copolymers
Styrene-butadiene rubber (SBR)
AQUARES T85E Properties
Property Value & Unit
Test Condition Test Method
Boiling point/range 100 °C
Melting point/range 0 °C
Relative density 0.900 - 1.00
Solubility Properties Element
Test Condition Test Method
Miscible in water

E1102
Aquent Impex
Aliphatic C5 hydrocarbon resin. Acts as a tackifier. It is a light colored
amorphous, glassy, low-molecular-weight polymer that promotes
adhesion and tack. Offers high thermal stability, polymer...

E1102
Technical Datasheet | Supplied by Aquent Impex
Aliphatic C5 hydrocarbon resin. Acts as a tackifier. It is a light colored
amorphous, glassy, low-molecular-weight polymer that promotes
adhesion and tack. Offers high thermal stability, polymer compatibility
and low odor. Used in hot-melt as well as pressure-sensitive adhesives.
Product Type
Tackifiers > Hydrocarbon Resins > Aliphatic
Tackifier > > Hydrocarbon Resin > > Aliphatic > > C5
Chemical Composition Aliphatic C5 hydrocarbon resin
CAS Number 64742-16-1
Product Status COMMERCIAL
Applications/ Recommended for Adhesives > Hot melts > Pressure
sensitive (HMPSA)
E1102 Properties
Property Value & Unit
Test Condition Test Method
Softening point 99 °C
Initial Color (YI) 28

E1202
Aquent Impex
Aliphatic C5 hydrocarbon resin. Acts as a tackifier. It is a light colored
amorphous, glassy, low-molecular-weight polymer that promotes
adhesion and tack. Offers high thermal stability, polymer...

E1202
Technical Datasheet | Supplied by Aquent Impex
Aliphatic C5 hydrocarbon resin. Acts as a tackifier. It is a light colored
amorphous, glassy, low-molecular-weight polymer that promotes
adhesion and tack. Offers high thermal stability, polymer compatibility
and low odor. Used in hot-melt as well as pressure-sensitive adhesives.
Product Type
Tackifiers > Hydrocarbon Resins > Aliphatic
Tackifier > > Hydrocarbon Resin > > Aliphatic > > C5
Chemical Composition Aliphatic C5 hydrocarbon resin
CAS Number 64742-16-1
Product Status COMMERCIAL
Applications/ Recommended for Adhesives > Hot melts > Pressure
sensitive (HMPSA)
E1202 Properties
Property Value & Unit
Test Condition Test Method
Softening point 98 °C
Initial Color (YI) 23
E1204 LS
Aquent Impex
Aliphatic C5 hydrocarbon resin. Acts as a tackifier. It is a light colored
amorphous, glassy, low-molecular-weight polymer that promotes
adhesion and tack. Offers high thermal stability, polymer...

E1204 LS
Technical Datasheet | Supplied by Aquent Impex
Aliphatic C5 hydrocarbon resin. Acts as a tackifier. It is a light colored
amorphous, glassy, low-molecular-weight polymer that promotes
adhesion and tack. Offers high thermal stability, polymer compatibility
and low odor. Used in hot-melt as well as pressure-sensitive adhesives.
Product Type
Tackifiers > Hydrocarbon Resins > Aliphatic
Tackifier > > Hydrocarbon Resin > > Aliphatic > > C5
Chemical Composition Aliphatic C5 hydrocarbon
resin
CAS Number 64742-16-1
Product Status COMMERCIAL
Applications/ Recommended for Adhesives > Hot melts > Pressure
sensitive (HMPSA)
E1204 LS Properties
Property Value & Unit
Test Condition Test Method
Softening point 100 °C
Initial Color (YI) 31

E1304
Aquent Impex
Aliphatic C5 hydrocarbon resin. Acts as a tackifier. It is a light colored
amorphous, glassy, low-molecular-weight polymer that promotes
adhesion and tack. Offers high thermal stability, polymer...

E1304
Technical Datasheet | Supplied by Aquent Impex
Aliphatic C5 hydrocarbon resin. Acts as a tackifier. It is a light colored
amorphous, glassy, low-molecular-weight polymer that promotes
adhesion and tack. Offers high thermal stability, polymer compatibility
and low odor. Used in hot-melt as well as pressure-sensitive adhesives.
Product Type
Tackifiers > Hydrocarbon Resins > Aliphatic
Tackifier > > Hydrocarbon Resin > > Aliphatic > > C5
Chemical Composition Aliphatic C5 hydrocarbon resin
CAS Number 64742-16-1
Product Status COMMERCIAL
Applications/ Recommended for Adhesives > Hot melts > Pressure
sensitive (HMPSA)
E1304 Properties
Property Value & Unit
Test Condition Test Method
Softening point 101 °C
Initial Color (YI) 29

E1310
Aquent Impex
Aliphatic C5 hydrocarbon resin. Acts as a tackifier. It is a light colored
amorphous, glassy, low-molecular-weight polymer that promotes
adhesion and tack. Offers high thermal stability, polymer...

E1310
Technical Datasheet | Supplied by Aquent Impex
Aliphatic C5 hydrocarbon resin. Acts as a tackifier. It is a light colored
amorphous, glassy, low-molecular-weight polymer that promotes
adhesion and tack. Offers high thermal stability, polymer compatibility
and low odor. Used in hot-melt as well as pressure-sensitive adhesives.
Product Type
Tackifiers > Hydrocarbon Resins > Aliphatic
Tackifier > > Hydrocarbon Resin > > Aliphatic > > C5
Chemical Composition Aliphatic C5 hydrocarbon
resin
CAS Number 64742-16-1
Product Status COMMERCIAL
Applications/ Recommended for Adhesives > Hot melts > Pressure
sensitive (HMPSA)
E1310 Properties
Property Value & Unit
Test Condition Test Method
Softening point 93 °C
Initial Color (YI) 25

803L
Arakawa Chemical
803L by Arakawa Chemical is terpene phenolic resin derived from
rosin, resin from pine trees. Used as a tackifier in chloroprene and hot
melt adhesives. 803L offers high softening point and heat...

803L
Technical Datasheet | Supplied by Arakawa Chemical
803L by Arakawa Chemical is terpene phenolic resin derived from
rosin, resin from pine trees. Used as a tackifier in chloroprene and hot
melt adhesives. 803L offers high softening point and heat stability.
Product Type Tackifiers > Terpenes > Terpene phenol
Chemical Composition Terpene Phenolic Resin
CAS Number 9003-74-1
Physical Form Lumps
Product Status COMMERCIAL
Applications/ Recommended for Adhesives > Hot melts
Bio Based Yes
Bio Based Content Comments Rosin, resin from pine
trees
803L Properties
Property Value & Unit
Test Condition Test Method
Color, APHA <7
Acid Value 45 - 60
Softening Point 145 - 160 °C
Ring and Ball
Akron M-100
Arakawa Chemical
Akron M-100 by Arakawa Chemical is a hydrogenated hydrocarbon
resin. Offers good weather resistance and compatibility with EVA and
block rubber. Listed by FDA (U.S. Food and Drug Administration) and.

Akron M-100
Technical Datasheet | Supplied by Arakawa Chemical
Akron M-100 by Arakawa Chemical is a hydrogenated hydrocarbon
resin. Offers good weather resistance and compatibility with EVA and
block rubber. Listed by FDA (U.S. Food and Drug Administration) and
Japan Hygienic Olefin and Styrene Plastics Association. Akron M-100
is used as a tackifier in pressure sensitive and hot melt adhesives.
Product Type Tackifiers > Hydrogenated Hydrocarbon Resins
Chemical Composition Hydrogenated hydrocarbon resin
Physical Form Pellets
Product Status COMMERCIAL
Applications/ Recommended for Adhesives > Hot melts > Pressure
sensitive (HMPSA)
Food contact approval Yes
Bio Based No
Labels/Agency Rating FDA (U.S. Food and Drug Administration) and
Japan Hygienic Olefin and Styrene Plastics Association
Akron M-100 Properties
Property Value & Unit
Test ConditionTest Method
Softening Point 95 - 105 °C

Akron M-115
Arakawa Chemical
Colourless, odorless, hydrogenated hydrocarbon resin. Used as a
tackifier in pressure sensitive and hot melt adhesives. Offers good
weather resistance and compatibility with EVA and block rubber...

Akron M-115
Technical Datasheet | Supplied by Arakawa Chemical
Colourless, odorless, hydrogenated hydrocarbon resin. Used as a
tackifier in pressure sensitive and hot melt adhesives. Offers good
weather resistance and compatibility with EVA and block rubber.
Product Type Tackifiers > Hydrogenated Hydrocarbon Resins
Chemical Composition Hydrogenated hydrocarbon resin
Physical Form Pellets
Applications/ Recommended for
Adhesives > Hot melts > Pressure sensitive (HMPSA)
Polymers > Synthetic Rubbers
Polymers > Ethylene Co-terpolymers - Solids (EVA, EMA)
Akron M-115 Properties
Property Value & Unit
Test Condition Test Method
Color value, Hazen < 100
Softening point, R&B 115 °C

Akron M-135
Arakawa Chemical
Colourless, odorless, hydrogenated hydrocarbon resin. Used as a
tackifier in pressure sensitive and hot melt adhesives. Offers good
weather resistance and compatibility with EVA and block rubber...

Akron M-135
Technical Datasheet | Supplied by Arakawa Chemical
Colourless, odorless, hydrogenated hydrocarbon resin. Used as a
tackifier in pressure sensitive and hot melt adhesives. Offers good
weather resistance and compatibility with EVA and block rubber.
Product Type Tackifiers > Hydrogenated Hydrocarbon Resins
Chemical Composition Hydrogenated hydrocarbon resin
Physical Form Pellets
Applications/ Recommended for
Adhesives > Hot melts > Pressure sensitive (HMPSA)
Polymers > Synthetic Rubbers
Polymers > Ethylene Co-terpolymers - Solids (EVA, EMA)
Akron M-135 Properties
Property Value & Unit
Test Condition Test Method
Color value, Hazen < 100
Softening point, R&B 135 °C

Akron M-90
Arakawa Chemical
Colourless, odorless, hydrogenated hydrocarbon resin. Used as a
tackifier in pressure sensitive and hot melt adhesives. Offers good
weather resistance and compatibility with EVA and block rubber...
Akron M-90
Technical Datasheet | Supplied by Arakawa Chemical
Colourless, odorless, hydrogenated hydrocarbon resin. Used as a
tackifier in pressure sensitive and hot melt adhesives. Offers good
weather resistance and compatibility with EVA and block rubber.
Product Type Tackifiers > Hydrogenated Hydrocarbon Resins
Chemical Composition Hydrogenated hydrocarbon resin
Physical Form Pellets
Applications/ Recommended for
Adhesives > Hot melts > Pressure sensitive (HMPSA)
Polymers > Synthetic Rubbers
Polymers > Ethylene Co-terpolymers - Solids (EVA, EMA)
Akron M-90 Properties
Property Value & Unit
Test Condition Test Method
Color value, Hazen < 100
Softening point, R&B 90 °C
Tackifiers and Properties 02

Tamanol 520S
Arakawa Chemical
Alkyl phenolic resin. Used as a tackifier in CR adhesive. Offers
tackiness retention time. Possesses good phasing stability, heat
resistance and adhesion strength...
Tamanol 520S
Technical Datasheet | Supplied by Arakawa Chemical
Alkyl phenolic resin. Used as a tackifier in CR adhesive. Offers
tackiness retention time. Possesses good phasing stability, heat
resistance and adhesion strength.
Product Type Tackifiers > Alkylphenols
Chemical Composition Alkyl phenolic resin
Applications/ Recommended for
Adhesives
Polymers > Synthetic Rubbers > Chlorinated Rubbers /
Chloroprene’s (CR)
Tamanol 520S Properties
Property Value & Unit
Test Condition Test Method
Softening point, R&B 120 °C

Tamanol 521
Arakawa Chemical
Alkyl phenolic resin. Used as a tackifier in CR adhesives. Offers long
tackiness retention...
Tamanol 521
Technical Datasheet | Supplied by Arakawa Chemical
Alkyl phenolic resin. Used as a tackifier in CR adhesives. Offers long
tackiness retention.
Product Type Tackifiers > Alkylphenols
Chemical Composition Alkyl phenolic resin
Physical Form Lumps
Applications/ Recommended for
Adhesives
Polymers > Synthetic Rubbers > Chlorinated Rubbers / Chloroprene’s
(CR)
Tamanol 521 Properties
Property Value & Unit
Test Condition Test Method
Softening point, R&B 100 - 115 °C

Tamanol 526
Arakawa Chemical
Tamanol 526 by Arakawa Chemical is a general-purpose alkyl phenolic
resin. Tamanol 526 is used as a tackifier in CR adhesives...
Tamanol 526
Technical Datasheet | Supplied by Arakawa Chemical
Tamanol 526 by Arakawa Chemical is a general-purpose alkyl phenolic
resin.
Tamanol 526 is used as a tackifier in CR adhesives.
Product Type Tackifiers > Alkylphenols
Chemical Composition Alkyl phenolic resin
Physical Form Lumps
Product Status COMMERCIAL
Applications/ Recommended for Adhesives
Tamanol 526 Properties
Property Value & Unit
Test Condition Test Method
Softening Point 115 - 130 °C
Ring and Ball

Tamanol 531
Arakawa Chemical
Pure phenolic resin. Used as a tackifier in NBR adhesives. Provides
addition of hardness...
Tamanol 531
Technical Datasheet | Supplied by Arakawa Chemical
Pure phenolic resin. Used as a tackifier in NBR adhesives. Provides
addition of hardness.
Product Type Tackifiers > Phenolics
Chemical Composition Phenolic resin
CAS Number 9003-35-4
Physical Form Powder
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives
Polymers > Synthetic Rubbers
Bio Based No
Tamanol 531 Properties
Property Value & Unit
Test Condition Test Method
Softening point, R&B 80 - 88 °C

Tamanol 581
Arakawa Chemical
Alkyl phenolic resin. Used as a tackifier in CR adhesive. Offers
tackiness retention time. Possesses good phasing stability, heat
resistance and adhesion strength...
Tamanol 581
Technical Datasheet | Supplied by Arakawa Chemical
Alkyl phenolic resin. Used as a tackifier in CR adhesive. Offers
tackiness retention time. Possesses good phasing stability, heat
resistance and adhesion strength.
Product Type Tackifiers > Alkylphenols
Chemical Composition Alkyl phenolic resin
Applications/ Recommended for
Adhesives
Polymers > Synthetic Rubbers > Chlorinated Rubbers /
Chloroprene’s (CR)
Tamanol 581 Properties
Property Value & Unit
Test Condition Test Method
Softening point, R&B 100 °C
Voltic® 3
Arkema
Voltic® 3 by Arkema is poly-tert-amyl phenol disulfide. Acts as a
nitrosamine-free vulcanizing agent, antioxidant and tackifier. Designed
for normal and high temperature sensitive adhesives based on.
Vultac® 3
Technical Datasheet | Supplied by Arkema
Vultac® 3 by Arkema is poly-tert-amylphenol disulfide.
Acts as a nitrosamine-free vulcanizing agent, antioxidant and
tackifier.
Designed for normal and high temperature sensitive adhesives based on
natural rubber and SBR.
Vultac® 3 has a shelf life of 3 years.
Product Type
Tackifiers
Crosslinking / Curing / Vulcanizing Agents
Antioxidants > Phenolics
Chemical Composition Poly-tert-amylphenol Disulfide
CAS Number 68555-98-6
Physical Form Pastilles
Appearance Reddish-brown to Dark brown
Product Status COMMERCIAL
Applications/ Recommended for Adhesives
Vultac® 3 Properties
Property Value & Unit
Test Condition Test Method
Sulphur Content 27.0 - 29.0 %wt
SOP QC - 113 e
Softening Point 95 - 115 °C
SOP QC - 092 e
Bulk Density 800 g/l
At 20°C. Pastilles
Flash Point 340 °F
Closed Cup
Density 1200 g/l
At 120°C. Liquid
Viscosity 4000 cP
At 150°C
Solubility Properties Element
Test ConditionTest Method
Soluble in Toluene
Insoluble in Water
Insoluble in Hexane

Vultac® 710
Arkema
Vultac® 710 by Arkema is a mixture of poly-tert-amylphenol disulfide
and stearic acid.
Acts as a nitrosamine-free vulcanizing agent with antioxidant and
tackifying properties.
It imparts improved...
Vultac® 710
Technical Datasheet | Supplied by Arkema
Vultac® 710 by Arkema is a mixture of poly-tert-amylphenol disulfide
and stearic acid.
Acts as a nitrosamine-free vulcanizing agent with antioxidant and
tackifying properties. It imparts improved shelf aging, retention of
tack, heat aging and adhesion.
Vultac® 710 has a shelf life of 3 years.
Product Type
Crosslinking / Curing / Vulcanizing Agents
Plasticizers
Tackifiers
Chemical Composition Poly-tert-amylphenoldisulfide and
Stearic acid
CAS Number 68555-98-6, 57-11-4
Physical Form Pastilles
Appearance Brown greyish
Product Status COMMERCIAL
Applications/ Recommended for Adhesives
Vultac® 710 Properties
Property Value & Unit
Test Condition Test Method
Sulphur Content 26.4 - 28.4 %wt
SOP QC - 113 e
Softening Point 75 - 90 °C
SOP QC - 092 e
Bulk Density 800 g/l
At 20°C. Pastilles
Stearic Acid Content 9 - 11 %wt
SOP QC - 115 e
Density 1200 g/l
At 100°C. Molten
Viscosity 10000 cP
At 120°C
Viscosity 800 cP
At 150°C
Flash Point > 200 °C
Closed Cup ASTM D3278
Solubility Properties Element
Test Condition Test Method
Soluble in Toluene
Insoluble in Water
Insoluble in Hexane

6002 Glycerol
Atul Polychem
6002 Glycerol by Atul Polychem is an ester gum. It acts as a tackifier. It
shows infinite solvent tolerance in mineral turpentine oil (MTO).
6002 Glycerol is recommended for rubber-based adhesive...
6002 Glycerol
Technical Datasheet | Supplied by Atul Polychem
6002 Glycerol by Atul Polychem is an ester gum.
It acts as a tackifier.
It shows infinite solvent tolerance in mineral turpentine oil (MTO).
6002 Glycerol is recommended for rubber based adhesive applications.
Product Type Tackifiers
Chemical Composition Ester gum
Appearance Pale yellow
Product Status COMMERCIAL
Applications/ Recommended for Adhesives > Solvent based
6002 Glycerol Properties
Property
Value & Unit
Test Condition Test
Method
Softening Point by Ball & ring method
90 - 100 °C
Acid Value
< 15
Viscosity @ 30°C, Ford Cup No. B4, in 50% solution in Toluene
14 - 16

Acronal® 4 F
BASF
Acronal® 4 F by BASF is a solvent-free tackifier based on n-butyl
acrylate resin. It is a light-stable grade for plasticizing nitrocellulose and
chlorinated binders to yield coatings of great...
Acronal® 4 F
Technical Datasheet | Supplied by BASF
Acronal® 4 F by BASF is a solvent-free tackifier based on n-butyl
acrylate resin. It is a light-stable grade for plasticizing nitrocellulose and
chlorinated binders to yield coatings of great flexibility, outstanding
adhesion and aging-resistance. Acronal® 4 F is suitable for construction
adhesives. It is compatible with nitrocellulose vinyl chloride
copolymers, polyvinyl ethers, polyacrylates, natural resins like rosin
and plasticizers. It has a shelf life of 1 year. Compliance with U.S. Food
and Drug Administration Title 21 Code of Federal Regulations 175.105,
175.300, 176.170, 176.180, and 177.1210. It is a non-APEO product.
Product Type
Plasticizers
Tackifiers > Resin Dispersions
Chemical Composition n-butyl acrylate resin
CAS Number 9003-49-0
Physical Form Dispersion
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives
Buildings & constructions
Food contact approval Yes
Bio Based No
Labels/Agency Rating FDA 21 CFR 175.105,
FDA 21 CFR 175.300,
FDA 21 CFR 176.170,
FDA 21 CFR 176.180,
FDA 21 CFR 177.1210
Acronal® 4 F Properties
Property Value & Unit
Test Condition Test Method
Solid Content 99 %
Glass Transition Temperature (Tg), DSC -40 °C
Non-volatile Content @ 125°C, 1 hr, ISO 3251, DIN 53216, part 1 >
98.5 %
Viscosity @ 23°C, in 50% in ethyl acetate, ISO 3219, DIN 53019/DIN
53214
130 - 200 mPa.s

Shear Gradient 25 1/s

Iodine Color, DIN 6162 0-1
Flash Point, ISO 2719, DIN 51758 150 °C
Solubility Properties Element
Test Condition Test Method
Soluble in esters
Soluble in glycol ethers
Soluble in glycol ether acetates
Soluble in ketones
Soluble in aromatics
Soluble in mineral spirits
Soluble in turpentine
Soluble in chlorinated hydrocarbons
Soluble in only some alcohols
Acronal® A 107
BASF
Acronal® A 107 by BASF is acrylic dispersion which functions as a
tackifying blending component. Used in impregnated and expandable
foams...
Acronal® A 107
Technical Datasheet | Supplied by BASF
Acronal® A 107 by BASF is acrylic dispersion which functions as a
tackifying blending component. Used in impregnated and expandable
foams.
Product Type Tackifiers
Physical Form Dispersion
Product Status AVAILABILITY NOT CONFIRMED *
Applications/ Recommended for Sealants > Foam
Bio Based No
Acronal® A 107 Properties
Property Value & Unit
Test Condition Test Method
Solids Content 50 %
pH 6 - 7.5
Viscosity 40 - 150 mPa-s
At 23°C
Glass Transition Temperature (Tg) -46 °C

BITONER® BT-1102
Bitoner Resin
Thermoplastic, low molecular weight, modified aliphatic resin. Acts as
a tackifier. Possesses good chemical stability. Use in hot melt adhesives
and PSA...
BITONER® BT-1102
Technical Datasheet | Supplied by Bitoner Resin
Thermoplastic, low molecular weight, modified aliphatic resin. Acts as
a tackifier. Possesses good chemical stability. Use in hot melt adhesives
and PSA.
Product Type Tackifiers > Hydrocarbon Resins > Aliphatics
Chemical Composition Thermoplastic modified aliphatic
resin
Product Status COMMERCIAL
Applications/ Recommended for Adhesives > Hot melts > Pressure
sensitive (HMPSA)
Bio Based No
BITONER® BT-1102 Properties
Property Value & Unit
Test Condition Test Method
Color (50% resin solid in Toluene) < 5 Ga#
Softening point (Ring & Ball) 95 - 105 °C
Melt viscosity @ 200°C < 200 mpas
Acid value 1.0 - 2.0 mgKOH/g
Specific gravity @ 25°C 0.94 - 0.99 20/20°C

BITONER® BT-1200
Bitoner Resin
Thermoplastic, low molecular weight, aliphatic resin. Obtained from
petroleum-derived monomers. Acts as a tackifier. Possesses excellent
balance of tack and of adhesive as well as cohesive...
BITONER® BT-1200
Technical Datasheet | Supplied by Bitoner Resin
Thermoplastic, low molecular weight, aliphatic resin. Obtained from
petroleum-derived monomers. Acts as a tackifier. Possesses excellent
balance of tack and of adhesive as well as cohesive properties. Has
excellent heat stability, wide compatibility and solubility. Also
possesses good chemical stability, low volatility and water resistance.
Used in hot melt adhesive, pressure sensitive adhesive and packaging
tapes.
Product Type Tackifiers > Hydrocarbon Resins > Aliphatics
Chemical Composition Thermoplastic aliphatic
resin
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives > Hot melts > Pressure sensitive (HMPSA)
Tapes
Bio Based No
BITONER® BT-1200 Properties
Property Value & Unit
Test Condition Test Method
Color (50% resin solid in Toluene) < 3 Ga#
Softening point (Ring & Ball) 95 - 105 °C
Melt viscosity @ 200°C < 230 mpas
Acid value < 0.30 mgKOH/g
Specific gravity @ 25°C 0.92 - 0.99 20/20°C
Volatile content, 150°C 1hr < 1.0 wt%

BITONER® C5 BT-100
Bitoner Resin
Thermoplastic, low molecular weight, aliphatic resin. Acts as a
tackifier. Owing to its excellent tack and tack retention, it is also used in
hot melt adhesives and PSA. Possesses good chemical...
BITONER® C5 BT-100
Technical Datasheet | Supplied by Bitoner Resin
Thermoplastic, low molecular weight, aliphatic resin. Acts as a
tackifier. Owing to its excellent tack and tack retention, it is also used in
hot melt adhesives and PSA. Possesses good chemical stability and
water resistance.
Product Type Tackifiers > Hydrocarbon Resins > Aliphatics
Chemical Composition
Thermoplastic aliphatic resin
Product Status COMMERCIAL
Applications/ Recommended for Adhesives > Hot melts >
Pressure sensitive (HMPSA)
Bio Based No
BITONER® C5 BT-100 Properties
Property Value & Unit
Test ConditionTest Method
Color (50% resin solid in Toluene) < 5 Ga#
Softening point (Ring & Ball) 95 - 105 °C
Melt viscosity @ 200°C < 200 mpas
Acid value < 0.30 mgKOH/g
Specific gravity @ 25°C 0.92 - 0.99 20/20°C
Volatile content (wt%), 150°C 1hr < 1.0 wt%

BITONER® C9 BP-100
Bitoner Resin
Thermoplastic aromatic hydrocarbon resin. Acts as a tackifier.
Possesses light color and less odor. Used in hot melt adhesives, shoes
adhesives and solvent adhesives...
BITONER® C9 BP-100
Technical Datasheet | Supplied by Bitoner Resin
Thermoplastic aromatic hydrocarbon resin. Acts as a tackifier.
Possesses light color and less odor. Used in hot melt adhesives, shoes
adhesives and solvent adhesives.
Product Type Tackifiers > Hydrocarbon Resins > Aromatics
Chemical Composition Thermoplastic aromatic
hydrocarbon resin
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives > Hot melts
Adhesives > Solvent based
Footwear & leather
Bio Based No
BITONER® C9 BP-100 Properties
Property Value & Unit
Test ConditionTest Method
Softening point (Ring & Ball) 95 - 105 °C

BITONER® C9 BP-120
Bitoner Resin
Thermoplastic aromatic hydrocarbon resin. Acts as a tackifier.
Possesses light color and less odor. Used in hot melt adhesives, shoes
adhesives and solvent adhesives...
BITONER® C9 BP-120
Technical Datasheet | Supplied by Bitoner Resin
Thermoplastic aromatic hydrocarbon resin. Acts as a tackifier.
Possesses light color and less odor. Used in hot melt adhesives, shoes
adhesives and solvent adhesives.
Product Type Tackifiers > Hydrocarbon Resins > Aromatics
Chemical Composition Thermoplastic aromatic
hydrocarbon resin
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives > Hot melts
Adhesives > Solvent based
Footwear & leather
Bio Based No
BITONER® C9 BP-120 Properties
Property Value & Unit
Test Condition Test Method
Softening point (Ring & Ball) 115 - 125 °C

TACTEX B 600
Brancotex
Rosin ester. Acts as a tackifier. Provides a significant increase in
surface tack. Flexible, sticky, transparent, milky-white yellow liquid
dispersion. Compatible with water, plasticizers and resins...
TACTEX B 600
Technical Datasheet | Supplied by Brancotex
Rosin ester. Acts as a tackifier. Provides a significant increase in
surface tack. Flexible, sticky, transparent, milky-white yellow liquid
dispersion. Compatible with water, plasticizers and resins PSA. Used in
the formulation of special adhesives.
Product Type Tackifiers > Rosin Esters
Chemical Composition Rosin ester dispersion
Physical Form Liquid, Milky white, yellow
Appearance Transparent
Product Status COMMERCIAL
Applications/ Recommended for Adhesives
Bio Based Yes
Bio Based Content Comments Obtained from pines
TACTEX B 600 Properties
Property Value & Unit
Test Condition Test Method
Viscosity, Brookfield 400 - 1000 cps
Solids content 58 - 62 %
pH (sol. 5%) 6-8

EMULTROL E-100
Concentrol
Rosin ester. Acts as a tackifier. It is highly stabilized against the effects
of oxidation and the action of UV rays. Offers excellent adhesion
properties over a wide range of temperatures and good...
EMULTROL E-100
Technical Datasheet | Supplied by Concentrol
Rosin ester. Acts as a tackifier. It is highly stabilized against the effects
of oxidation and the action of UV rays. Offers excellent adhesion
properties over a wide range of temperatures and good tack-shear ratio.
Also offers good wetting properties on silicone release paper. It
improves the tack values with no significant effect upon cohesion
values.

Used for pressure sensitive adhesives (PSA) based on acrylic resin

dispersions, PVA, EVA, SBR, NBR and water based polyurethane
dispersions. Also used for tapes and labels applications.
Product Type
Tackifiers > Resin Dispersions
Tackifiers > Rosin Esters
Chemical Composition Rosin ester
Physical Form Dispersion
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives > Water-based > Pressure sensitive (PSA)
Polymers > Polyvinyl Acetate Emulsions & Derivatives (PVAc)
Polymers > Ethylene Co-terpolymers - Solids (EVA, EMA)
Polymers > Polyurethanes > Polyurethane Dispersions (PUDs)
Polymers > Acrylics & Acrylic Copolymers
Styrene-Butadiene Rubber (SBR) Nitrile Butadiene Rubber
(NBR)
Tapes
Labels / Signs / Decals
Bio Based Yes
Bio Based Content Comments Based on the pine
EMULTROL E-100 Properties
Property Value & Unit
Test Condition Test Method
Solids 54 - 56 %
Viscosity < 1500 mPa.s
pH 6.0 - 8.0
Particle size < 0.5
Acid value < 20
R&B-C 60 - 70

EMULTROL E-177
Concentrol
EMULTROL E-177 by Concentrol is a highly stable esterified rosin
resin emulsion. Acts as a tackifier. Improves adhesion upon non-polar
substrates and polymeric dispersion cardboard. Offers good...
EMULTROL E-177
Technical Datasheet | Supplied by Concentrol
EMULTROL E-177 by Concentrol is a highly stable esterified
rosin resin emulsion. Acts as a tackifier. Improves adhesion upon non-
polar substrates and polymeric dispersion cardboard. Offers good
wetting properties on silicone paper.
The emulsion is comprised of extremely fine particles and the product
is highly stable during storage. It is highly stabilized against the effects
of oxidation and the action of ultra-violet rays.
The addition of additives with a highly acid pH and cationic substances
should be avoided. Shows excellent compatibility with acrylic, EVA,
SBR, NBR, latex, polychloroprene and polyurethane aqueous
dispersions. EMULTROL E-177 by Concentrol is used in adhesives.
Complies with FDA regulations.
Product Type Tackifiers > Rosin Esters
Chemical Composition Esterified rosin resin dispersion
Physical Form Liquid
Appearance White
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives
Polymers > Ethylene Co-terpolymers - Solids (EVA, EMA)
Polymers > Polyurethanes
Polymers > Acrylics & Acrylic Copolymers
Polymers > Silicones (Si)
Polymers > Styrene Copolymers (SBR …)
Polymers > Synthetic Rubbers > Chlorinated Rubbers / Chloroprenes
(CR)
Polymers > Polyvinyl Acetate Emulsions & Derivatives (PVAc)
Food contact approval Yes
Bio Based Yes
Bio Based Content Comments Rosin ester
EMULTROL E-177 Properties
Property Value &
Unit
Test Condition Test
Method
Density 1.01 - 1.03
kg/l
Active material content 54 - 56 %

Viscosity @ 20ºC (RV8, spindle 3, 50 r.p.m.) < 1500 cps

pH 6-8
Boiling point 100 °C
Residue soft point 65 - 75 °C
Tackifier recommended proportion 20 - 40 %

Particle equal to or larger than 0.1 mm < 0.01 %

Stability (sedimentation after 15 minutes, 3500 r.p.m.) <1%

Acid Index < 30 mg KOH/ g residuum
Glass transition temperature (Tg) 5 - 10 °C

EMULTROL E-177 RE
Concentrol
Rosin ester. Acts as a tackifier. It is highly stabilized against the effects
of oxidation and the action of UV rays. Offers excellent adhesion
properties over a wide range of temperatures and...
EMULTROL E-177 RE
Technical Datasheet | Supplied by Concentrol
Rosin ester. Acts as a tackifier. It is highly stabilized against the effects
of oxidation and the action of UV rays. Offers excellent adhesion
properties over a wide range of temperatures and effective tackification
with high shear performance. Also offers good wetting properties on
silicone release paper and high performance on low energy surfaces. It
improves the tack values with no significant effect upon cohesion
values.

Used for pressure sensitive adhesives (PSA) based on acrylic resin

dispersions, PVA, EVA, SBR, NBR and water based polyurethane
dispersions. Also used for tapes and labels applications.
Product Type
Tackifiers > Resin Dispersions
Tackifiers > Rosin Esters
Chemical Composition Rosin ester
Physical Form Dispersion
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives > Water-based > Pressure sensitive (PSA)
Polymers > Acrylics & Acrylic Copolymers
Polymers > Polyurethanes > Polyurethane Dispersions (PUDs)
Polymers > Ethylene Co-terpolymers - Solids (EVA, EMA)
Polymers > Polyvinyl Acetate Emulsions & Derivatives (PVAc)
Styrene-Butadiene Rubber (SBR) Nitrile Butadiene Rubber (NBR)
Labels / Signs / Decals
Tapes
Bio Based Yes
Bio Based Content Comments Based on the pine
EMULTROL E-177 RE Properties
Property Value & Unit
Test Condition Test Method
Solids 54 - 56 %
Viscosity < 1500 mPa.s
pH 6.5 - 8.5
Particle size < 0.5
Acid value < 35
R&B-C 70 - 78

EMULTROL E-185
Concentrol
EMULTROL E-185 by Concentrol is a highly stable esterified rosin
resin emulsion. Acts as a tackifier. It is alkylphenol ethoxylate (APEO)-
free and solvent-free. Improves polymeric dispersion...
EMULTROL E-185
Technical Datasheet | Supplied by Concentrol
EMULTROL E-185 by Concentrol is a highly stable esterified rosin
resin emulsion. Acts as a tackifier. It is alkylphenol ethoxylate (APEO)-
free and solvent-free. Improves polymeric dispersion adhesion upon
non-polar substrates and cardboard. Offers good wetting properties on
silicone paper.
The emulsion is comprised of extremely fine particles and the product
is highly stable during storage. It is highly stabilized against the effects
of oxidation and the action of ultra-violet rays. The addition of additives
with a highly acid pH and cationic substances should be avoided.
Shows excellent compatibility with acrylic, EVA, SBR, NBR and
polyurethane aqueous dispersions. EMULTROL E-185 is used in
adhesives. Complies with FDA regulations.
Product Type Tackifiers > Rosin Esters
Chemical Composition Esterified rosin resin dispersion
Physical Form Liquid
Appearance White
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives
Polymers > Styrene Copolymers (SBR …)
Polymers > Synthetic Rubbers
Polymers > Polyvinyl Acetate Emulsions & Derivatives (PVAc)
Polymers > Acrylics & Acrylic Copolymers
Polymers > Silicones (Si)
Polymers > Ethylene Co-terpolymers - Solids (EVA, EMA)
Polymers > Polyurethanes
Food contact approval Yes
Bio Based Yes
Bio Based Content Comments Rosin ester
EMULTROL E-185 Properties
Property Value & Unit
Test Condition Test Method
Density 1.01 - 1.03 kg/l

Active material content 52.5 - 54.5 %

Viscosity @ 20ºC (RV8, spindle 3, 50 r.p.m.) < 1500 cps
pH 7.5 - 8.5
Boiling point 100 °C
Glass transition temperature (Tg) 5 - 10 °C
Recommended tackifier proportion 20 - 40 %
Particle equal to or larger than 0.1 mm < 0.01 %
Stability (sedimentation after 15 minutes, 3500 r.p.m.) <1%
Acid Index < 50 mg KOH/ g
residuum
Softening point (R & B) 80 - 90 °C
EMULTROL E-185 TP
Concentrol
EMULTROL E-185 TP by Concentrol is an alkylphenol ethoxylate-free
and solvent-free esterified rosin resin emulsion. Acts as a highly stable
tackifier. Improves polymeric dispersion adhesion upon...
EMULTROL E-185 TP
Technical Datasheet | Supplied by Concentrol
EMULTROL E-185 TP by Concentrol is an alkylphenol ethoxylate-free
and solvent-free esterified rosin resin emulsion. Acts as a highly stable
tackifier. Improves polymeric dispersion adhesion upon non-polar
substrates and cardboard. Offers good wetting properties on silicone
paper. The emulsion is comprised of extremely fine particles and the
product is highly stable during storage. It is highly stabilized against the
effects of oxidation and the action of ultra-violet rays. The addition of
additives with a highly acid pH and cationic substances should be
avoided. Shows excellent compatibility with acrylic, EVA, SBR, NBR
and polyurethane aqueous dispersions. EMULTROL E-185 TP by
Concentrol is used in adhesives. Complies with FDA regulations.
Product Type Tackifiers > Rosin Esters
Chemical Composition Esterified rosin resin dispersion
Physical Form Liquid
Appearance White
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives
Polymers > Silicones (Si)
Polymers > Ethylene Co-terpolymers - Solids (EVA, EMA)
Polymers > Polyurethanes
Polymers > Acrylics & Acrylic Copolymers
Polymers > Styrene Copolymers (SBR …)
Polymers > Synthetic Rubbers
Polymers > Polyvinyl Acetate Emulsions & Derivatives (PVAc)
Food contact approval Yes
Bio Based Yes
Bio Based Content Comments Rosin ester
EMULTROL E-185 TP Properties
Property Value & Unit
Test Condition Test Method
Density 1.01 - 1.03 kg/l

Active material content 52.5 - 54.5 %

Viscosity @ 20ºC (RV8, spindle 3, 50 r.p.m.) < 1500 cps
pH 8-9
Boiling point 100 °C
Tackifier recommended proportion 20 - 40 %
Particle equal to or larger than 0.1 mm < 0.01 %

Stability (sedimentation after 15 minutes, 3500 r.p.m.) <1%

Acid Index < 25 mg
KOH/ g residuum
Softening point (R & B) 80 - 90 °C

Cleartack® W 100
Cray Valley (Total Group)
Cleartack® W 100 is a water white pure aromatic hydrocarbon resin.
Acts as a tackifier. It is produced by cationic polymerization of pure
styrenic monomers, mainly alphamethylstyrene. Used in hot...
Cleartack® W 100
Technical Datasheet | Supplied by Cray Valley (Total Group)
Cleartack® W 100 is a water white pure aromatic hydrocarbon resin.
Acts as a tackifier. It is produced by cationic polymerization of pure
styrenic monomers, mainly alphamethylstyrene. Used in hot melt
adhesives and sealants.
Product Type Tackifiers > Hydrocarbon Resins > Aromatics
Chemical Composition Hydrocarbon resin
Physical Form Solid
Appearance water-white
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives > Hot melts
Sealants
Food contact approval Yes
Bio Based No
Cleartack® W 100 Properties
Property Value & Unit
Test Condition Test Method
Softening point, R&B 100 °C
Coloration (50% in toluene) < 60 Hazen
Acid number < 0.1
Saponification number < 1.0
Specific gravity @ 25°C 1.05 - 1.07
Molar weight Mn 750 g/mol
Molar weight Mw 1400 g/mol
Glass transition temperature 50 °C
Solubility Properties Element
Test Condition Test Method
Soluble in aromatic hydrocarbons
Soluble in aliphatic hydrocarbons
Insoluble in ethanol
Insoluble in glycols

Cleartack® W 110
Cray Valley (Total Group)
Cleartack® W 110 is a water white pure aromatic hydrocarbon resin.
Acts as a tackifier. It is produced by cationic polymerization of pure
styrenic monomers, mainly alphamethylstyrene. Used in hot...
Cleartack® W 110
Technical Datasheet | Supplied by Cray Valley (Total Group)
Cleartack® W 110 is a water white pure aromatic hydrocarbon resin.
Acts as a tackifier. It is produced by cationic polymerization of pure
styrenic monomers, mainly alphamethylstyrene. Used in hot melt
adhesives and sealants.
Product Type Tackifiers > Hydrocarbon Resins > Aromatics
Chemical Composition Hydrocarbon resin
Physical Form Solid
Appearance water-white
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives > Hot melts
Sealants
Food contact approval Yes
Bio Based No
Cleartack® W 110 Properties
Property Value & Unit
Test Condition Test Method
Softening point, R&B 110 °C
Coloration (50% in toluene) < 60 Hazen
Acid number < 0.1
Saponification number < 1.0
Specific gravity @ 25°C 1.05 - 1.07
Molar weight Mn 850 g/mol
Molar weight Mw 1600 g/mol
Glass transition temperature 60 °C
Solubility Properties Element
Test Condition Test Method
Soluble in aromatic hydrocarbons
Soluble in aliphatic hydrocarbons
Insoluble in ethanol
Insoluble in glycols

Cleartack® W 120
Cray Valley (Total Group)
Cleartack® W 120 is a water white pure aromatic hydrocarbon resin.
Acts as a tackifier. It is produced by cationic polymerization of pure
styrenic monomers, mainly alphamethylstyrene. Used in hot...
Cleartack® W 120
Technical Datasheet | Supplied by Cray Valley (Total Group)
Cleartack® W 120 is a water white pure aromatic hydrocarbon resin.
Acts as a tackifier. It is produced by cationic polymerization of pure
styrenic monomers, mainly alphamethylstyrene. Used in hot melt
adhesives and sealants.
Product Type Tackifiers > Hydrocarbon Resins > Aromatics
Chemical Composition Hydrocarbon resin
Physical Form Solid
Appearance water-white
Product Status COMMERCIAL
Applications/ Recommended for
Adhesives > Hot melts
Sealants
Food contact approval Yes
Bio Based No
Cleartack® W 120 Properties
Property Value & Unit
Test Condition Test Method
Softening point, R&B 120 °C
Coloration (50% in toluene) < 60 Hazen
Acid number < 0.1
Saponification number < 1.0
Specific gravity @ 25°C 1.05 - 1.07
Molar weight Mn 950 g/mol
Molar weight Mw 2000 g/mol
Glass transition temperature 70 °C
Solubility Properties Element
Test Condition Test Method
Soluble in aromatic hydrocarbons
Soluble in aliphatic hydrocarbons
Insoluble in ethanol
Insoluble in glycols

Cleartack® W 130
Cray Valley (Total Group)
Cleartack® W 130 is a water white pure aromatic hydrocarbon resin.
Acts as a tackifier. It is produced by cationic polymerization of pure
styrenic monomers, mainly alphamethylstyrene. Used in hot...

Cleartack® W 140
Cray Valley (Total Group)
Cleartack® W 140 is a water white pure aromatic hydrocarbon resin.
Acts as a tackifier. It is produced by cationic polymerization of pure
styrenic monomers, mainly alphamethylstyrene. Used in hot...

Rositene 653
Crowley Chemical
Pine rosin. Contains neither dipentene nor benzene. Used as a
tackifier...

Deotack® LRE
DOG Chemie
Deotack® LRE by DOG Chemie is a liquid rosin ester resin. Acts as a
polar tackifying resin with low odor. It is soluble in esters, aliphatic
solvents, acetone or petroleum but insoluble in water and...

CRYSTAZENE 110
DRT
CRYSTAZENE 110 by DRT is water-white, odorless, highly stabilized
terpene modified tackifying resin. It exhibits outstanding thermal
stability. It is compatible with ethylene/vinyl acetate...

DERCOLYTE A 115
DRT
DERCOLYTE A 115 by DRT is alpha pinene terpene resin, used as a
tackifier. It is designed for use in hot-melt pressure sensitive adhesives
based on SIS or SBS. It is also used in solvent-based...

DERCOLYTE A 125
DRT
DERCOLYTE A 125 by DRT is alpha pinene terpene-based tackifier. It
is suitable for the formulation of solvent-based and pressure-sensitive
hot-melt adhesives based on SIS or SBS. DERCOLYTE A 125...

DERCOLYTE L 120
DRT
DERCOLYTE L 120 by DRT is delta limonene-based polyterpene
resin, used as a tackifier. It is suitable for formulations of high-quality
gum bases for chewing gum (based on butyl rubber). DERCOLYTE L...

DERCOLYTE LTG
DRT
DERCOLYTE LTG by DRT is a low-VOC, low softening point,
polyterpene resin-based tackifier. This additive is produced from the
polymerization of terpenes. It is recommended to plasticize and to...

Struktol LT 356 and Struktol LT 357 are part of a new

generation of tackifier dispersions with a very fine particle size and are
well suited for high performance applications, e.g. water-based adhesive
systems.

STRUKTOL® LT 357
Aqueous dispersion of hydrocarbon resin
35 % active material
S. P.: 50 °C
Effective, general purpose Tackfier
Usage:
Water based adhesive systems
NR, IR, SBR and other latex types

STRUKTOL® LT 357-C
Aqueous dispersion of hydrocarbon resin
35 % active material
S. P.: 50 °C
Effective, general purpose Tackfier
Complies with 21 CFR 177.2600 (FDA) and 21 CFR 175.105 (FDA)
(Max. concentration must be considered)
Usage:
Water based adhesive systems
NR, IR, SBR and other latex types

STRUKTOL® LT 395
Aqueous dispersion of rosin ester resin
45 % active material
S. P.: 52 °C
Effective, general purpose Tackfier
Usage:
Water based adhesive systems
NBR, ABS, NR and other latex types

STRUKTOL® LT 395-C
Aqueous dispersion of rosin ester resin
45 % active material
S. P.: 51 °C
Effective, general purpose Tackfier
Complies with 21 CFR 177.2600 (FDA) and 21 CFR 175.105 (FDA)
(Max. concentration must be considered)
Usage:
Water based adhesive systems
NBR, ABS, NR and other latex types

STRUKTOL® VP 4459
Aqueous dispersion of hydrocarbon resin
45 % active material
S. P.: 50 °C
Effective, general purpose Tackfier
Usage:
Water based adhesive systems
CR, NR and other latex types
STRUKTOL® VP 4471-C
Aqueous dispersion of alkylphenol resin
35 % active material
S. P.: 70 °C
Effective, general purpose Tackfier
Higher softening point
Usage:
Water based adhesive systems
NR, IR, SBR and other latex types
The Nature and Action of Tackifier Resins
Derek W. Aubrey1
1London School of Polymer Technology, Polytechnic of North
London, London N7, England
Abstract

A good tackifier resin appears to require a combination of high T9

at low molecular weight, and for this a highly condensed alicyclic
structure appears to be desirable. Except for the rosin derivatives,
the chemical structures of common tackifier resins are not fully
resolved and some more definitive studies are needed. In addition,
a high degree of miscibility of resin with rubber is important.
Although some common tackifier resins cause phase separation
over certain concentration ranges when blended with rubbers, this
is probably exceptional, and it seems likely that most adhesive
compositions are single phase in this respect. Where phase
separation does occur, there is a need for fuller elucidation of the
phase morphology and composition of the phases. The widely held
view that a two-phase morphology is necessary for the
development of high tack appears to be incorrect. The few studies
which have been carried out so far indicate that the surface energy
of a rubber is modified only slightly by the incorporation of a
tackifier resin. It is unlikely that this surface energy change can
seriously affect the tack value as measured by the common form of
probe test. The viscoelastic behaviour of rubber-resin blends
provides an adequate explanation for the phenomenon of tack.
Over long response times, the low modulus (high compliance) of
the blend compared with that of the rubber alone allows a high
degree of intermolecular contact to be achieved during the bonding
stage of a tack test. Over short response times, corresponding to
the de-bonding stage of the test, the blend shows transition zone
response with high energy dissipation and consequent high
separation force. For further progress in our understanding,
however, there is a need to distinguish clearly between the bonding
and debonding effects of the resin and for a more definitive study
of the factors controlling the bonding stage.
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Using Hydrogenated Rosin Resins to Optimize
Adhesive Formulations
This article is the second in a series designed
to address the fundamentals of adhesive and
sealant formulation.

Editor's note: This is the second in a series of

articles designed to address the fundamentals of adhesive and sealant
formulation. See ASI June 2005 for the previous installment.

The growing demand for ultra-clear tapes and labels, as well as the
increased use of plastic parts in automobile design and manufacture, has
made formulating adhesives more difficult. Many of these substrates
present unique adhesion challenges. In addition, adhesives for these
higher-end uses require excellent clarity and long-term color stability.
These demanding criteria necessitate using well-designed tackifiers to
meet these stringent requirements.

Formulating adhesives with hydrogenated rosin resins can help enhance

adhesion to difficult substrates while maintaining the color, clarity, heat
and age stability of the adhesives. These resins also help to achieve
strong long-term adhesion with the right balance of cohesion, creating
superior properties. This article offers a brief look at the characteristics
of hydrogenated rosin resins, and discusses the core benefits of
formulating these resins into high-
performance adhesives.

Figure 1. Thermal Stability (Color)

of a Hot-Melt Adhesive
A Stable, Compatible Resin
Rosin and rosin derivatives have long been produced and remain
excellent tackifiers for adhesives. They offer three important
formulation benefits: compatibility with a variety of polymers, which
provides formulation flexibility and reliability; the ability to be
chemically tailored to provide unique adhesive performance; and they
are derived from a renewable, natural source.

Although rosin resins are highly susceptible to oxidation, they can be

stabilized through hydrogenation. Hydrogenation reduces oxygen
uptake in the resin and produces a tackifier with significantly lighter
color. These more thermal and oxidatively stable rosin-derived resins
extend the life of hot-melt adhesives (HMA).

Eastman's Foralyn and Foral E

rosin resins are hydrogenated to
provide these important properties.
In addition, Foralyn rosin resins
are further processed to reduce
their odor. This can be important
during both adhesive production
and use.

Table 1. Influence of Hydrogenation on Adhesion

Why Use Hydrogenated Rosin Resins?

In formulating adhesives for difficult substrates, formulators need a
tackifier that achieves the optimum combination of adhesion and initial
clarity, oxidation, and thermal- and long-term aging stability, as well as
the right resin/polymer compatibility. Resin/polymer compatibility
determines the strength of the adhesive bond to the substrate, and initial
clarity, color, and aging stability are key indicators of adhesive quality.

Simple rosin esters offer excellent adhesion to many surfaces but do not
have the stability and clarity that end users require. Conversely,
hydrogenated hydrocarbon resins provide good clarity and stability, but
do not adhere well to low-energy surfaces. Hydrogenated rosin resins
provide an optimum combination of adhesion, clarity and stability.
These benefits translate into important production and performance
attributes for formulating higher-end adhesives for plastic assembly and
other uses.

Thermal stability enables resins to sustain high temperatures for longer

periods of time, increasing the processing window of an HMA from 24
hours to as much as 96 hours, thus reducing adhesive waste. Heat
stability also prevents gel formation during processing and on
production gluing equipment, thus eliminating an expensive and time-
consuming process that can slow worker productivity and increase
equipment downtime.

The degree of hydrogenation for a resin used in a hot-melt pressure-

sensitive adhesive (HMPSA) determines thermal and color stability.
Figure 1 shows that, at processing temperatures of 175°C, highly
hydrogenated rosin resins exhibit no char or gel formation, and less
color degradation over time, than non-hydrogenated resins.

Table 2. Influence of Hydrogenation

on Cohesion
Managing Compatibility with
Hydrogenation
The degree of hydrogenation of a
rosin resin also determines the
compatibility of resins with various polymers, and therefore the
resulting strength of their adhesive and cohesive bonds. The high
polarity and low molecular weight of these resins, as compared to other
tackifiers, give strong grip with good cohesive performance,
particularly on low-surface-energy substrates such as PP and PE. Due to
their aliphatic character, hydrogenated rosin resins are compatible in all
ethylene-vinyl-acetate (EVA) types and amorphous poly-alpha olefins
(APAOs), styrene-isoprene-styrene- (SIS), styrene-butadiene-styrene-
(SBS), and polyisobutylene- (PIB) based adhesives, as well as in
popular acrylic adhesives.

Tables 1-2 show the overall impact of hydrogenation on adhesion and

cohesion. These tables highlight Foralyn and Foral E hydrogenated
rosin resins, formulated into an HMPSA formulation used for specialty
tape applications. The figures show equal or better adhesion than non-
hydrogenated resins, and excellent cohesive performance at higher
temperatures.

Formulating for block copolymers is a particular challenge because they

exhibit two glass-transition temperatures - one for the mid-block and
one for the end-block. Again, hydrogenated rosin resins are an excellent
formulating choice because their range of compatibility helps balance
adhesive and cohesive properties in block copolymers.

As shown in Table 3, in styrene block copolymer- (SBC) based

adhesives, the high mid-block compatibility of the hydrogenated resin
results in excellent adhesion, initial tack and optimum wetting out. The
low end-block compatibility results in excellent cohesion with better
shear resistance and a slightly higher viscosity at higher processing
temperatures. An SBC-based PSA formulated this way, such as a
repositionable adhesive for automobile carpets (known as a "peel and
stick" application), would produce a clear adhesive with strong grip and
enough cohesive strength to allow the repositioning of a poorly
positioned carpet with no detrimental effects.

Formulating adhesives for difficult substrates, such as polyethylene or

foams, can be tricky. Formulators should consider a tackifier resin that
exhibits good wetting out, good thermal stability and the right
polymer/resin compatibility to ensure strong adhesive and cohesive
perfor-mance, as well as manufacturing ease. Hydrogenated rosin resins
are an excellent choice for such formulations because they offer a
reliably strong bond.
 Table 3. Hydrogenated Rosin
Resins Improve Adhesion in
SBC-Based PSA
Conclusion
Hydrogenated rosin resins, such
as Foral E and Foralyn, provide
adhesive formulators with a
powerful combination of stability
in processing and end-use
application. Their compatibility and adhesion characteristics prove
useful in formulating a variety of high-performance adhesives for
difficult substrates.
19. Resin Dispersions and their Role
 IIIIII IIIIIIII IIlll llllllllllllllllllllllllllllll
111111111111111111
c19 ) United States US 20070135542Al
c12 ) Patent Application Publication c10 ) Pub. No.: US 2007/0135542 Al
Boonstra et al. (43) Pub. Date: Jun. 14, 2007

(54) EMULSIFIERS FOR USE IN WATER-BASED Publication Classification

TACKIFIER DISPERSIONS
(51) Int. Cl.
(76) Inventors: Lykele Jan Boonst r a, Hoof dplaat (NL); COSJ 3/ 02 (2006.01)
Clazina Cor nelia Adriana Adr laanse, C09D 11/ 02 (2006.01)
Heinkenszand (NL); Michaela (52) U.S. Cl. 524/270; 106/238
Hofbauer , Roosendaal (NL); Joost
Huber t Maas, Rotterdam (NL)

Correspondence Address:
(57) ABSTRACT
Tammye L. Taylor
Eastman Chemical Company
P.O. Box 511 Anionic emulsifiers based on rosin acid or derivatives
Kingsport, TN 37662-5075 (US) thereof, and to methods of preparing said emulsifiers. The
emulsifiers are useful for preparing tackifier dispersion s
(21) Appl. No.: 11/604,497
having improved properties with respect to foam stability.
(22) Filed: Nov. 27, 2006 As such , said tackifier dispersions are advantageously used
in water-based adhesives providing improved adhesive and
Related U.S. Application Data cohesive properties. The adhesives may be used for labels on
any kind of surface , packaging applications, flooring adhe•
(60) Provisional application No. 60/748,669, filed on Dec. sives, road markings or f or any type of water-based tapes,
8, 2005. barrier coatings or sealants.
Patent Application Publication Jun. 14, 2007 US 2007/0135542 Al

Figure 1
US 2007/0135542 Al
1
EMULSIFIERS FOR USE IN WATER-BASED
TACKIFIER DISPERSIONS
[0001] This application claims benefit of
provisional application entitled, EMULSIFIERS FOR
USE IN WATER• BASED TACKIFIER DISPERSION S,
Ser. No. 60/ 748,6 69, filed Dec. 8, 2005, in corpor ated by
ref erence herein.
FIELD OF THE INVENTION
[0002] The present invention generally pertains to the
field of emulsifiers and to the preparation of stable
dispersions therewith.
BACKGROUND OF THE INVENTION
[0003] Emulsifiers (a term underst ood to be
synon ym ous with the term "surf act ant" for the
purposes of the present invention ) provide stability
and prevent coalescence of particles formed durin g
emulsifica tion . Emulsifiers further• more prevent the
coagulation or aggregation of particles in the final
dispersion . Due to their amphiphilic ch aract er,
emulsifier molecules have an affinity for both oil and
water phases. As a result, a balance exists be tween
emulsifier molecules present at the oil-water interf ace
and molecules present in the oil and water phases. In
the context of the present in vention , the f unction ality
of the inventive emul• sifiers is primarily discussed in
the context of tackifier dispersions. However, it is
understood that the inventive emulsifier may readily
be used to decrease the viscosity and/or impr ove
emulsification of any other conceivable dispersion s.
DESCRIPTION OF RELATED PRIOR
ART
[0004] U.S. Pat. No. 2,194,429 relates to a process for
the production of condensation products on the basis
of resin alcohols and resin amines suit able as
assistants in the lacq ue r and other in dustrie s. The
product obtained accordin g to U.S. Pat. No. '4 29
comprises an abietinyl moiety con• nected to a (poly)
oxyalkyl or oxyalkyl ether m oie ty. The link between
abietinyl moiety and the chain is lim ited to an ether
linkage. The length of the ether chain is seen as
increasin g water suitability and thus the general
use f uln ess of the compounds for formin g dispe rsions.
U.S. Pat. No.
'429 describes the functionalization of the f ree
termin al
hydroxyl group with sulphonating agents. U.S. Pat. No.
'429 is primarily concerned with providing softening
agents in lacquers.
[0005] U.S. Pat. No. 5,13 7,572 describes an
emulsifier molecule consisting of a tall oil rosin aci d
moie ty, a phos• phate functionality and a hydrocarbon
oxide portion. The total quantity of oxide units in the
emulsifier according to U.S. Pat. No. '572 range s
be tween 50-10 0. The large number of oxide units is due
to the use of the emulsifier to create mixing grade
asphaltic emulsions. The disclosure of U.S. Pat. N o.
'572 is limited to preparing said asphaltic emul• sion s.
[0006] U.S. Pat. No. 6,2 74,657 relates to a surf actant
for formin g stable dispersions of rosin esters
com patible with elastomeric latexes. The surf actant has
the formula R 1-R 2 -
R3. R 1 and R 3 are each rosin (i. e. rosin, a rosin dimer
or a
mixture of rosin and rosin dimer). R2 is se lected from
the group consisting of polyethylene glycol and
modified PEG
Jun. 14,2007
material with polyethylene glycol. These com pounds
are used to stabilize rosin esters in tackifier dispe rsions.
[0007] All sur f act ants as described in U.S . Pat. N o.
'657 are non-ionic and water-sol ubility is achieved by
introd uc• ing particularly long PEG chains (i. e., by
having a large number of ethylene oxide units). A
similar in vention is described in U.S . Pat. No.
5,552,519 , which also relates to a non-ionic surf actant
based on a rosin acid moiety wherein the hydrophilic
functionality is provided by high molecular weight
polyethylene glycol ch ains.
[0008] A m ajo r concern in the production of water-
base d tackifier dispe rsion s is the form ation and the
st ability of foa m. "Foam " can be regarded as air
bubbles stabiliz ed by emulsifier molecules that are
present in the water phase. Stable foam can lead to the
form ation of coarse particles in the dispe rsion . The
course particles are of ten the result of desiccation and
may lead to filter blockage. Coarse particles also m ay
induce dewetting of a film of the final prod uct
comprising the dispe rsion as applied on a substrate,
thus causing holes in the final coating on the substrate.
Foam form ation induce d by re cycle flows in coatin g
processes is also undesirable because air bubbles m ay
cause holes in the final coating. Re cycling of a coa tin g
applied to a su bstrate is common in the
labe li ng/pa ck agin g in dust rie s and in evitably brings the
product in contact with air- e ven if the adhesives and/or
the tackifier dispersions were formulated in the
absence of air.
[0009] Foam form ation needs to be avoided, limited
or broken down to minimize these and other potential
draw• backs. Among other f actors, breakdown of foam
is influ• enced by the stability of air/liquid interf ace s
an d the rate at which air bubbles move to the su rface of
the dispersion due to prevailing density differen ce s. The
latter can be controlled by adju stin g the overall
viscosity of the dispe rsion . In general, the foa min g
behavior im prov es, i. e. less foam is pr od uce d, as the
viscosity of the dispersion is reduce d.
[0010] Water-based tackifier dispe rsion s as known
from the prior art typically comprise alkyl phenol or
alk yl alcohol ethoxylated anionic emulsifiers.
Dispersion s prepared with these emulsifiers are limited
with respe ct to their foamin g behavior and/or their total
solids content and/or their particle size. In general, at
le ast on e of the followin g problems occurs using these
emulsifiers: either foamin g is observed or the solid
content is not high enough or the particles are too large.
The use of these emulsifiers known from the prior art
typically leads to in crease d foam form ation upon
in creasin g the solid content of the dispe rsion .
[0011] The characteristics of emulsifiers can also
have a significant effect on the cohesive and adhesive
properties of adhesives. This is particularly true for
water-based adhe• sives. Anionic emulsifiers known
from the prior art, in particular alkyl phenol or alkyl
alcohol ethoxylated anionic emulsifiers, are known to
act as plasticizers and theref ore decrease the coh esive
stren gth of adhesives. Other sur fac• tants known f rom
the prior art tend to be non-ionic and are theref ore not
well suited for water-base d dispe rsion s with impr oved
foaming ch aracteristics.
[0012] Further, emulsifiers containing alk yl
ph enol ethoxylates are gradually being phased out of
adhesives and other applications, due to the toxicity an d
oestrogenic activ• ity of these compounds. Thus, there
remains a need in the art to provide emulsifiers that are
US 2007/0135542 Al
2
[0013] There also remains a need in the art to provide
emulsifiers that can be used for preparing tackifier disper•
sions that are not as limited with respect to total solids
content and/or particle size as dispersions using emulsifiers
known from the prior art in particular prior art dispersions
comprising commonly used alkyl phenol or alkyl alcohol
ethoxylated anionic emulsifiers. Ideally, increased solid con•
tent and/or decreased particle size should be achieved while
still obtaining a reasonable foaming behavior.
[0014] Lastly, there remains a need in the art to provide
tackifier dispersions to be used in adhesives, that avoid the
disadvantages of the prior art while providing improved
cohesive strength of the adhesives and/or to improved
adhesion on a substrate.
BRIEF SUMMARY OF THE INVENTION
[0015] The present invention relates to novel emulsifiers
and to the preparation thereof . The invention further relates
to the application of said emulsifiers to prepare novel
water-based tackifier dispersions.
[0016] One aspect of the present invention pertains to
emulsifiers for use in tackifier dispersions. The emulsifiers
include at least one rosin acid moiety or at least one rosin
acid derivative moiety, a polar chain attached to said rosin
acid or rosin acid derivative, and an anionic head group
attached to the polar ch ain, wherein the polar chain com•
prises at le ast two repeating units comprising at least one
carbon-oxygen bond in at least one repeating unit.
[0017] Another aspect of the present invention pertains to
water-based tackifier dispersions. Said water-base d tackifier
dispersions according to the present invention comprises at
least one emulsifier according to the invention in combin a•
tion with water and at le ast one of the followin g tackifiers:
(i) at le ast one rosin ester, (ii) at least one hydrocarbon resin,
for example, a C 5 -C 9 hydrocarbon resin, (iii) at least one low
molecular weight acrylate, or (iv) at least one terpene resin.
Suitably, any mixture of two or more of these tackifiers, or
of one of these tackifiers with another tackifier may be used.
[0018] A further aspect of the present invention pertains to
the use of these water-based tackifier dispersions, in com•
bination with elastomeric latexes. For example , the water•
based tackifier dispersions according to the present inven•
tion may be used in combination with acrylic polymers or
styrene butadiene rubber (SBR), to prepare water-based
adhesives. The adhesives according to the present invention
may be employed in the f ollowing field s: labels on any kind
of surf ace , packaging applications, flooring adhesives, road
markings or any type of water-based tapes, barrier coatings
or sealants.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 illustrates the equilibrium of the emulsifier
molecules present in the tackifier dispersions.
DETAILED DESCRIPTION OF THE
INVENTION
[0020] The present invention may be understood more
readily by ref erence to the f ollowing detailed description of
the invention and to the Examples included therein.
[0021] Bef ore the present compositions of matter and
methods are disclosed and described, it is to be understood
Jun. 14,2007
that this invention is not limited to specific synthetic meth•
ods or to particular formulations, unless otherwise indicated,
and, as such, may vary from the disclosure. It is also to be
understood that the terminology used is for the purpose of
describing particular embodiments only, and is not intended
to limit the scope of the invention.
[0022] The sin gular forms "a", "an", and the "the" include
plural ref erents, unless the context clearly dictates other•
wise.
[0023] Optional or optionally means that the subsequently
described event or circumstances may or may not occur. The
description in cludes instance s where the event or circum•
stance occurs, and instances where it does not occur.
[0024] Ranges may be expressed herein as from about one
particular value, and/or to about another particular value.
When such a range is expr essed, it is to be understood that
another embodiment is from the one particular value and/or
to the other particular value, along with all combinations
within said range.
[0025] Throughout this application, where patents or pub•
lications are ref erenced, the disclosures of these references
in their entireties are intended to be incorpor ated by ref er•
ence in to this application, in order to more fully describe the
state of the art to which the invention pertains.
[0026] The present in vention provides an emulsifier that
improves the foaming behavior of dispersions, in particular
tackifier dispersions. Without being bound to any theory, one
reason why this improved foamin g behavior may be
achieved can be attributed to a reduction in dispersion
viscosity. This reduction in the viscosity of the water phase
is schematically illustrated in FIG. 1. The left panel of FIG.
1 represents a tackifier particle. As illustrated, an equilib•
rium exists between emulsifier molecules (prevailing as
individual molecules or as micelles) present in the tackifier
oil-ph ase , emulsifier molecules present at the tackifier oil•
water interface and emulsifier molecules present in the
water-phase.
[0027] The emulsifiers of the present invention may also
be functionalized to have an in creased affinity for
the oil-water interf ace. This results in a decrease of
emulsifier molecules present in the water-ph ase. As a
consequence, a different equilibrium as shown in the right
panel of FIG. 1 arises. Since fewer emulsifier molecules
are present in the water-phase, the viscosity of the water-
phase is reduced thus leadin g to a reduced viscosity of
the dispersion overall. Furthermore, since fewer emulsifier
molecules are present in the water-phase fewer molecules
are available f or st abilizin g air-water interface s. Stabilized
air-water interfaces can be seen as one reason for
incr eased foam production and foam st ability. Thus, without
being bound by any theory the emulsifiers of the present
invention may im prove the foam• ing behavior of
dispersions prepared therewith by provid in g anionic
emulsifiers that have a decreased tendency to be present
in the water phase due to the inclusion of a hydro• phobic
moiety.
[0028] The emulsifiers of the present in vention may com•
prise a hydrophobic rosin acid moiety or a derivative
thereof . Attached thereto, the emulsifier comprises a polar
chain consisting of at le ast two repeating units comprising at
least one carbon-oxygen bond. The oxygen atoms of the
polar chain contribute to the hydrophilic functionality of the
US 2007/0135542 Al
3
(overall) amphiphilic emulsifier. Attached to the other end of
the polar chain, the emulsifier further comprises an anionic
head group thus rendering the overall emulsifier anionic.
The anionic head group also contributes to the hydrophilic
character of the amphiphilic emulsifier.
[0029] Another aspect of the present invention relates to
the adhesive characteristics of adhesive formulations pre•
pared with the inventive tackifier dispersions. Adhesion is a
surf ace phenomenon and therefore may be affected by the
choice of emulsifier present in the adhesive. Generally,
emulsifiers have a tendency to migrate to the interface
between air and adhesive. Therefore, emulsifiers may
change the surface properties and adhesion energy of the
adhesive. This invention relates to the effect according to
which adhesive properties of adhesives comprising a (water•
based) tackifier dispersion ( comprising anionic emulsifiers)
can be significantly influenced by the type of emulsifier
used. The presence of viscosity altering emulsifiers may also
have an effect on the cohesive properties of the adhesive.
[0030] Some relevant technical terms as used in the con•
text of the present invention are meant to be understood as
follows (unless spe cifically indicated otherwise throughout
the description).
[0031] "Adhesion" (or adhesive properties) in the mean•
ing of the present invention relate(s) to the interaction of the
adhesive formulation with the substrate to which it is
applied. Characteristically, adhesive f orce s mainly concern
the interf ace between adhesive and substrate. Suitable tests
to measure adhesion are, f or example, the "loop tack" test
and the "peel strength" test. These tests are described in the
FINAT Technical Handbook, 6th edit ion , 2001.Loop tack is
measured according to FIN AT Test Method (FTM) 9 (page
22 et seq. of the Handbook). Peel Strength is measured
according to FTM 1 (page 6 et seq. of the Handbook).
[0032] "Cohesion" (or cohesive properties) in the meaning
of the present invention relates to in teraction/f orce s within
the adhesive. Typically, cohesive for ces mainly concern the
bulk phase of the adhesive. A suitable test to measure
cohesion is the "shear cohesion" test. Shear Cohesion is
measured according to FTM 8 (page 20 et seq. of the
Handbook).
[0033] A "rosin acid" according to the present invention
relates to an entity that has the f ollowing molecular back•
bone:
R1 COOR
[0034] In one embodiment, R 1 -R 4 each may be any alkyl
group, such as, for example ethyl or methyl. In another
embodiment, the structure comprises two conjugated double
bonds. In a further embodiment, the rosin acid
molecule
comprises 20 carbon atoms. Structural isomers of this back•
bone are suitable as well.
Jun. 14,2007
[0035] At least one of the three rings may be aromatic. A
"rosin acid" accordin g to the present invention is understood
to also comprise a mixture of various rosin acid molecules.
Mixtures of this kind that are readily available and occur in
nature in clude, but are not limited to, tall oil rosin, gum rosin
or wood rosin. These natural mixtures may comprise rosin
acids of the abietic type and/or the pimaric type such as
abietic acid, palustric acid, neoabietic acid, levopirmaric
acid, pimaric acid, isopimaric acid or dehydroabietic acid,
among others, in varying amounts. Any such mixture is
considered a rosin acid as long as at least one of the
molecules of the mixture has the above described rosin acid
backbone, or a structural isomer thereof .
[0036] In addition to rosin acids with one carboxylic acid
function ality, rosin acids with two or more carboxylic acid
functionalities are also considered as rosin acids in the
meaning of the present invention.
[0037] A "rosin acid derivative" according to the present
invention is any molecule that has the molecular rosin acid
backbone as described above but is mod ified in at least one
of the f ollowing ways. In one embodiment, at least one
double bond is hydrogenated (hydrogenation). In another
embodiment, at le ast one of the rings of the rosin and
backbone is dehydrogenated so that an aromatic ring results
(dehydrogenation). In a further embodiment, the carboxy•
functionality of the rosin acid is mod ified, for example into
an alcohol functionality (for example: methylated and
hydrogenated gum rosin is converted to Abita! by means of
hydrogenolysis). In another embodiment, the carboxy-f unc•
tionality is modified into an amide funct ionality. In yet
another embod iment, adducts to the conju gated double
bonds of the rosin acid backbone are included, in particular
the addition of maleic anhydride in a Diels-Alder type
reaction. The resulting adduct is considered one type of a
rosin acid derivative according to the present invention.
[0038] A "rosin ester" according to the present invention
is any molecule in which at least two rosin acid or rosin acid
derivative units are connected by means of at le ast one ester
linkage. Any molecule with at least two hydroxyl groups can
be used to provide the ester linkage between at least two
rosin acids units. Common examples include, but are not
limited to, glycerol esters, penta erythritol esters and (tri•
ethylene) glycol esters.
[0039] The "solid content" of a tackifier dispersion
is given in % weight per overall weight of the
dispersion (unless indicated otherwise). A test protocol
illustratin g how to measure the solid content is given in
the "Examples" section.
[0040] "Water-based" tackifier dispersion s according to
the present invention are dispersions of tackifier entities
wherein the solvent is generally water or an aqueous solu•
tion. However, mixtures of water with a non-aqueous sol•
vent, in particular an organic solvent, would also be suitable
as lon g as the foaming properties or other dispersion prop•
erties are not negatively affected. Mixtures of water with
other water-soluble solvents could also be used as well.
Emulsifiers According to the Invention
[0041] In one embodiment of the present invention, the
emulsifier molecule comprises at least the following func•
tional entities (moieties):
US 2007/0135542 Al
4
[0042] at least one rosin acid moiety or at least one rosin
acid derivative moiety,
[0043] a polar chain attached to said rosin acid or rosin
acid derivative,
[0044] an anionic head group attached to the polar
chain.
[0045] Mixtures of two or more types of emulsifier mol•
ecules of this structure are also an emulsifier according to the
present invention.
[0046] The rosin acid (derivative) moiety is seen as
imparting hydrophobic (lipophilic) character on the emulsi•
fier molecule . The polar chain and the anionic head group
are both seen as imparting hydrophilic (lipophobic) charac•
ter on the emulsifier molecule.
[0047] In one embodiment of the present invention, the
hydrophobic moiety is a rosin acid. When a rosin acid is
used as the hydrophobic moiety, low viscosity values
together with good f oaming behavior and a particle size
below 250 nm can be obtained. If a rosin acid is used as the
hydrophobic moiety and the polar chain comprises oxygen,
the resulting linkage between the hydrophobic moiety and
the polar chain is typically an ester linkage.
[0048] In another embodiment, the rosin acid is obt ained
from a naturally occurring source such as tall oil rosin, gum
rosin or wood rosin. Fractions or mixtures of these sources
may be used as well. The mixtures may be a combination of
two or more of the natural products with each other or the
natural products may be mixed with purified or synthetically
produced rosin acids as well. No limitations exist with
respect to the degree of hydrogenation, dehydrogenation or
variation of any of the "R" groups of the rosin acid as long
as the carboxyl-f unction ality remains intact for at le ast some
of the molecules.
[0049] In another embodiment, the carboxyl f unction ality
of the rosin acid is converted into a hydroxyl functionality,
for example by hydrogenolosis of a methylated rosin acid.
[0050] In another embod iment, the polar chain comprises
a repetition of at le ast two units comprising at le ast
one carbon atom linked to at least one oxygen atom , i. e. at
least one carbon-oxygen bond per repeating unit . For
example, a unit consisting of ethylene oxide (EO), i. e. ----
C2 H4 ---0- , would be suit able thus resulting in
polyethylene oxide
chains. The polar chain does not need to be terminated by a
group containing oxygen or to exclusively comprise C, 0
and H atoms. Amine terminated polar chains would be
suit able as well. Block copolymers, for example compr ising
polypropylene blocks and polyethylene blocks ("pluronics")
are also seen as polar chains according to the present
invention.
[0051] In a further embodiment, the polar chain comprises
about 2 to 50 (repeating) units. For example , about 3 to 20
units or about 4 to 20 units may be used. Likewise, about 4
to 15 units, or about 4 to 11 units, or even about 5 to 9 units
would be suitable accordin g to the present invention.
[0052] The number of units forming the polar chain of the
emulsifier may have an effect on the size of the
tackifier particles in the dispersion generated with the
emulsifier. A sm all particle size is generally favor able f or
the following reasons. First , the smaller the tackifier
particles, the less lik ely the particles will settle
gravitationally thus destabi• liz ing the dispersion. Tackifier
dispersions prepared with the inventive emulsifier with the
proper length of the polar chain
Jun. 14,2007
can be stable f or years. Next, a sm all tackifier particle size
may le ad to an in cr eased overall surf ace area thus bindin g
more emulsifier molecules to the oil phase and reducing the
emulsifier content in the water phase. This should lead to a
reduced viscosity of the overall dispersion. Lastly, it has
been f ound that tackifiers with large particle siz es may lead
to incr easin gly poor f oamin g behavior . For polyethylene
oxide chains, it has been found that the smalle st particle size
of tackifiers in the dispersion can be achieved when using
emulsifiers with polar chains having EO units in the range
from about 4 to about 15. For example, from about 4 to about
11 units or from about 5 to about 9 units would be suitable.
[0053] With respect to the anionic head group, any group
that imparts a (partial) negative charge to the end group of
the polar chain is suit able . For example, the end group of the
polar chain could be functionalized with a mineral acid such
as a (poly) phosphoric or a sulphuric acid . For phosphory•
lation, oxides or halogenides, such as phosphorous pe ntaox•
ide (P2 0 5) , phosphorous trichloride (PC13 ) or phosphorous
oxyc hloride (POC1 3 ) may be employed. F or sulf ation, the
corresponding sulfuir oxides or halogenides may be used. In
another embodiment, the polar chain may be modified to
result in a carboxylic acid functionality (e.g . esterification).
Any method would be acceptable accordin g to the present
invention provided that the head group renders an anionic
emulsifier.
[0054] Using an anionic head group in the context of the
present in vention appears to provide repulsive electrost atic
for ces that prevent particle agglom eration/coagulation.
Using an anionic head group also may allow for shorter
polar chains in the present invention as compared to emul•
sifiers known in the prior art since not all of the hydrophilic
character needs to come from the (long) polar chain.
[0055] The hydrophobic moiety according to the pr esent
invention, for example , the rosin acid (derivative) moiety,
may lead to an emulsifier that has an increase d affinity for
hydrophobic tackifiers such as rosin esters, hydrocarbon
resins, or mixtures thereof , as compared to emulsifiers
comprising hydrophobic parts as known f rom the prior art
such as, for example, alkyl phenols or alkyl alcohols.
[0056] Providing an emulsifier with a rosin acid (deriva•
tive) hydrophobic moiety may theref ore be seen as improv•
ing the selectivity of the emulsifier for the oil-water interface
in tackifier dispersions, thus resulting in a decrease of
emulsifier molecules present in the water phase of the
water-based tackifier dispersion . As a consequence , the
viscosity of the water phase may be reduced. Theref ore, the
viscosity of the overall dispersion may also be reduced.
Tackifier Dispersion According to the Invention
[0057] The tackifier dispersion accordin g to the present
invention comprises water, at least one emulsifier as
described above and at least one of the following tackifiers:
at least one rosin ester or at least one hydrocarbon resin or
at le ast one resin produced from vinyl aromatics mon omers
such as styrene, indene, alpha-methyl styrene, divinylben•
zene, divinylbenzene with one or more alkyl groups, at least
one terpene resin or any mixture of at le ast two of these
tackifiers.
[0058] For example , at least one of the tackifiers can be a
rosin ester. In this embodiment the structural similarity
between the rosin ester and the rosin acid moiety used in the
emulsifier may decrease the migration of the emulsifier to
the surface. Migration potentially may be detrimental to the
adhesive properties of adhesives comprising said emulsifier.
US 2007/0135542 Al
Suitably, in embodiments where a hydrocarbon resin is used
as a tackifier, alone or in a mixture with a rosin ester, C5 -C9
hydrocarbon resins may be used.
[0059] In one embodiment of the present invention, the
rosin ester may have an acid number (i. e. a number given
in mg of KOH necessary to neutralize 1 g of the acid) of less
than 25. In another embod iment, the hydrocarbon resin has
a weight-averaged molecular weight ranging from about 200
to about 20,000 g mole " , f or example, from about 4,000 to
.
about 7,000 g mole- 1
[0060] In another embodiment, at least one tackifier of the
tackifier dispersion may have a sof tenin g point ranging from
about - 30° C. to about 160° C., such as f or example, ranging
from about 20° C. to about 120° C. [as measured according
to the "ring-and-ball" method of ASTM E28-99 (2004)
Standard Test Method for sof tenin g point of resins derived
from naval stores by ring-and-ball apparatus].
[0061] The average particle siz e of the tackifiers in
the tackifier dispersions as discussed above is suitably less
than about 2 µm. For example, the average particle size
of the tackifier is less than about 1 um, or even less than
about 500 nm. In another embodim ent, the average particle
size of the tackifiers is less than about 250 nm. Generally,
particle sizes and particle size distributions are measured
with (laser) light scattering methods.
[0062] In a further embod iment, the tackifier dispersion s
have a Brookfield viscosity of less than about 300 mPa ·s or
less than about 250 mPa s. Generally, viscosities are mea•
sured with a Brookfield LVT Viscometer. Emulsifiers with
higher viscosities are covered by the present invention as
lon g as the foam behavior is acceptable and the solid content
is within the specified ranges.
[0063] The solid content of a tackifier dispersion accord•
ing to the present invention suitably ranges from about 50%
to about 70% by weight, such as for example from about
55% to about 65% by weight.
Adhesive Formulation According to the Invention
[0064] The in ventive emulsifiers as applied to tackifier
dispersions according to the present invention result in
improved cohesion and adhesion properties of water-based
adhesives prepared with said tackifier dispersions. For
example, such adhesives can be advantageously used in the
labe ling and packaging industries, for water-based sticky
tapes, road markings and flooring applications. In the af or e•
mentioned applications, the adhesive is pressure-sensitive.
Other applications, in which the adhesive is not pressure
H 11.... �
O - ll_
+ ' o1 <:> Un.... H
Jun. 14,2007
5
sensitive, are included as well. Such applications
include,
but are not limited to barrier coatings or sealants.
[0065] In another embodiment of the present invention,
the tackifier dispersion using the inventive emulsifier can be
used to prepare an adhesive formulation. The adhesive
formulation comprises at least one tackifier dispersion as
described above and at least one polymer component. In
general, the polymer component is an elastomeric compo•
nent in cluding elastomeric latexes, such as acrylics or sty•
rene-butadiene rubber. Other polymers suitable for use with
the tackifier dispersions according to the present invention
include but are not limited to:
[0066] suspensions of natural rubber,
[0067] acrylic polymers derived from 2-ethylhexyl
acrylate, butyl acrylate, methyl methacrylate, meth•
acylic polystyrene,
[0068] acid, and acrylic acid or mixtures thereof ,
[0069] styrene-butadiene copolymers,
[0070] polymers derived from vinyl acetate, such as
ethylene vinyl acetate,
[0071] poly chloroprene, or
[0072] acrylonitrile-butadiene copolymers.
[0073] Any mixture of two or more of these polymers
could suitably be used as well.
[0074] In order to prepare the inventive wet adhesive
formulation (i.e . water-base d), a tackifier dispersion accor d•
ing to the present invention and latex may be blended.
Generally, the adhesive formulation consists of about 15% to
about 50 % of tackifier, such as f or example about 20% to
about 40% (based on dry weight).
Exemplary Methods of Preparing the Emulsifier According
to the Present Invention:
[0075] Schematic synthesis routes for preparing nonionic
intermediates and anionic emulsifiers according to the
present invention based on polyethylene oxide chains as the
polar chain are described by way of example in the follow•
ing:
[0076] (I) Possible Synthesis Route: Esterification Route:
[0077] (a) esterif ying rosin acid with excess polyethyl•
ene glycol (PEG);
[0078] (b) separation of intermediate product (A) from
step (a) from unreacted PEG;
T- 280- 290'
C.
30-50 hrs
(A)
US 2007/0135542
Al
[0079] (c) reaction of product from step (b) with a
mineral or carboxylic acid to arrive at anionic emulsi•
fier; here, (poly) phosphoric acid is used.
[0080] The primary molecular structure of the anionic
emulsifier comprising a hydrophobic rosin acid based part is
shown schematically in the following:
[0081] The product mixture may also contain low amounts
of di-phosphate ester and free phosphoric acid (20-60 mole
%), among others. Purification steps as necessary may be
perfor med according to st andard methods known from the
prior art.
[0082] (II) Alternate Synthesis Route: Ethoxylation Route:
[0083] (a) a rosin acid derivative is prepared by con•
version of the carboxyl-group to a hydroxyl group
[0084] (b) ethoxylation of hydroxyl functionality with
ethylene oxide (EO), to arrive at a polyethylene oxide
chain;
Lr.'o KOH
+ n
[0085] (c) raw product is vacuum stripped to remove
unreacted EO;
[0086] (d) reaction of intermediate product (B) from (c)
with a mineral or carboxylic acid, here: polyphosphoric
acid.
[0087] While the ethoxylation of a rosin acid derivative is
described here, a rosin acid may be used as well.
The
Jun. 14,2007
6
primary molecular structure of the anionic emulsifier com•
prising a hydrophobic hydroxyl modified rosin acid moiety
is shown schematically in the following:
[0088] This product mixture may also contain low
amounts of di-ph osph ate ester and free phosphoric acid
(20-60 mole% ), among others. Purification steps as neces•
sary may be performed accordin g to st andard method s
known from the prior art.
[0089] The typical product according to both routes is a
semi-solid, becomes liq uid at elevated temperatures and has
a moderate solubility in water. Typically, in its salt -f orm, the
product has good water solubility.
[0090] In one method of preparing the nonionic interme•
diate (A) according to the esterification route, rosin acid
(mixtures) is/are reacted with a molar excess of polyethylene
glycol in the presence of at le ast one metal oxide catalyst.
Typically, the reaction temperature is from about 270° C. to
about 290° C. The reaction is pref erably conducted under
inert nitrogen con ditions. Generally, polyethylene glycol as
used in this method has a number-averaged molecular
weight ranging from about 10 0 to about 1,000 g mole " ,
such as for example from about 200 to about 500 g mole- 1 .
[0091] Typical reaction times are about 30 hours, reaching
a conversion rate between about 90 and about 99%. In one
embodiment, unreacted polyethylene glycol is removed
from the intermediate reaction product by repeated water•
diethyl ether extractions. In another embodiment, less than
about 2% by weight of NaCl is added to the water in order
to obtain a good phase separation in the extraction steps.
Typically, about five extraction steps are needed to reach a
polyethylene glycol level of l ess than about 2% by weight in
the intermediate nonionic product . If the PEG chain is made
lon ger than about 7 EO units, unwanted solubility of the
nonionic intermediate is f ound; on the other hand, if the PEG
chain is made shorter than about 5 EO units, significant
unwanted solubility of PEG in ether is found.
[0092] In another embodiment, the molar ratio of rosin
acid to polyethylene glycol ranges from about 1:2 to about
1:10 , such as f or example, from about 1:3 to about 1:7. By
further example, a ratio of 1:5 is also suitable.
[0093] An alternative method of preparing the nonionic
intermediate comprises the reaction of a rosin acid or of a
rosin acid derivative having at le ast one hydroxyl function•
ality with ethylene oxide, or a molecule with similar func•
tionality (ethoxylation). This reaction is typically conducted
in the presence of a catalytic amount of KOH. In addition,
the reaction is carried out at temperatures between about
US 2007/0135542
Al
160° C. to about 190° C., preferably under inert nitrogen
conditions. Further, a pressure from about 4 to about 5 bar
is generally applied. One advantage of this method over the
esterification route described above is that the extraction
steps are not nece ssary, thus not limitin g the number of EO
units.
[0094] The anionic emulsifier accordin g to the pr esent
invention may be prepared by reaction of the
nonionic intermediate (A) or (B), or of a mixture thereof , as
described above, with a mineral acid, a carboxylic acid or
any mixture thereof .
[0095] In another embodiment, (poly) phosphoric acid
may be used. Equivalents of polyphosphoric acid are typi•
cally expressed in % phosphoric acid. This can be con verted
into an equivalent mass of P4 0 10 . This equivalent mass can
react with an equivalent mass of hydroxyl. In this case the
molecular ratio of hydroxyl to P4 0 10 suitably ranges
from about 5:1 to about 1:5 such as for example about
3:l(which corresponds to an excess of hydroxyl).
[0096] If phosphorylation is employed, the phosph oryla•
tion step pref erably comprises the slow addition of poly•
phosphoric acid to the nonionic intermediate (A) or (B), or
a mixture thereof , at a temperature ranging from about 60°
C. to about 70° C.
[0097] Polyphosphoric acid is added at timed intervals
ranging f rom about 1 to about 90 minutes, such as for
example from about 10 to about 70 minutes. In one embodi•
ment, the reaction temperature may be increased to about
10 0° C. f or 3 to 4 hours after the addition of polyphosphoric
acid.
[0098] Accordin g to the present invention, with respect to
manuf acturin g of the emulsifier, ethoxylation may be used
instead esterification due to the money-saving omission of
extraction steps. It is also suitable to ethoxylate a rosin acid
rather than a rosin acid derivative to provide ester linkages
rather than ether linkages. Overall, the suit able methods of
manuf acturin g the emulsifier according to the present inven•
tion may comprise at least one of the following steps: (a)
ethoxylation of at least one rosin acid with ethylene oxide;
(b) reaction of the intermediate product f rom (a) with a
mineral or a carboxylic acid.
Exemplary Method of Preparing Tackifier Dispersions
Using the Emulsifier according to the present invention.
[0099] In one embodiment to arrive at tackifier dispersions
based on the emulsifiers according to the present invention,
said tackifier dispersion s may be prepared according to a
batch inversion process.
[0100] In another embod iment, the tackifier, or a tackifier
mixture, may be heated approximately 10 to 30° C. above
the softening point of the tackifier/the mixture of tackifiers.
The emulsifier according to the present invention then may
be added to said tackifier/tackifier mixture. In a further
embodiment, the emulsifier may be added together with a
neutralizing agent. Suitable neutralizing agents include
NaOH, KOH or triethanol amine.
[0101] In a further step, water may be slowly added to the
tackifier mixture under agitation until phase inversion is
reached. In one embodiment, the resulting emulsion is
further diluted to the desired total solid content. The result•
ing dispersion is then slowly cooled under gentle agitation .
Jun. 14,2007
7
[0102] The amount of emulsifier added to the tackifier is
suit ably between about 4 to 5 about 9 parts, such as, for
example, from about 5 to about 8 parts, per 100 parts
tackifier, respectively (in parts per weight). The amount of
neutralizing agent added is adju sted in a manner so that the
final dispersions have pH values ranging from about 4 to
about 10 or from about 6 to about 8.
[0103] This in vention can be further illustrated by the
following examples of potential embodiments thereof ,
although it will be understood that these examples are
included merely f or the purposes of illustration and are not
intended to limit the scope of the invention unless otherwise
specifically indicated.
EXAMPLES
Example 1
Preparation of Intermediate Product A
(Esterification)
[0104] An electrically heated 2 liter glass reactor,
equipped with agitator, thermocouple, nitrogen inlet and
Dean-Stark trap with cooler, was charged with Gum Rosin
(Eastman Chemical Com pany, Middelburg, NL) and poly•
ethylene glycol (PEG300; Aldrich Chemical Company Mil•
waukee, Wis.) with a number average molecular weight of
300 in a molar equivalent ratio of COOH:OH =1:10. The
mixture was heated under inert nitrogen conditions to 180°
C. and 0.01 % ZnO (based on the weight of Gum Rosin) was
added as esterification catalyst. The mixture was further
heated to 290° C. and water was continuously distilled off.
[0105] The reaction mixture was allowed to react until a
conversion of at least 90% was reached. Typical reaction
times were between 25 and 30 hours. The raw intermediate
was cooled to ambient and dissolved in diethyl ether. 100
parts raw product was dissolved in 80 parts diethyl ether. 67
parts of an aqueous NaCl-solution (2% by weight) were
added to the solution. The mixture was vigorously sh aken in
a separation funnel and left to stand until two or three
separate layers were obtained. The aqueous layer, con taining
residual PEG300 and NaCl, was removed. This procedure
was repeated four times with the original diethyl ether
solution , until at le ast 98% of the residual PEG300 was
removed from the adduct. Diethyl ether was removed, using
a rotation film evapor ator, at a temperature of 70 to 80° C.
under reduced pressure (100 to 200 mbar) until no diethyl
ether vapors could be determined.
Example 2
Preparation of Intermediate Product B
(Esterification)
[0106] The procedure of Example 1 was repeated
by replacing PEG 300 by polyethylene glycol (PEG200;
Ald• rich Chemical Company Milwaukee, Wis.) with a
number average molecular weight of 200.
Example 3
Preparation of Intermediate Product C
(Ethoxylation)
[0107] A 1 liter autoclave, equipped with agitator, ther•
mocouple, nitrogen inlet and pressure gauge was heated to
US 2007/0135542 Al Jun. 14,2007
8

approximately 85° C. and charged with 300 g Abita! E
(Eastman Chemical Company, Middelburg, NL) and 0.3 g
KOH-powder. Agitation was st arted at 50 0 rpm . The react or
was inerted three times with nitrogen. The mixture was
heated to 180° C. Ethylene oxide (generally 5, 7, 9 or 11
moles) was continuously added to the reactor in about 16
hours, using a dosing vessel pressurized to 5 bars. The
pressure in the reactor was 4.7 bars. The mixture was
allowed to react overnight. The reactor was inerted three
times with nitrogen and cooled to ambient temperature and
discharged. The pref erred molar ratio Abita! E:E O is 1:7.
Example 4
Preparation of Anionic Emulsifiers
[0108] An electrically heated 250 ml three-neck glass
reactor, equipped with agit ator, thermocouple , nitrogen inlet,
dropping funnel and cooler, was ch arged, in separate
batches, with the intermediate products from Examples 1, 2
and 3 and heated to 120 to 140° C. Traces of water were
removed under reduced pressure (200 to 400 mbar) and
nitrogen purge until the adduct had a water content less than
500 ppm. The adduct was cooled to 80° C. and polyphos•
phoric acid (115% H3P04; Aldrich Chemical Company
Milwaukee, Wis.) was slowly added in the equivalence ratio
OH:P 4 0 10 =3:1. An exotherm of about 10 ° C. was observed.
After addition of the polyphosphoric acid, the reaction
temperature was in creased to 10 0° C. and left to react for 3
to 4 hours. The progress of the reaction was monitored by
determining the titration curve.
Example 5
Example 1 (nonionic intermediate), Example 4 (anionic
surf actant) and Example 5 (dispersion). Dispersion C is like
dispersion A and B except that the dispersion has been
obtained according to Example 6 described below. Disper•
sion Di s Example 3-Example 4-Example 5. Dispersion Ei s
Example 3-Example 4-Example 6 and Dispersion F is
Example 2-Example 4-Example 5.
Example 6
Preparation of Tackifier Dispersions-3.5 kg scale
[0111] In a 4 liter electrically heated, st ainless steel reac•
tor, equipped with a ribbon type of agitator and a scraper,
moving in opposite directions, 10 0 parts of Precursor 105
resin (Eastman Chemical Company, Middelburg, NL) was
heated to approximately 10 0° C. 7 parts of
surfact ant (obtained f rom Example 4) and 20% sod ium
hydroxide were added to the molten resin. The weight ratio
of surf actant and sodium hydroxide were chosen in such
way that the pH of the final dispersion was between 6 and
7. The mixture was homogenized f or one minute with an
agitation speed of 150 rpm . The agitation speed was
increased to 250 rpm. Hot water was slowly added at a
rate of 50 g/min. The tempera• ture dropped to
approximately 90° C. until the system inverts to a
water-in-oil dispersion . Generally, inversion takes place
when between 10 and 20% water is added (based on the
weight of r esin). The dispersion was further diluted to the
desired solid content at a rate of 100 g/min. The
dispersion was then cooled to ambient and disch arged f rom
the react or. The resulting dispersions have a pH between 6
and 7 and a mean particle sizes between 200 and 300 nm.

Preparation of Tackifier Dispersions-200 g scale
[ 0109] A stainless steel beaker was charged with 100 parts
of Precursor 10 5 resin (Eastman Chemical Com pany, Mid•
delburg, NL) and heated to approximately 100° C. 6 to 8
parts of surfact ants (obtained f rom example 4) and 20%
sodium hydroxide were added to the molten resin. The
weight ratio of surf actant and sodium hydroxide were cho•
sen in such way that the pH of the final dispersion
was between 6 and 9. The mixture was reheated to a
temperature between 90 and 100° C. The agitation spe ed
was incr eased to 1800 rpm and hot water was slowly added
to the viscous mixture until the systems in verted to a
water-in-oil disper• sion. The dispersion was further diluted
to the desired solid content. The dispersion was then cooled
to ambie nt. The resulting dispersions have a pH between 6
and 9 and a mean particle sizes between 200 and 300 nm.
[0110] Properties of different dispersions are summarized
in table 1. Dispersions A and B have been prepared from
[0112] Properties of different dispersions are summarized
in table 1 (see Example 5).
Example 7
Preparation of Pressure Sensitive Adhesives
[0113] Acrylic latex (Acronal V215, obtained f rom BA SF
AG, Ludwigsh af en, D) and the tackifier dispersions from
example 5 and 6 were blended and le ft to stand overnight.
The resulting wet adhesive for mulation had a resination
level of 25% (based on dry weight). The wet adhesive
formulation was coated on silicon release paper (90 gsm)
and dried in a preheated oven for 60 se conds at a tempera•
ture of 110 ° C. The adhesive coating was then transf erred on
a paper backing (78 gsm; Crown van Gelder) and stor ed for
one night (at 23° C. and 50% RH). Adhesive properties, like
loop tack , peel strength and shear cohesion were measured.
The measurements were performed accordin g to FINAT
Standard Methods.
[0114] Adhesive properties are summarized in table I

TABLE I
Shear
Solid Brookfield Loop Peel Peel Cohesion
Particle Content LVT Viscosity Foam Tack to strength strength to steel
dispersion'" Linkage ? pH Size (nmr" (wt) (cP)4> bchavior'" PE (N) 6l to PE(N) 7) to CB (N)7l (hrs) 8)
%) 3
A Ester 7.0 240 125 +++ 13 17 15 21
B 58.9 280 ++ 12 16 16 10
c Ester
Ester 6.3
6.9 230
205 370 +++ 12 17 13 9
60.7
Ethe 59.2 390 ++ 11 15 12 10
D
r 6.4 280
60.9
US 2007/0135542 Jun. 14,2007
Al 9

TABLE I-continued

Shear
Solid Brookfield Loop Peel Peel Cohe sion
Particle C ontent LVT Visc os ity Foam Tack to strength strength to
stee l dispe rsion'" Linkage ? pH Size (nm r " (wt% ) 3 l (cP) 4 > be havior'? PE (N)6 l to PE (N )7 > to CB
(N)7 >
(hrsj'" E Ether 6.4 240 58.8 240 ++9) 10 16 12
9
F Est er 8.8 250 54 .2 18 0 ++ 10 15
27
Prior art10 > 6.8 19 0 50.2 700 ++ 11 16 11
0 >see Exampleprior
5 forartdetails of the manufacture of the respective dispersions
6.8 200 54 .8 250 + 11 11
1 >chemical linkage between hydrophobic and hydrophilic moiety.
10
2
>Determined by laser scattering (Horiba LA -900)
3 >Determined by method as described in "Example Section" (Labwave 9000)
4 >Brookfield LVT Viscosity: All measurements were performed at 60 rpm and spindle
2.
5 >+ - moderate foam behavior (free of air within 24 hours)

++ - good foam behavior (free of air within 16 hours)

+++ - excellent foam behavior (free of air within 8 hours)
6
lFJNAT Test Method 9; PE - polyethylene substrate
7 lFJNAT Test Method 1; CB - card board
8 lFJNAT Test Method 8
9 >Dispersion shows excellent foam behavior when diluted to a solid content of 55%
10
>prior art emulsifiers to prepare dispersion are phosphate esters of nonyl phenol
Test Method for Measuring the Solid Content ofTackifier in
ethoxylates What is claimed is:
a Tackifier Dispersion 1. An emulsifier for use in a tackifier dispersion compris•
ing:
[0115] The method for measuring the total solids content
of resin dispersions as used in the context of the (i) at least one rosin acid moiety or at least one rosin acid
prese nt description makes use of a Lab Wave 9000 derivative moiety,
Microwave.
(ii) a polar chain attached to the rosin acid or rosin acid
[0116] Accordin g to the test method, the sample is ana• derivative, and
lyzed by using the method of Constant Weight. The sample
is dried until a constant weight is achieved. Dryness is (iii) an anionic head group attached to the polar chain,
specified by defining a maximum acceptable weight loss wherein the polar chain comprises at least two repe at•
over a spe cified time interval. During the specified time ing units comprising at least one carbon-oxygen bond
interval, when the loss is equal to or less than the loss as in at least one repeating unit.
specified, the analysis stops and results are calculated. The 2. The emulsifier according to claim 1, wherein
Constant Weight procedure permits analysis of a sample the number of repeating units in the polar chain ranges
without prior knowledge of the required drying time. from about 3 to about 20.
[0117] Parameters Constant Weight 3. The emulsifier according to claim 1, wherein
the number of repeating units in the polar chain ranges
from about 5 to about 9.
Microwave Power: 75% (487.5 Watt; 100% equals 650 4. The emulsifier according to claim 1, wherein
Watt max. output)
Time interval: 10 seconds the repeating unit is an ethylene oxide unit.
Weight loss differentia l: 0.1 mg 5. The emulsifier according to claim 1, wherein the polar
Maximum nm time: 10 minutes
chain is attached to the rosin acid or rosin acid derivative
Balance set points
moiety via an ester linkage.
Minimum weight: 1 gram 6. The emulsifier according to claim 1, wherein the rosin
Maximum weight: 2 gram acid or rosin acid derivative is obtained from a tall oil rosin,
gum rosin or wood rosin or f rom mixtures or fractions
thereof .
[0118] In drawings and specification there have been dis• 7. The emulsifier according to claim 1, wherein
closed typical preferred embodiments of the invention and, the anionic head group is introduced into the emulsifier
although specific terms are employed, they are used in a by at least one of the following methods: phosphorylation,
generic and descriptive sense only and not for purposes of sulf a• tion or carboxylation.
limitation, the scope of the invention being set forth in the 8. A tackifier dispersion for use in an adhesive f ormulation
following claims. comprising:
[0119] The invention has been described in detail with (i) water,
particular ref erence to pr ef erred embod iments thereof , but it
will be understood that variations and mod ifications can be (ii) at least one emulsifier according to any one of claims
effected within the spirit and scope of the invention. 1-7 and
US 2007/0135542
Al
(iii) at least one of the following tackifiers: (a) at least one
rosin ester or (b) at least one hydrocarbon resin or (c)
at least one resin produced from vinyl aromatics mono•
mers such as styrene, indene, alpha-methyl styrene,
divinylbenzene, divinylbenzene with one or more alkyl
groups or (d) at least one terpene resin or (e) a mixture
of at least two of these tackifiers or one of these
tackifiers with at least one other tackifier.
9. The tackifier dispersion according to claim 8, wherein
the tackifier comprises a rosin ester with an acid number of
less than about 25.
10. The tackifier dispersion according to claim 8, wherein
the tackifier comprises a hydrocarbon resin with a chain
length ranging from C5 to C9 .
11. The tackifier dispersion according to claim 8, wherein
the average particle size of the tackifiers in the
tackifier dispersion is less than about 2 µm.
12. The tackifier dispersion according to claim 8, wherein
the average particle size of the tackifiers in the
tackifier dispersion is less than about 1 µm.
13. The tackifier dispersion according to claim 8, wherein
the average particle size of the tackifiers in the tackifier
dispersion is less than about 500 nm.
14. The tackifier dispersion according to claim 8, wherein
the average particle size of the tackifiers in the tackifier
dispersion is less than about 250 nm.
15. The tackifier dispersion according to claim 8, wherein
the solid content of the tackifier dispersion ranges from
about 55% to about 65% by weight.
Jun. 14,2007
10
16 . An adhesive formulation comprising at least one
tackifier dispersion accordin g claim 8 and at least
one polymer component.
17. The adhesive formulation according to claim 16,
wherein the polymer component is an elastomeric latex.
18 . The adhesive f ormulation accordin g to claim 17 ,
wherein the elastomeric latex is se le cted from the group
consisting of acrylic polymers, styrene-butadiene copoly•
mers, suspensions of natural rubber, or polymers derived
from vinyl acetate, poly chloroprenes or acrylonitrile-buta•
diene copolymers.
19. The adhesive formulation according to claim 16,
wherein the adhesive formulation consists of about 20% to
about 40% of tackifier based on dry weight.
20. A method for manufacturing the emulsifier of claim 1
comprising:
(a) ethoxylating at least one rosin acid with ethylene
oxide;
(b) reacting the intermediate product of (a) with at least
one mineral acid and/or at least one carboxylic acid.
21. An adhesive f or attaching labels onto any kind of
surf ace; for packaging applications, for flooring applica•
tions, for road marking; or for any type of water-base d tapes,
barrier coatings or sealants comprising the adhesive f ormu•
lation of claim 16.
* * * * *
 IIIII IIIIIII Illllllllllll lllll l lllllllllllll lllllllll
111111111111111111
US006900274B2
(12) United States Patent (10) Patent No.: US 6,900,274 B2
Ruckel et al. (45) Date of Patent: May 31, 2005

(54) TERPENE RESIN-AND 4,857,563 A * 8/1989 Croft et al. 523/173

HYDROCARBON RESIN-BASED 5,268,399 A 12/1993 Wouters et al. 523/336
5,552,519 A 9/1996 Hemmings et al. 530/216
SURFACTANTS AND AQUEOUS 5,674,823 A * 10/1997 Ricca et al. 510/102
DISPERSION OF TACKIFIER RESINS 6,274,657 Bl 8/2001 Geoghegan et al. 524/270
6,369,146 Bl 4/2002 Lassila et al. 524/310
(75) Inventors: Erwin R. Ruckel, Wilton, CT (US); 6,461,728 B2 10/2002 Weiss et al. 428/345
Kerry L. Thompson, Savannah,
GA (US); George L. Gergely, Jr., FOREIGN PATENT DOCUMENTS
Richmond Hill, GA (US) EP 0 088 510 A2 9/1983
FR 961575 5/1950
(73) Assignee: Arizona Chemical GB 2273294 A 6/1994
Company, GB 2288179 A 10/1995
Jacksonville, FL (US) JP 2002-11337 A 1/2002
( *) Notice: Subject to any disclaimer, the term of this WO WO 00/30591 6/2000
patent is extended or adjusted under 35
U.S.C. 154(b) by O days. OTHER PUBLICATIONS
Esp@cenet Database abstract for JP 2002-11337. Available
(21) Appl. No.: 10/360,585 from ep.espacenet.com.
(22) Filed: Feb. 6, 2003 * cited by examiner
(65) Prior Publication Primary Examiner-Peter Szekely
Data (74) Attorney, Agent, or Firm-Thomas W. Barnes, III
US 2004/0158003 Al Aug. 12, 2004
(57) ABSTRAC
(51) Int. Cl.7 C08F 8/46; C08F 32/00; T
C091 145/00 A process for preparing a surfactant, useful for dispersing
(52) U.S. Cl. 525/333.3; 524/270; 524/499; tackifier resins in aqueous media, comprises reacting an
525/210; 525/211; 525/327.4; 525/327.9; a �-unsaturated carboxylic acid or anhydride, or an ester
428/355 R
thereof , with a terpene- or hydrocarbon-based resin to form
(58) Field of 524/270, 499;
an adduct, then reacting the adduct with a polyalkylene
Search 525/210---211, 285, 327.4, 327.9, 333.3;
polyol to yield the surfactant. In a related embodiment, the
428/355 R
surfactant is subsequently functionalized. Also disclosed are
(56) References Cited surfactants prepared using a disclosed process; compositions
comprising a disclosed surfactant and a tackifier resin;
U.S. PATENT DOCUMENTS aqueous dispersions comprising a disclosed surf actant;
tackifier resin and water; adhesive compositions comprising
2,993,880 A 7/1961 Aldridge et al.
3,965,059 A * 6/1976 Kerridge et al. 525/416 a disclosed aqueous dispersion and a polymer latex; and
4,382,128 A 5/1983 Li pressure sensitive adhesive overlays prepared using a dis•
4,477,613 A 10/1984 Evans et al. 524/77 closed adhesive composition.
4,670,504 A 6/1987 Cardenas et al. 524/504 58 Claims, No
Drawings
 US 6,900,274 B2
1 2
TERPENE RESIN-AND HYDROCARBON Methods for the self-emulsification of resins have been
RESIN-BASED SURFACTANTS AND described. See, e.g., U.S. Pat. Nos. 4,670,504 and 5,268,399,
AQUEOUS DISPERSION OF TACKIFIER and Great Britain Patent Nos. 2,273,294 and 2,288,179. In
RESINS these methods, a resin is treated so that hydrophilic groups
5 are added to a small portion of the bulk resin. That is, a small
amount of hydrophilic groups are added to a resin, so that
BACKGROUND OF THE INVENTION hydrophilic groups are introduced to a small fraction of the
1. Field of the Invention bulk resin mol ecules. The resin molecules containing these
The present invention generally pertains to hydrophilic groups then act as a surfactant when water, and
surfactants, more specifically, to surfactants useful for 10 optionally some co-solvent, are added to the resin/modified
preparing aque• ous dispersions of tackifier resins, where resin mixture.
the resins may be blended with latex to provide waterborne Accordingly, there remains a need in the art for surfac•
adhesives. tants that are useful for preparing tackifiers that, when
2. Description of the Related Art blended with latex, yield waterborne adhesives, in particular,
15 PSAs, having improved adhesion, improved adhesive sub•
The ongoing development of improved waterborne (i.e.,
water-dispersed) adhesives to replace solvent based adhe- strate wet tability, greater mechanical strength for high-speed
sives has largely been motivated by government regulation coating operations, and an improved shelf-life. The present
of solvents, stemming from the perceived health and envi• invention fulfills these needs and provides further related
ronmental hazards thereof. As a result, waterborne adhesives advantages as described herein.
20
have become extensively used to adhere various substrates
BRIEF SUMMARY OF THE INVENTION
together. Such adhesives often comprise both a high molecu-
lar weight elastomeric latex (or mixture of latexes, such as In brief, the present invention is directed to processes for
acrylic and styrene-butadiene rubber latex), and at least one preparing a surfactant having utility for dispersing resins,
water-dispersed tackifier resin. It is possible to prepare a particularly tackifier resins, in water, where the dispersed
25
functional waterborne adhesive without a tackifier resin. tackifier resin is then used for preparing waterborne adhe•
However, inclusion of the latter is generally required to sives. The present invention is also directed to surfactants
economically produce an adhesive exhibiting an adhesion to prepared using the disclosed processes, as well as to
various substrates that allows for commercial applicability compositions, for example, aqueous dispersions and adhe•
of the adhesive. sive compositions comprising a disclosed surfactant.
30
A significant portion of commercial waterborne adhesives In one aspect, the present invention is directed to a
are pressure sensitive adhesives ("PSAs"). The latter are process for preparing a surfactant. The process includes
used, for example, for adhesive tapes; to adhere labels to the selecting a resin, where the resin comprises the pol ymeriza•
cellulosic, polyolefinic and polar-polymeric substrates of tion residues of monomers, and the monomers are, or
bottles and other packaging containers; and to adhere cabi• 35 include, unsaturated hydrocarbons. The selected resin is
net and wall decorations and the like. reacted with an a,�-unsaturated carboxylic acid, or anhy•
While PSAs generally exhibit good adhesion to a variety dride or ester thereof, to provide a carbonyl-containing resin,
of substrates, their adhesive performance is limited. For also referred to herein as an adduct. The adduct is then
example, the adhesion of PSAs to substrates is generally reacted with a reactive poly(alkylene oxide) to provide a
inferior to that of their solvent-based counterparts. This 40 surfactant of the present invention. This surfactant may be
deficiency may be attributed, at least in part, to the surf actant chemically modified by phosphorylation or sulfation.
used to disperse the tackifier resin or prepare the latex or In one representative embodiment, the present invention
blend of latexes used for the PSA . Surfactants inherently is directed to a process for preparing a surfactant compris•
plasticize polymer-tackifier resin blends, which reduces ing: (1) reacting an a ,�-unsaturated carboxylic acid or
adhesive shear. Also, surfactants of ten impede adhesion by 45 anhydride, or an ester thereof , with a resin selected from the
migrating to the substrate interface, thereby interfering with group consisting of a polyterpene resin, a terpene-phenol
the ability of the adhesive to stick thereto. resin, a terpene-hydrocarbon resin, a hydrocarbon resin, or
Waterborne PSAs are also characterized by a limited shelf a vinylaromatic-modified hydrocarbon resin, to provide an
life, by a limited ability to wet adhesive substrates (i.e., the adduct; and (2) reacting the adduct with a hydroxy•
substrates used to make adhesive tapes, labels, and the like), 50 terminated poly(alkylene oxide) to provide the surfactant. In
and by a mechanical stability that is less than ideal for one related embodiment, the apunsaturated acid is maleic
high-shear and high-speed applications. Extended shelf life acid, and the corresponding anhydride is maleic anhydride
is generally desirable. Exceptional adhesive substrate wet• ("MA"). In another related embodiment, the pol y(alkylene
ting and superior mechanical stability are important for oxide) is polyethylene glycol.
high-speed coating of an adhesive substrate by an adhesive. 55 The present invent ion, in anot her representat ive
High-speed coaters, such as gravure, reverse gravure and embodiment, is directed to a process for preparing a surfac•
slot die coaters, are now commonly used to produce lower tant that comprises the two steps of the above-described
coat weights and allow for increased throughputs. representative embodiment, and further comprises modify•
Again, the surfactant used in preparing the tackifier resin ing the surfactant provided thereby by means of phospho•
dispersion is a limiting factor. Use of nonylphenol-based 60 rylation or sulfation to provide a functionalized surfactant.
surfactants has yielded tackifier resin dispersions and, Further representative embodiments of the present inven•
therefrom, PSAs that exhibit substrate wetting and mechani- tion are directed to the surfactants prepared using the
cal stability that is compatible with the above-mentioned above-described processes; to compositions comprising a
high-speed coating methods. However, governmental regu• disclosed surfactant and a tackifier resin; to aqueous disper•
latory activity has been increasingly directed to nonylphe• 65 sions comprising a disclosed surfactant, a tackifier resin and
nols and their derivatives to reduce or eliminate their pres- water; and to adhesive compositions comprising a disclosed
ence in the marketplace, as well as in chemical plant surfactant, a tackifier resin, a polymer latex and water. A
aqueous effluents.
 US 6,900,274 B2
3 4
related embodiment is directed to a pressure sensitive adhe•
sive article prepared from a disclosed adhesive composition.
These and other aspects of the invention will be evident
upon reference to the following description of the invention.
DETAILED DESCRIPTION OF IBE
INVENTION
In one aspect, the present invention is directed to a
process for preparing a surfactant. The process includes
selecting a resin, where the resin comprises the pol ymeriza•
tion residues of monomers, and the monomers are, or
include, unsaturated hydrocarbons. The selected resin is
reacted with an a,�-unsaturated carboxylic acid, or anhy•
dride or ester thereof , to provide a carbonyl-containing resin,
also referred to herein as an adduct. The adduct is then
reacted with a carboxyl-reactive poly(alkylene oxide), e.g.,
a hydroxyl- or amine-terminated poly(alkylene oxide), or
with an alkylene oxide so as to generate the poly(alkylene
oxide) in situ, so as to provide a surfactant of the present
invention. Depending on its structure, the surfactant may be
chemically modified by phosphorylation or sulfation.
The resin utilized in the process of the present invention
is prepared in whole or part from hydrocarbon monomers. In
one exemplary embodiment the hydrocarbon is a terpene, 25 disclosure directed to making �
and the resulting resin may be, e.g., a polyterpene resin (i.e.,
a resin prepared from terpene as the sole hydrocarbon
monomer), a terpene hydrocarbon resin (i.e ., a resin pre•
pared from terpene as well as non-terpene hydrocarbon
monomer(s)), and a terpene phenolic resin (i.e., a resin 30 Limonene may be obtained as a byproduct of the citrus
prepared from terpene and phenolic compound), where
collectively these resins are referred to herein as "terpene
resins". In one embodiment, the resin is a terpene hydro•
carbon resin, e.g., a terpene vinylaromatic resin. In anot her
embodiment the resin is a terpene phenolic resin. In yet 35 dues from the above terpenes, the residues of various
another embodiment the resin is a polyterpene resin.
Terpene resins that may be used in the process of the
present invention include any resins prepared, in whole or
part, from an unsaturated terpene Cl O hydrocarbon (i.e., a
terpene containing ten carbons), where exemplary terpenes 40 trisubstituted alkenes, vinylcyclohexene, as well as pi p•
incl ude, without limi tation, 1\-2-carene, 1\-3-carene,
dipentene, limonene, myrcene, � -phellandrene, a -pinene,
� -pinene, a-terpinene, y-terpinene, and terpinolene.
In one aspect, the selected terpene resin is prepared, at
least in part, from a -pinene. In another aspect the selected
terpene resin is prepared, at least in part, from � -pinene. In
another aspect, the selected terpene resin is prepared, at least
in part, from limonene. In another aspect, the selected
terpene resin is prepared, at least in part, from a carene. Each
of these terpenes may be obtained from various commercial 50 65 to 35 percent by weight of polymeric units derived from
suppliers, e.g., Aldrich Chemical (Milwaukee, Wis.), Ari•
zona Chemical Company (Jacksonville, Fla.), Millennium
Specialty (Jacksonville, Fla.), International Flavors and Fra•
grances (formerly Bush Boake Allen in Jacksonville, Fla.),
or DRT (Les Derives Resiniques et Terpeniques of Dax,
France) or by transformations such as the isomerization of
a -pinene to dipentene or of 1\-3-carene to 1\-2-carene or the
pyrolysis of � -pinene to myrcene. a-Pinene, � -pinene, 1\-3-
carene and dipentene are of ten ultimately obtained from
trees, particularly pine trees. Limonene can be obtained from 60 presence of a catalyst, e.g., an acid catalyst). Examples of
the citrus processing industry.
In one aspect, the resin is the cationic polymerization
product of a terpene, e.g., it may be prepared by cationic
polymerization of resin-grade � -pinene monomer, limonene
monomer, or a mixture of the two monomers. Cationic 65
polymerization of terpenes may be achieved by treating the
terpene with a Lewis acid catalyst. More specifically,
cata-
lysts that may be used include aluminum chloride (A1Cl 3 )
and boron trifluoride (BF 3 ) and their derivatives (e.g., their
etherates or other solvated form); as well as acidic clays,
antimony halides, strong protic acids such as hydrofluoric
5 acid and sulfuric acid, and titanium tetrachloride. The cata•
lysts may be removed from the resin by any number of
processes known to those skilled in the art. The terpene
resins, so produced, may be further subjected to treatment at
elevated temperature to distill away solvent and remove
10 co-products, and thereby achieve a desired softening point
for the resin.
A preferred terpene from which to prepare a terpene resin
is � -pinene. � -pinene monomer is commonly obtained by
15 distillation of crude sulfate turpentine, which is a by-product
of the paper industry. Resin-grade � -pinene is generally
about 80% by weight � -pinene with much of the remainder
being a-pinene. Higher purity grades of � -pinene, such as
20
the so-called aroma-chemical grade thereof, which is greater
than 90% by weight � -pinene, may also be used in preparing
the terpene resins. See, e.g., U.S. Pat. No. 4,487,901 for
-pinene resin. The resin may
also be prepared from a-pinene (see, e.g., U.S. Pat.
Nos.
4,113,653 and 4.057,682).
Other preferred terpenes are limonene and dipentene.
industry. Dipentene obtained by pyrolysis or catalytic crack•
ing of a-pinene (i.e., racemic limonene) may also be used in
preparing the terpene resins.
The terpene resin may comprise, in addition to the resi•
non-terpenic unsaturated compounds, particularly unsatur•
ated hydrocarbons, e.g., olefins and dienes. Examples
thereof include, but are not limited to: isobut ylene,
diisobutylene, 1-alkenes (e.g., 1-octadecene), 2-alkenes,
erylene and dicyclopentadiene streams obtained from steam
cracking of petroleum distillates. The latter streams gener•
ally include piperylene, isoprene, 2-methyl-2-butene,
2-methyl-1-butene, cyclopentene, an acyclic pentene,
45 cyclopentadiene, and dicyclopentadiene. See, e.g., U.S. Pat.
Nos. 6,121,392 and 3,959,238 for disclosure directed to
resins made from � -pinene and various unsaturated hydro•
carbons.
An exemplary terpene-hydrocarbon resin contains from
dicyclopentadiene and from 35 to 65 percent by weight of
polymeric units derived from ,�pinene. In one aspect, the
molar ratio of the dicyclopentadiene to beta-pinene in the
polymerization reaction starting materials ranges from
55 about
1:2to about 2:1. The polymerization reaction between dicy•
clopentadiene and � -pinene may be a thermal (i.e.,
no
catalyst is employed) or catalyzed (i.e., conducted in the
acid catalysts that may be used include Bronsted acid and
Lewis acid-type catalysts, such as H2 S0 4 , HCl, H3 P0 4 ;
metal halides such as BF 3 , BC13 , A1Cl 3 , A1Br 3 ,
SnCl 4 , ZnC12 , SbCl3 as well as the etherates thereof. In
the
cata• lyzed polymerization process, the amount of catalyst
may range from about 0.1 to about 20 weight percent of
catalyst based on the total weight of reactants to be
polymerized. The polymerization reaction may be carried
out neat (without solvent) at or above the melting points of
the reactants, or can be carried out in the presence of a
solvent. The reaction pressure may vary and range from
about one atmosphere to about 100 atmospheres with a
pressure of from about two
atmospheres to about ten atmospheres being preferred. The
 US 6,900,274 B2
5 6
reaction time of about 1- 8 hours is generally sufficient terpene-derived residues. For example, CS
to achieve a desired molecular weight distribution of unsaturated hydrocarbons may be used to prepare
from about 550 to about 55,000 (weight average suitable hydrocarbon resins. Such resins may be
molecular weight), and a sof tening point ranging from prepared by cationic polyme r- ization of pi perylene
about 10 0 to about 17 0° C. Other limonene-containing 5 streams, obtained by steam cracking of petrol eum
hydrocarbon res- ins include those described in U.S. Pat. distillate s. While the com position of these streams
Nos. 6,357,499 and is quite variable, they generally include cis- and trans-
6,228,944 piperylenes, isoprene, 2-met hyl-2-bytene, 2-methyl-1-
. butene, cyclopentene, acyclic pentanes, cyclopentadiene
Suitable terpene resins that may be used in the 10 and dicyclopentadiene.
above• disclosed process of the present invention Olefinic monomers may be co-reacted with the CS
include, but are not limited to, commercially-available unsat• urated hydrocarbons present in such streams.
terpene resins sold by the Arizona Chemical Company Examples include 1-alken es such as isobutylene and
(Jacksonville, Fla.) desig• nated as SY LVARES® diisobutylene, vinylaromatic monomers such as styrene,
terpene resins M-1115, B-115, 7100, 15 terpenes such as those mentioned above, and mixtures
7115, 7125, 1085, 1100, 1115, 1125, and A- thereof . Also, olefins such as 2-methyl-2-butene may be
25. added to such streams to increase the amount of the
corresponding olefin already present therein. Catalysts
Terpene-vinylaromatic resins (also known as that may be used include Lewis acids such as A1Cl 3 ,
3 3
aromatic
their modified terpene
derivatives, may resins)
be used. that may be used
Acidic for
clays, BF 3 and derivatives thereof.
the above•halides,
antimony disclosed
strongprocess of thesuch
protic acids present invention, 20
as hydrofluoric Another type of the hydrocarbon resin that may
maysulfuric
and be prepared
acid, byandacid catalyzed
titanium polymerization,
tetrachloride, may in alsoa be utilized to prepare a surfactant according to the
suitable solvent, using any of the
be used . The vinylaromatic monomers that may be above-mention ed present invention is prepared using therm al
terpenes
used with buta vinylaromatic
include, are not limited monomer. Lewisindene,
to: styrene, acid polymerization of streams rich in dicyclopentadiene,
catalysts, including and
methylstyrenes, A1Cl para•
and BFalkylstyrenes,
or including 25 including its isomers and derivatives. A ddition ally, these
mixtures thereof. These resins may be post-created with monomers may be thermally co-polymerized with a
iodine or by way of other decolorizing processes. Some mixture of vinylaromatic monomers, such as those listed
specific examples of terpene-vinylaromatic resins, previously, as well as with pure styrene or pure alkyl
suitable for use in the above-disclosed process of the styrenes, such as those mentioned above. The
present invention, are products designated as 30 hydrocarbon resins may be used as prepared, or may
SYLVARES® ZT l OSL T and 5100 resins, sold by the be partially or completely hydrogenated. How ever
Arizona Chemical Company (Jacksonville, Fla.). completely or substantially hydrogenated hydrocarbon
Terpene-phenol resins that may be used for the resins are not pref erred because they can be more
above• disclosed process of the present invention difficult to react to form an adduct. In one aspect of the
("the terpene• phe nol resins") may be prepared by 35 invention, the hydrocarbon resin contains unsaturation,
acid catalyze d polymerization, in a suitable solvent, i.e., contains double and/or triple carbon-carbon
of any of the above• mentioned terpenes with phenol bonds. In another aspect of the inven• tion the
and/or a derivative thereof . This chemistry is well known hydrocarbon resin has not undergone a hydrogena-
in the art. See, e.g., U.S. Pat. Nos. 5,723,566 and tion treatme nt prior to reaction with an a ,�-
5,844,063. Lewis acids, including but not limited to 40 unsaturated
boron trifluoride and derivatives or complexes thereof , carboxylic acid or anhydride or
and strong protic acids such as those listed above, may ester.
be used. The phenolic portion of the terpene phenol Some of the processes that may be used to prepare
resin may be, e.g., phenol itself , or substituted phenols the abo v e - d e s c ri be d te r pe n e , ter pe n e -p h e n ol ,
45
such as, for ex amp l e , m on osubstitute d ph e n ol ter pe n e • vinylaromatic and hydrocarbon resins, are
includ in g monoalkylsubstituted phenol, disubstituted described in the Kirk-Othmer Encyclopedia of Chem ical
phenol including dialkylsubstituted phenol, Technology, Fourth Edition, Volume 13 , pp. 717 - 743,)
trisubstituted phenol including trialkylsubstituted John R 3 ) -C(=O)-OH
C=C(Wiley & Sons, New wheYork, ach .of R 1 , R2 and R 3 is
re e N.Y
phenol, and a naphthalene compound having a 50 The from
selected hydrocarbon
selected hydrogen, halogenresin is reacted
and organic withThus,
groups. an
hydroxyl substituent attached to the ring. a,�•
Non-terpene olefins and dienes that may be used in an a�-unsaturated carboxylic acid has at least one double
unsaturated carboxylic acid, or anhydride or ester thereof,
addition to the terpenes for preparing the terpene-phenol bond between adja cent carbon atoms, wherein at least one of
to provide a carbonyl-containing resin, also referred to
resins, include those listed above for the terpene resins. For these carbon atoms is bonded to a carboxyl group. The term
herein
instance, residues of the following non-terpene olefins and 55 "a,� -unsaturated carboxylic anhydride" simply refers to the
as an adduct. As used herein, "a,�-unsaturated carboxylic
diolefins may be present in the terpene-phenolic resin: anhydrides thereof, which may be mixed anhydrides 1 (i.e.,
acid" refers to compounds that have the structure (R )(R2
vinylaromatics such as styrene, indene, a -methylstyrene, formed from two different carboxylic acids) or may be
divinylbenzene, a divinylbenzene with one or more alkyl homogeneous anhydrides (i.e., formed from two molecules
groups, isobutylene, diisobutylene, a 1-alkene, a 2-alkene, a having the same structure), or may be internal anhydrides
trisubstitut ed alkene, vinylcyclohexane, pipe r yl ene, 60 (i.e., one molecule has two carboxylic acid groups, and those
isop r en e , 2- m e t h yl -2 -b yt e n e, 2-m e t h yl -1- b y ten e , two groups react together to form an anhydride, e.g., maleic
cyclopentene , an acycl i c pentene, cyclope nt adi ene, anhydride).
dicyclopentadiene, and alkylaromatic styrenes. Grafting unsaturated acids and anhydrides onto resins
Some specific examples of terpene-phenol resins, suitable using a thermal condensation process is described in, for
for use in the above-disclosed process of the 65 example, U.S. Pat. Nos. 3,379,663 and 3,953,407. Free
present
Someinvent ion, are resins
hydrocarbon com meuseful
r ci al produ
in thectspreparation
desi gnat ed radical grafting has also been disclosed in U.S. Pat. Nos.
as SYVARES®
surfactants of of theTP present
300, 2040, 2040 HM,
invention may 2019,
have 7042
little and
or 3,279,925; 3,005,800; and 3,161,620. Either of
3523
no resins, sold by Arizona Chemical Company these approaches may be utilized to prepare an
(Jacksonville, Fla.). adduct in the
 US 6,900,274 B2
7 8
process of the present invention. The grafting reaction
may be carried out without solvent at a temperature
ranging from
170° C. to 240° C. Alternatively, a solvent may be
used. Excess, unreacted acid or anhydride may be
removed by, for example, distillation. Reaction time
may vary from 2-24 hours.
In one particular embodiment of the process of the
present invention, the a ,�-unsaturated carboxylic acid
is maleic acid, and the a,�-unsaturated carboxylic
anhydride is maleic
anhydride. Ot her a ,�-unsaturated carboxylic acids
and
anhydrides thereof that may be used for the adduct-
f orming reaction include, but are not limited to,
fumaric, citraconic and it acon i c ac ids and thei r
respective anhydrides .
Furthermore, esters of an a ,�-unsaturated carbox ylic 20
acids
may be used for the adduct-forming reaction. In
general, about 1-30 wt% of the a,�-unsaturated
carboxylic acid is reacted with the resin, based on the
total weight of a,�•
unsaturated carboxylic acid and resin. For instance,
when maleic anhydride is used for the adduct-form ing
reaction, about 1- 30 parts of maleic anhydride are
reacted with 10 0 parts of resin. In various aspects of the
invention, the residue
from the a ,�-unsaturated carboxylic acid or anhydride
or
ester thereof constitutes at least 3 wt %, or at least 4 wt
%, or at least 5 wt %, or at least 6 wt %, or at least 7
wt % of
the weight of the adduct. When the residue from the
a,�-
unsaturated carboxylic acid or anhydride or ester
thereof constitutes less than about 3- 4 wt % of the
adduct weight, the subsequently-f ormed surfactant may
not have enough hydrophilic character to function as a
surfactant. Thus, in
various additional aspects, the residue from the
a ,�-
unsaturated carboxylic acid or anhydride or ester thereof
that is present in the adduct constitutes 3- 30 wt % of the
adduct weight, or 3- 25 wt%, or 3- 20 wt% , or 3- 15
wt% , or 3- 10 w t% , or 4--25 w t % , or 4- 20 w t% , or 4-
15 w t% , or 4- 10 w t% , or 5- 25 w t% , or 5- 20 wt% , or 50 range of 5 and
5- 15 w t% , or 5- 10 wt %, each percent value based on
the total weight of adduct. Such weight measurements
can be made by measuring the weight of the starting
material hydrocarbon resin, and then weighing the
product adduct. The difference is attributed to
the weight contribute d by the residue from the
a ,�-
unsaturated carboxylic acid or anhydride or ester
thereof. When this difference is too small, the adduct
does not have the desired surfactancy characteristics.
In a pref erred embodiment, a terpene resin is rea cted
with maleic anhydride to provide an adduct, and this
adduct is reacted so as to incorporate poly(alkylene oxide)
groups. For instance, the adduct may be reacted with
alkylene oxide, e.g., ethylene oxide, and thereby form
poly(alkylene oxide) directly on the adduct.
Alternativel y, the poly( alkylene oxide) may be formed
separately, and then reacted with the adduct. Methods for
reacting alkylene oxide with a carboxy- lie acid group so as
to convert the acid into the correspond• ing poly(alkylene
oxide) ester, and methods for reacting pol y(alkylene
oxide) with a carboxylic acid group, are both well know n
in the art.
For example, in one aspect the invention, the adduct may
from 1,000- 20,000 that contains repetitive alk ylen e
ether groups. An alk ylen e et her group is
represented by
- R- 0 - where "R" represents a Cc C 6 alkylene
5 group and "O" represents oxygen, where the PAO has
repetitive
- R- 0 - groups, denoted (- R- 0 - )m where R is
inde• pendently selected at each occurrence. A preferred
alkylene group is a C2 alkylene group, i.e., an ethylene
10 group. The PAO has at least one carbox yl-rea ctive
group, e.g., a hydroxyl or amino group. In one aspect,
the PAO has two
carboxyl-reactive groups, where in a pref erred
embodiment both of these carboxyl-reactive groups are
15 hydroxyl groups. Two or more different PAOs may be
reacted with the adduct, where these PAOs may differ in
various ways, e.g ., compo• sitionally in that one PAO
may contain more ethylene oxide residues than anot her
PAO, or by molecular weight in that one PAO may
have a larger average (either number average or weight
average) molecular weight than another PAO.
In one specific embodiment, the PAO is
polyethylene glycol (hereinafter, "PEG"). In a related
embodiment, the molecular weight of the PEG ranges
25
from 1,000 to 20,000. The molecular weight of the
PEG, in another related embodiment, ranges from
2,000 to 8,000. In a pref erred embodiment, the PAO
has two hydroxyl groups, one of which reacts with
30 the adduct, and the other of which is available for
further functional group modification as dis• cussed
below .
The amount of PAO reacted with the adduct may
range from about 0.8 to 1.8 equivalents of hydroxyl per
35
equivalent of carboxyl group present in the adduct. The
temperature at which the adduct is reacted with the
PAO may range from about 240° C. to 290° C. A more
narrow temperature range of from 240° C. to 265° C.
may be used instead. In one embodiment, the rea ction
40
between the adduct and PAO is carried out until an
acid number of 25 or less is reached, while in another
embodiment the reaction is carried out until an acid
number of less than 5 is reached. Thus, in one aspect, the
45
surfactant has an acid number of less than 25, while in
another aspect the surfactant has an acid number of less
than
5. In another aspect surfactant has an acid number within
the
25.
Furthermore, while not required, a catalyst may be
used for the above esterification reaction between the
PAO and the resin adduct. Catalysts that may be used
55 include, but are not limited to, acids such as
phosphoric, hypophosphorus and sulfuric acids;
alkylsulfonic and arylsulfonic acids; and oxides,
hydroxides and carboxylates of Group I and Group II
elements (alkaline and alkaline earth).
60
The present invent ion, in anot her representative
embodiment, is directed to a process for preparing a surfac•
tant that comprises forming an adduct and reacting that
adduct with PAO, as described above, and then modifying
the surfactant by means of phosphorylation or sulfation to
65
provide a functionalized surfactant. In a pref erred
embodiment, the reaction between the adduct and the PAO
provides a surfactant molecule that has a plurality of poly•
alkylene polyol chains, such as PEG chains, grafted to the
adduct backbone. Many of the plurality of chains terminate
with a hydroxyl group. Thus, at the sites of the hydroxyl
groups, the chains may be functionalized to yield surf actants
having different properties, depending upon the pendent
functionality imparted thereto.
Imparting pendent functionality to the surfactant by sul•
 US 6,900,274 B2
9 10
therefrom. Imparting pendent functionality to the surf actant arom a t i c -m o d i fie d hyd roc a rbo n tack i fie r re s i n/
by phosphorylation of the hydroxyl-terminated chains may vinylaromatic-modified hydrocarbon resin-MA-PEG surfac•
be accomplished using reactants that include, but are not tant. Each of these combinations is a separate aspect of the
limited to, phosphorus pentoxide (P 2 0 5 ) , phosphorus
present invention, where "MA" indicates that maleic anhy•
trichloride (PC13 ) , polyphosphoric acid, and phosphorus 5 dride was reacted with the indicated resin to form the adduct,
oxychloride (POC13). and PEG indicates that a polyethylene glycol molecule was
Thus, in various aspects, the present invention is directed reacted with the indicated adduct. In each of these separate
to a surfactant prepared by reacting a resin with an a,�• aspects, the criteria as set forth above, e.g., acid
unsaturated carboxylic acid or ester or anhydride to thereby number, extent of adduction as measured in weight percent,
form an adduct; optionally reacting the adduct with a 10 molecu- lar weight of the PEG, et c., may be used to further
poly(alkyleneoxide) (PAO) to provide a surfactant; and charac• terize the products and processes of the present
optionally treating the surfactant under sulfation or phos• invention.
phorylation conditions to provide a modified surfactant. An exemplary aqueous dispersion that is suitable for use
In one aspect of the invention, the surfactant is isol ated in waterborne adhesives may have a solids content ranging
prior to being used as a surfactant, i.e., it is isolated and/or 15 from 50- 60% or from 55- 60%, a pH ranging from 4- 9 or
purified prior to being combined with water. Thus, the 6-8; a viscosity that is less than 8000 cps or less than 1500
invention provides, in one aspect, surfactant that is anhy• cps or less than 1000 cps (Brookfield #5/20 rpm or #3/50
drous at room temperature and pressure. This isolated sur• rpm); a particle size of less than 2 µm or less than 1 µm; and
factant can then be added to other compositions, e.g., a mechanical stability sufficient to pass industry screening
tackifier resins, to provide an aqueous dispersion of the 20 tests related to pumping, formulating operations, and the
tackifier. Thus, in one aspect, the adduct is provided in like. Further, the aqueous dispersions of the present inven•
isolated form, while in another aspect the surfactant is tion may comprise, in addition to a disclosed surfactant, a
provided in isolated form, each at room temperature and co-surfactant that may be anionic, nonionic or polymeric.
pressure. In one aspect, "isolated form" means free from The present invention, in another aspect, is directed to an
25
water. adhesive composition comprising a tackifier resin, a poly-
The present invention, in yet further aspects, is directed to mer latex, water, and at least one of: a surfactant prepared by
compositions comprising a surfactant as described herein reacting a resin with an a,�-unsaturated carboxylic acid
and a tackifier resin, and to aqueous dispersions comprising or
these two components. As used herein, "t ackifier resin" ester or anhydride to thereby form an adduct; optionally
30
refers to a resin that enhances the adhesive properties of an reacting the adduct with a poly(alkyleneoxide) (PAO) to
adhesive formulation. Such adhesive properties include, provide a surfactant; optionally treating the surfactant under
without limitation, tackiness, peel-resistance and ease of sulfation or phosphorylation conditions to provide a modi•
surface wetting. Suitable tackifier resins include the terpene, fied surfactant
terpene-hydrocarbon, terpene-phenol, and hydrocarbon res• 35 The adhesive compositions may be prepared by blending
ins described previously. Another suitable tackifier resin is a an aqueous tackifier dispersion of the present invention with
rosin ester tackifier resin. a natural or synthetic polymer latex or blend of latexes,
Compositions of the present invention, comprising a according to techniques well known to those of skill in the
disclosed surfactant and a tackifier resin, may be prepared by art. Suitable polymer latexes include aqueous suspensions of
melting the tackifier resin, then adding the surfactant and 40 natural rubber or synthetic elastomers. The latter elastomeric
mixing it with the resin by stirring. Aqueous dispersions of polymers include, but are not limited to, acrylic polymers
surfactant/tackifier resin may be prepared by adding hot derived from 2-ethylhexyl acrylate, butyl acrylate, methyl
water to the melted tackifier resin having the surfactant met ha cr yl ate, m ethacrylic acid, and acr yl ic aci d;
mixed therewith. The hot water may be added to first form polystyrene, a styrene-butadiene copolymer; a pol ymer
a water-in-oil emulsion. More water is then added to bring 45 derived from a vinyl acetate such as ethylene vinyl acet ate;
about an inversion to an oil-in-water emulsion and, then, to polychloroprene; an acrylonitrile-butadiene copolymer.
provide the aqueous dispersion having a desired solids In a further aspect, the present invention is directed to a
content. The emulsion is then cooled to a temperature of 50° pressure sensitive adhesive overlay, prepared by applying a
C. or less, and, if needed, biocides may be added. layer of a disclosed adhesive composition to a surface of a
Some specific examples of tackifier resin/surfactant com• 50 substrate, serving as an adhesive carrier, and drying the
binations that are present in the disclosed compositions and layer. As used herein, the term "overlay" refers to any
aqueous dispersions of the present invention include: (1) substrate having a layer of adhesive material applied to at
rosin ester tackifier resin/terpene-vinylaromatic resin-MA• least a portion of its surface ("first surface") and, thereby,
PEG surfactant; (2) rosin ester tackifier resin/ terpene-phenol adapted to be adhesively applied to a surface of another
resin-M A -PEG sur f actant ; (3) rosi n est er tackifier 55 substrate ("second surface") by bringing the first and second
resinvinylaromatic-modified hydrocarbon resin-MA -PEG; surfaces into contact under pressure.
(4) terpene tackifier resin/terpene resin-MA-PEG surfactant; A substantial portion of the commercial production of
(5) terpene tackifier resin/hydrocarbon resin-MA-PEG sur• waterborne adhesives is used for the manufacture of pres•
factant; (6) terpene-vinylaromatic tackifler resin/terpene• sure sensitive adhesives (PSAs) for adhesive overlays such
vinylaromatic resin-MA-PEG surfactant; (7) terpene• 60 as labels, tapes, decorative appliques, and the like. Suitable
vi ny Iarornati c tackifier resi n/ vinyl arom at ic-m odified substrates serving as adhesive carriers may be prepared
hydrocarbon resin-MA-PEG surfactant; (8) terpene-phenol using non-woven material such as, for example, paper,
tackifier resin/terpene-phenol resin-MA-PEG surfactant; (9) plastic, metal or foam; or may be prepared using woven
hydrocarbon tackifier resin/ terpene-MA-PEG, (10) hydro• material, such as, for example, woven cotton or woven
carbon tackifier resin/hydrocarbon resin-MA-PEG surfac• 65 synthetic polymers. Some exampl es of the latter are
tant; (11) aromatic-modified hydrocarbon tackifier resin/ polyethylene, polypropylene, polyvinyl chloride, polyester,
terpen-vinylaromatic resin-M A-PEG surfactant; (12) and polyamide.
The following examples are provided for the purpose of
illustration, not limitation.
 US 6,900,274 B2
11 12
EXAMPLES All of the above U.S. patents, U.S. patent application
publications, U.S. patent applications, foreign patents, for•
Example 1 eign patent applications and non-patent publications referred
to in this specification and/or listed in the Application Data
Preparation of an Adduct by Reacting Maleic
5 Sheet, are incorporated herein by reference, in their entirety.
Anhydride with a Terpene-Vinylaromatic Resin From the foregoing it will be appreciated that, although
A four-neck, l L round-bottom flask was charged with 450 specific embodiments of the invention have been described
grams Sylvares® ZT105LT terpene-vinylaromatic resin herein for purposes of illustration, various modifications
(Arizona Chemical Company, Jacksonville, Fla.) and heated may be made without deviating from the spirit and scope of
to 150° C. under 2LPM nitrogen purge. When the resin had 10 the invention. Accordingly, the invention is not limited
except as by the appended claims.
melted and was sufficiently fluid, stirring was started at What is claimed is:
about 250 rpm. To the stirred resin was added 50.0 grams of 1. A process for preparing a surfactant comprising:
maleic anhydride. The contents of the flask were placed reacting an a,�-unsaturated carboxylic acid or anhydride,
under a nitrogen atmosphere, and heated to 200° C. The or an ester thereof, with a resin comprising hydrocar•
agitation was increased to 300 rpm. The reaction mass was 15 bon monomeric residues, to provide an adduct;
stirred for 16.5 hours at 200° C., then heated to 250° C. over reacting the adduct with either alkylene oxide or
about 5.5 hours. A sample was analyzed showing 97.1 % a carboxyl-reactive poly(alkylene oxide) to provide
conversion of the maleic anhydride. The temperature was the surfactant; and
lowered to 200° C., and the contents of the flask were spared modifying the surfactant by either phosphorylation or
with nitrogen to remove the unreacted maleic anhydride 20 sulfonation to provide a functionalized hydrophilic
until the acid value of a water-extract (equal weight surfactant.
to sample) was 0.3. The contents of the flask were 2. The process of claim 1 wherein the resin is selected
Analysis
discharged.of the adduct showed 6.54% maleic anhydride from the group consisting of a polyterpene resin, a terpene•
adducted by weight. phenol resin, a terpene-hydrocarbon resin, a terpene-vinyl
25 aromatic resin, a hydrocarbon resin, and a vinyl aromatic•
Example 2 modified hydrocarbon resin.
3. The process of claim 1 wherein the a,�-unsaturated
Preparation of Resin Dispersion Surfactant by carboxylic acid is maleic acid, and the a ,�-
Reacting the Adduct of Example 1with unsaturated
Polyethylene Glycol
30 carboxylic anhydride is maleic anhydride.
A l L, four-neck round-bottom flask equipped with a 4. The process of claim 1 wherein the resin is a polyter•
paddle stir shaft, nitrogen inlet and thermocouple was pene resin having a softening point of about 10° C. to about
charged with 100.0 grams of the adduct from example 1 and 150° c.
143.2 grams of polyethylene glycol having an average 5. The process of claim 1 wherein the resin comprises one
molecular weight of 2000 ("PEG 2000", Aldrich Chemical 35 or more monomeric residues independently selected from
Company, Milwaukee, Wis.). The contents of the flask were the group consisting of a-pinene, � -pinene, limonene,
heated, under lLPM nitrogen purge. Stirring was started
when the contents were molten and sufficiently fluid. When dipentene, � -phellandrene, 1\-3-carene, and 1\-2-carene.
the temperature reached 219° C., 0.54 grams of 75% phos• 6. The process of claim 5 wherein the resin further
phoric acid was charged and the flask placed under a 40 comprises one or more monomeric residues independently
nitrogen atmosphere, and heated to 250° C. The reaction selected from the group consisting of isobutylene, a
mass was stirred at this temperature for 20 hours. A sample 1-alkene, a 2-alkene, a trisubstituted alkene, and vinylcy•
of reaction mass had an acid number of 1.4. The contents of clohexene.
the flask were cooled to 157° C. and discharged. 7. The process of claim 5 wherein the resin further
45 comprises one or more monomeric residues independently
Example 3 selected from the group consisting of piperylene, isoprene,
2-methyl-2-bytene, 2-methyl-1-bytene, cyclopentene, an
Dispersion of a Rosin Ester Tackifier Resin with
acyclic pentene, cyclopentadiene, and dicyclopentadiene.
the Surfactant of Example 2 8. The process of claim 1 wherein the resin is a terpene•
A 1.SL resin flask was charged with 300.0 grams of 50 phenol resin and comprises one or more monomeric residues
Syl v are s®) RE-85 (A ri z on a Chem i c al Com p an y, independently selected from the group consisting of
Jacksonville, Fla.) and 18.0 grams of surfactant from a-pinene, � -pinene, 1\-3-carene and limonene.
example 2. The contents were heated under a 2LPM nitrogen 9. The process of claim 8 wherein the terpene-phenal resin
sweep to 98° C. Stirring was started, and the flask was further comprises one or more monomeric residues inde•
placed under a nitrogen blanket. A solution of 2.1 grams of 55 pendently selected from the group consisting of styrene,
50% potassium hydroxide in 47 grams distilled water was indene, a-methylstyrene , an alkyl arom atic st yren e,
prepared and heated to 80° C. When the temperature of divinylbenzene, a divinylbenzene with one or more alkyl
tackifier resin-surfactant blend was 112° C., the hot potas• groups, isobutylene, dilsobutylene, a 1-alkene, a 2-alkene, a
sium hydroxide solution was added to produce first a water• trisubstitut ed alkene, vinylcyclohexe ne, pipe r yl ene,
in-oil dispersion, which inverted to an oil-in-water disper• 60 isop r en e , 2-m e th yl - 2-b yt e ne , 2-m e t h yl -1- bu ten e ,
sion. The temperature of this dispersion was brought to 97° cyclopentene, an acyclic pentene, cyclopentadiene, and
C., and 160 grams of hot distilled water was added over 18 dicyclopentadiene.
minutes. The resulting diluted dispersion was cooled to 59° 10. The process of claim 8 wherein the phenol is inde•
C., and some biocide was added. After cooling further to 50° pendently selected from the group consisting of phenol, a
C., the dispersion was analyzed for a pH of 9.5. A sample of 65 monosubstituted phenol, a disubstituted phenol, a trisubsti•
the dispersion was adjusted to a pH of 7.5 and 58.8% solids tuted phenol and a hydroxyl-substituted naphthalene com-
and a mean particle size of 0.84 microns. pound.
11. The process of claim 1 wherein the resin comprises
one or more monomeric residues independently selected
 US 6,900,274 B2
13
from the group consisting of piperylene, isoprene, 2-methyl-
2-bytene, 2-methyl-1-butene, cyclopentene, an acyclic
pentene, cyclopentadiene, and dicyclopentadiene.
12. The process of claim 1 wherein the adduct is reacted
with poly(ethylene glycol) or a mixture of more than one
polyethylene glycol).
13. The process of claim 1, wherein the adduct is reacted
with ethylene oxide.
14. The surfactant of claim 1.
15. A composition comprising the surfactant of claim 1
and a tackifier resin.
16. An adhesive composition comprising:
the surfactant of claim 1;
a tackifier resin;
a polymer latex; and water.
17. An aqueous dispersion comprising water and a com•
position comprising a surfactant and a tackifier resin,
wherein the surfactant is prepared by a process comprising:
reacting an a,�-unsaturated carboxylic acid or anhydride, 20
or an ester thereof, with a resin comprising hydrocar•
bon monomeric residues, to provide an adduct, and
reacting the adduct with either alkylene oxide or
a
carboxyl-reactive poly(alkylene oxide) to provide the
surfactant.
18. The aqueous dispersion of claim 17 wherein the
resin comprising hydrocarbon monomeric residues is
selected from the group consisting of a polyterpene resin, a 30
terpene• phenol resin, a terpene-hydrocarbon resin, a
terpene• vinylaromatic resin, a hydrocarbon resin, and
a vinyl aromatic-modified hydrocarbon resin.
19. The aqueous dispersion of claim 17 wherein the
process further comprising modifying the surfactant by 35
either
20. phosphorylation or sulfonation
The aqueous dispersion to provide
of claim a function•
17 wherein the
alized surfactant. carboxylic acid is maleic acid, and
a ,�-unsaturated
the
a,�-unsaturated carboxylic anhydride is maleic anhydride.
21. The aqueous dispersion of claim 17 wherein the resin 40 vinyl aromatic-modified hydrocarbon resin.
comprising hydrocarbon monomeric residues is a polyter•
pene resin having a softening point of about 10° C. to about
150° c.
22. The aqueous dispersion of claim 17 wherein the resin
comprising hydrocarbon monomeric residues comprises one 45
or more monomeric residues independently selected from
the group consisting of a -pinene, � -pinene, limonene,
dipentene, � -phellandrene, 1\-3-carene, and 1\-2-carene.
23. The aqueous dispersion of claim 22 wherein the
resin comprising hydrocarbon monomeric residues further
com• prises one or more monomeric residues
independently selected from the group consisting of
isobutylene, a
1-alkene, A 2-alkene, a trisubstituted alkene, and vinylcy•
clohexene.
24. The aqueous dispersion of claim 22 wherein the
resin comprising hydrocarbon monomeric residues further
com- prises one or more monomeric residues
independently selected from the group consisting of
piperylene, isoprene,
2-methyl-2-bytene, 2-methyl-1-butene, cyclopentene, an
acyclic pentene, cyclopentadiene, and dicyclopentadiene.
25. The aqueous dispersion of claim 17 wherein the resin
comprising hydrocarbon monomeric residues is a terpene•
phenol resin and comprises one or more monomeric residues
independently selected from the group consisting of
a-pinene, � -pinene, 1\-3-carene and limonene.
26. The aqueous dispersion of claim 25 wherein
the terpene-phenol resin further comprises one or more
mono• meric residues independently selected from the
group con-
14
sisting of styrene, indene, a -methyl styrene, an alkyl
aro• matic styrene, divinylbenzene, a divinylbenzene with
one or more alkyl groups, isobutylene, diisobutylene, a 1-
alkene, a
5 2-alkene, a trisubstituted alkene, vinylcyclohexene,
piperylene, isoprene, 2-methyl-2-bytene, 2-met hyl-1-
butene, cyclopentene, an acyclic pentene, cyclopentadlene,
and dicyclopentadlene.
27. The aqueous dispersion of claim 25 wherein the
10 phenol is independently selected from the group consisting
of phenol, a monosubstituted phenol, a disubstituted phenol,
a trisubstituted phenol and a hydroxyl-substituted naphtha•
lene compound.
28. The aqueous dispersion of claim 17 wherein the resin
15 comprising hydrocarbon monomeric residues comprises one
or more monomeric residues independently selected from
the group consisting of piperylenei isoprene, 2-methyl-2-
bytene, 2-methyl-1-bytene, cyclopentene, an acyclic
pentene, cyclopentadiene, and dicycl opentadiene.
29. The aqueous dispersion of claim 17 wherein the
adduct is reacted with poly(ethylene glycol) or a mixture of
more than one poly(ethylene glycol).
30. The aqueous dispersion of claim 17 wherein the
adduct is reacted with ethylene oxide.
25 31. An adhesive composition comprising a surfactant,
a tackifier resin, a polymer latex, and water, wherein the
surfactant is prepared by a process comprising:
reacting an a,�-unsaturated carboxylic acid or anhydride,
or an ester thereof, with a resin comprising hydrocar•
bon monomeric residues, to provide an adduct, and
reacting the adduct with either alkylene oxide or
a
carboxyl-reactive poly(alkylene oxide) to provide the
surfactant.
32. The adhesive composition of claim 31 wherein the
resin comprising hydrocarbon monomeric residues is
selected from the group consisting of a polyterpene resin, a
terpene-phenol resin, a terpene-h ydroc arbon resin, a
terpene-vinyl aromatic resin, a hydrocarbon resin, and a
33. The adhesive composition of claim 31 wherein the
process further comprising modifying the surfactant by
either phosphorylation or sulfonation to provide a function•
alized surfactant.
34. The adhesive composition of claim 31 wherein the
a ,�-unsaturated carboxylic acid is malaic acid, and
the
50 a,� -unsaturated carboxylic anhydride is maleic anhydride.
35. The adhesive composition of claim 31 wherein the
resin comprising hydrocarbon monomeric residues is a
polyterpene resin having a softening point of about 10° C. to
about 150° C.
55
36. The adhesive composition of claim 31 wherein the
resin comprising hydrocarbon monomeric residues com•
prises one or more monomeric residues independently
selected from the group consisting of a-pinene, � -pinene,
limonene, dipentene, � -phellandrene, 1\-3-carene, and 1\-2-
60
carene.
37. The adhesive composition of claim 36 wherein the
resin comprising hydrocarbon monomeric residues further
comprises one or more monomeric residues independently
selected from the group consisting of isobutylene, a
65
1-alkene, a 2-alkene, a trisubstituted alkene, and vinylcy•
clohexene.
38. The adhesive composition of claim 36 wherein the
resin comprising hydrocarbon monomeric residues further
comprises one or more monomeric residues independently
selected from the group consisting of piperylene, isoprene,
2-methyl-2-bytene, 2-methyl-1-bytene, cyclopentene, an
acyclic pentene, cyclopentadiene, and dicyclopentadiene.
 US 6,900,274 B2
15
39. The adhesive composition of claim 31 wherein the
resin comprising hydrocarbon monomeric residues is a
terpene-phenol resin and comprises one or more monomeric
residues independently selected from the group consisting of
a-pinene, � -pinene, 1\-3-carene and limonene.
40. The adhesive composition of claim 39 wherein the
terpene-phenol resin further comprises one or more mono•
meric residues independently selected from the group con•
sisting of styrene, indene, a -methylstyrene, an alkyl aro•
matic styrene, divinylbenzene, a divinylbenzene with one or
more alkyl groups, isobutylene, diisobutylene, a 1-alkene, a
2-alkene, a trisubstitut ed alkens, vinyl cyclohexene,
piperylene, isoprene, 2-methyl-2-bytene, 2-met hyl-1-
butene, cyclopentene, an acyclic pentene, cyclopentadiene,
and dicyclopentadiene.
41. The adhesive composition of claim 39 wherein the
phenol is independently selected from the group consisting
of phenol, a monosubstituted phenol, a disubstituted phenol,
a trisubstituted phenol and a hydroxyl-substituted naphtha•
lene compound.
42. The adhesive composition of claim 31 wherein the
resin comprising hydrocarbon monomeric residues com•
prises one or more monomeric residues independently
selected from the group consisting of piperylene, isoprene,
2-methyl-2-bytene, 2-methyl-1-butene, cyclopentene, an
acyclic pentene, cyclopentadiene, and
dicyclopentadiene.
43. The adhesive composition of claim 31 wherein the
adduct is reacted with poly(ethylene glycol) or a mixture of
more than one poly(ethylene glycol).
44. The adhesive composition of claim 31 wherein the
adduct is reacted with ethylene oxide.
45. A pressure sensitive adhesive overlay prepared by
applying a layer of an adhesive composition to a surface of
a substrate, and drying the layer, wherein the adhesive
composition comprises a surfactant, a tackifier resin, a
polymer latex, and water, wherein the surfactant is prepared
by a process comprising:
reacting an a,�-unsaturated carboxylic acid or anhydride,
or an ester thereof, with a resin comprising hydrocar•
bon monomeric residues, to provide an adduct, and
reacting the adduct with either alkylene oxide or
a wherein the phenol is independently selected from the group
carboxyl-reactive poly(alkylene oxide) to provide the
surfactant.
46. The pressure sensitive adhesive overlay of claim 45
wherein the resin comprising hydrocarbon monomeric resi•
dues is selected from the group consisting of a polyterpene
resin, a terpene-phenol resin, a terpene-hydrocarbon resin, a
terpene-vinyl aromatic resin, a hydrocarbon resin, and a
vinyl aromatic-modified hydrocarbon resin.
47. The pressure sensitive adhesive overlay of claim 45
wherein the resin comprising hydrocarbon monomeric resi•
dues is selected from the group consisting of a polyterpene
resin, a terpene-phenol resin, a terpene-hyrdrocarbon resin,
a terpene-vinylaromatic resin, a hydrocarbon resin, and a
vinyl aromatic -modified hydrocarbon resin.
48. The pressure sensitive adhesive overlay of claim 45
wherein the a,�-unsaturated carboxylic acid is maleic acid,
and the a ,�-unsaturated carboxylic anhydride is maleic
anhydride.
16
49. The pressure sensitive adhesive overlay of claim 45
wherein the resin comprising hydrocarbon monomeric resi•
dues is a polyterpene resin having a softening point of about
10° C. to about 150° C.
5 50. The pressure sensitive adhesive overlay of claim 45
wherein the resin comprising hydrocarbon monomeric resi•
dues comprises one or more monomeric residues indepen•
dently selected from the group consisting of a -pinene,
� -pinene, limonene, dipentene, phellandrene, 1\-3-carene,
10
and 1\-2-carene.
51. The pressure sensitive adhesive overlay of claim 50
wherein the resin comprising hydrocarbon monomeric resi•
dues further comprises one or more monomeric residues
independently selected from the group consisting of
15 isobutylene, a 1-alkene, a 2-alkene, a trisubstituted alkene,
and vinylcyclohexene.
52. The pressure sensitive adhesive overlay of claim 50
wherein the resin comprising hydrocarbon monomeric resi•
20
dues further comprises one or more monomeric residues
independently selected from the group consisting of
piperylene, isoprene, 2-methyl-2-bytene, 2-met hyl-1-
butene, cyclopentene, an acyclic pentene, cyclopentadiene,
and dicyclopentadiene.
25
53. The pressure sensitive adhesive overlay of claim 45
wherein the resin comprising hydrocarbon monomeric resi•
dues is a terpene-phenol resin and comprises one or more
monomeric residues independently selected from the group
consisting of a-pinene, � -pinene, 1\-3-carene and limonene.
54. The pressure sensitive adhesive overlay of claim 53
30
wherein the terpene-phenol resin further comprises one or
more monomeric residues independently selected from the
group consisting of styrene, indens, a-metthylstyrene, an
alkyl aromatic styrene, divinylbenzene, a divinylbenzene
with one or more alkyl groups, isobutylene, diisobutylene, a
35
1- a l k en e , a 2- a l k e n e , a tr i s u bs t i t ut e d
al k e n e ,
vinylcyclohexene, piperylene, isoprene, 2-methyl-2-butene,
2-methyl-1-bytene, cyclopertene, an acyclic pentene,
eyclopentadiene, and dicyclopentadiene.
40
55. The pressure sensitive adhesive overlay of claim 53
consisting of phenol, a monosubstituted phenol, a disubsti•
tuted phenol, a trisubstituted phenol, and a hydroxyl•
45 substituted naphthalene compound.
56. The pressure sensitive adhesive overlay of claim 45
wherein the resin comprising hydrocarbon monomeric resi•
dues comprises one or more monomeric residues indepen•
dently selected from the-group consisting of piperylene,
50 isop r en e , 2-m e t h yl- 2- b yt e ne , 2-m e t h yl -1- b u te n e ,
cyclopentene, an acyclic pentene, cyclopentadiene, and
dicyclopentadiene.
57. The pressure sensitive adhesive overlay of claim 45
wherein the adduct is reacted with poly(ethylene glycol) or
55 a mixture of more than one poly(ethylene glycol).
58. The pressure sensitive adhesive overlay of claim 45
therein the adduct is reacted with ethylene oxide.
* * * * *
 I III IIIIII Illllllllllllllllllllllllllllllllllllllllll111111111111111111
US007452941B2

c12) United States Patent (IO) Patent No.: US 7,452,941 B2

Ruckel et al. (45) Date of Patent: *Nov. 18, 2008

(54) TERPENE RESIN AND HYDROCARBON (56) References Cited

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4,857,563 A * 8/19 89 Croft et al. .................. 523/173
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6,900,274 B2 * 5/2005 Ruckel et al. ............ 525/333.3
This patent is subject to a terminal dis•
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(21) Appl. No.: 11/699,203 Primary Examiner-Peter Szekely
(74)Attorney, Agent, or Firm-Gilbreth &Associates P.C.; J.
(22) Filed: Jan.29,2007 M. (Mark) Gilbreth; Mary A. Gilbreth

(57) ABSTRACT
(65) Prior Publication Data
US 2007/0207313 Al Sep. 6,2007
A process for preparing a surfactant, useful for dispersing
Related U.S. Application Data tackifier resins in aqueous media, comprises reacting an a,�•
(63) Continuation of application No. 10 /915,113, filed on unsaturated carboxylic acid or anhydride, or an ester thereof ,
Aug. 10 , 2004, now abandoned, which is a continua• with a terpene- or hydrocarbon-based resin to f orm an adduct,
tion of application No. 10 /360,585, filed on Feb. 6, then reacting the adduct with a polyalkylene polyol to yield
2003, now Pat. No. 6,900,274. the surf actant. In a related embodiment, the surfactant is
subsequently f unction alized. Also disclosed are surfact ants
(51) Int. Cl. prepared using a disclosed process; compositions comprising
COSF 8/46 (2006.01) a disclosed surf actant and a tackifier resin; aqueous disper•
COSF 32/00 (2006.01) sions comprising a disclosed surfact ant; tackifier resin and
C09J (2006.01) water; adhesive compositions comprising a disclosed aque•
(52) 14 5/ 00 525/210; 525/211; 525/285; ous dispersion and a polymer latex; and pressure sensitive
U.S. Cl. 525/327.4; 525/327.9; 524/270; 524/499 adhesive overlays prepared using a disclosed adhesive com•
(58) Field of Classification Search 525/210, position.
525/211, 285, 327.4, 327.9; 524/270, 499
See application file for complete search history. 13 Claims, No Drawings
 US 7,452,941
1 B2 2
TERPENE RESIN AND HYDROCARBON and Great Britain Patent Nos. 2,273,294 and 2,288,179. In
RESIN-BASED SURFACTANTS AND these methods, a resin is treated so that hydrophilic groups are
AQUEOUS DISPERSION OF TACKIFIER added to a sm all portion of the bulk resin. That is, a small
RESINS amount of hydrophilic groups are added to a resin, so that
hydrophilic groups are introduced to a sm all f raction of the
BACKGROUND OF THE INVENTION bulk resin molecules. The resin molecules containing these
hydrophilic groups then act as a surfact ant when water, and
1. Field of the Invention optionally som e co-solvent, are added to the resin/mod ified
The present invention generally pertains to surfactants, resin mixture.
more spe cifically, to surf act ants useful for preparing aqueous 1o Accordingly, there remains a need in the art for surfactants
dispersions of tackifier resins, where the resins may be that are useful for preparing tackifiers that, when blended
blended with latex to provide waterborne adhesives. with latex; yield waterborne adhesives, in particular, PSAs,
2. Description of the Related Art having improved adhesion, improved adhesive substrate wet•
The ongoing development of im proved waterborne (i.e., tability, greater mechanical strength for high-speed coating
water-d ispersed) adhesives to replace solvent-based adhe- 15 operations, and an improved shelf-life. The present invention
sives has largely been motivated by government regulation of fulfills these needs and provides further related advantages as
solvents, stemming from the perceived health and environ• described herein.
mental hazards thereof . As a result, waterborne adhesives
have become extensively used to adhere various substrates BRIEF SUMMARY OF THE INVENTION
together. Such adhesives of ten comprise both a high molecu- 20
lar weight elastomeric latex (or mixture of latexes, such In brief, the present invention is directed to processes for
as acrylic and styrene-butadiene rubber latex), and at le ast preparing a surfactant having utility f or dispersing resins,
one water-dispersed tackifier resin . It is possible to particularly tackifier resins, in water, where the dispersed
prepare a functional waterborne adhesive without a tackifier tackifier resin is then used for preparing waterborne adhe-
resin. However, inclusion of the latter is generally required 25 sives. The present invention is also directed to surfactants
to eco• nomically produce an adhesive exhibiting an adhesion prepared using the disclosed processes, as well as to compo•
to various substrates that allows f or commercial applicability sitions, f or example , aqueous dispersions and adhesive com•
of the adhesive. positions comprising a disclosed surfactant.
A significant portion of commercial waterborne adhesives In one aspe ct , the present invention is directed to a process
are pressure sensitive adhesives ("PSAs"). The latter are used, 30 for preparing a surf act ant. The process in cludes selecting a
for example , for adhesive tapes; to adhere labels to the cellu• resin, where the resin comprises the polymerization resid ues
losic, polyolefinic and polar-polymeric substrates of bottles of monomers, and the monomers are, or include, unsaturated
and other packaging containers; and to adhere cabinet and hydrocarbons. The selected resin is reacted with an a ,�•
wall decorations and the like. unsaturated carboxylic acid, or anhydride or ester thereof ,to
While PSAs generally exhibit good adhesion to a variety of 35 provide a carbonyl-containing resin , also referred to herein as
substrates, their adhesive performance is limited. For an adduct . The adduct is then reacted with a reactive poly
example , the adhesion of PSAs to substrates is generally (alkylene oxide) to provide a surfactant of the present inven•
inferior to that of their solvent-based counterparts. This defi• tion. This surfactant may be chemically modified by phos-
ciency may be attributed, at least in part, to the surfactant used phorylation or sulf ation.
to disperse the tackifier resin or prepare the latex or blend of 40 In one representative embodim ent, the present invention is
latexes used for the PSA. Surfactants inherently plasticize directed to a process for preparing a surfactant comprising:
polymer-tackifierresin blends, which reduces adhesive (1) reacting an a,�-unsaturated carboxylic acid or anhydride,
shear. Also, surfactants often impede adhesion by migrating or an ester thereof, with a resin selected from the group
to the substrate interface, thereby interfering with the ability consisting of a polyterpene resin, a terpene-phenol resin, a
adhesive
of the to stick thereto. 45 terpene-hydrocarbon resin, a hydrocarbon resin, or a viny•
Waterborne PSAs are also characterized by a limited shelf laromatic-modified hydrocarbon resin, to provide an adduct;
lif e, by a limited ability to wet adhesive substrates (i.e., the and (2) reacting the adduct with a hydroxy-terminated poly
substrates used to make adhesive tapes, labels, and the lik e), (alkylene oxide) to provide the surfactant. In one related
and by a mechanical stability that is less than id eal f or high• embodiment, the a-�-unsaturated acid is maleic acid, and the
shear and high-speed applications. Extended shelf lif e is gen• 50 corresponding anhydride is maleic anhydride ("MA"). In
erally desirable. Exceptional adhesive substrate wetting and another related embodiment, the poly(alkylene oxide) is
superior mechanical stability are important f or high-speed polyethylene glycol.
coating of an adhesive substrate by an adhesive. High-speed The present invention, in another representative embodi•
coaters, such as gravure, reverse gravure and slot die coaters, ment, is directed to a process for preparing a surfactant that
are now commonly used to produce lower coat weights and 55 comprises the two steps ofthe above-described representative
allow for increased throughputs. embodiment, and further comprises modifying the surfactant
Again, the surfactant used in preparing the tackifier resin provided thereby by means ofphosphorylation or sulfation to
dispersion is a limiting factor. Use of nonylphenol-based provide a functionalized surfactant.
surfactants has yielded tackifier resin dispersions and, there• Further representative embod iments of the present inven-
from, PSAs that exhibit substrate wetting and mechanical 60 tion are directed to the surf act ants prepared using the above•
stability that is compatible with the above-mentioned high• described processes; to compositions comprising a disclosed
speed coating methods. However, governmental regulatory surf act ant and a tackifier resin; to aqueous dispersions com•
activity has been increasingly directed to nonylphenols and prising a disclosed surfact ant, a tackifier resin and water; and
their derivatives to reduce or eliminate their presence in the to adhesive compositions comprising a disclose d surf act ant, a
marketplace, as well as in chemical plant aqueous effluents. 65 tackifier resin, a polymer latex and water. A related embodi•
Methods for the self -emulsification of resins have been ment is directed to a pressure sensitive adhesive article pre•
described. See, e.g., U.S. Pat. Nos. 4,670,504 and 5,268,399, pared from a disclosed adhesive composition.
 US 7,452,941
3 B2
These and other aspects of the invention will be evident
upon reference to the following description of the invention.
DETAILED DESCRIPTION OF THE INVENTION
In one aspect, the present invention is directed to a process
for preparing a surfactant. The process includes selecting a
resin, where the resin comprises the polymerization residues
ofmonomers, and the monomers are, or include, unsaturated
hydrocarbons. The selected resin is reacted with an
a ,�-
unsaturated carboxylic acid, or anhydride or ester thereof, to
provide a carbonyl-containing resin, also ref erred to herein as
an adduct . The adduct is then reacted with a carboxyI-react ive
poly(alkylene oxide), e.g., a hydroxyl- or amine-terminated
poly(alkylene oxide), or with an alkylene oxide so as to gen-
erate the poly(alkylene oxide) in situ, so as to provide a
surf actant of the present invention. Depending on its struc•
ture, the surfactant may be chemically modified by phospho•
rylation or sulf ation.
The resin utilized in the process of the present invention is
prepared in whole or part from hydrocarbon monomers. In
one exemplary embodim ent the hydrocarbon is a terpene, and
the resulting resin may be, e.g., a polyterpene resin (i.e ., a
resin prepared from terpene as the sole hydrocarbon mono•
mer), a terpene hydrocarbon resin (i.e., a resin prepared from
terpene as well as non-terpene hydrocarbon monom er(s)),
and a terpene phenolic resin (i.e ., a resin prepared from ter•
pene and phenolic compound), where collectively these res-
ins are ref erred to herein as "terpene resins". In one embodi•
ment, the resin is a terpene hydrocarbon resin, e.g., a terpene
vinylaromatic resin. In another embodiment the resin is a
terpene phenolic resin . In yet another embodim ent the resin is
a polyterpene resin.
Terpene resins that may be used in the process of the
present invention in clude any resins pr epared, in whole or
part, from an unsaturated terpene Cl O hydrocarbon (i.e., a
terpene containing ten carbons), where exemplary terpenes
include, without limitation, 1\-2-carene, 1\-3-carene, dipen•
tenc, limon ene, myrcene, �
-phellandrene, a-
pinene,
� -pinene, o-terpinene, y-terpinene, and terpinolene.
In one aspect, the selected terpene resin is prepared, at least
in part, from a -pinene. In another aspect the selected terpene
resin is prepared, at least in part, from � -pinene. In another
aspect, the selected terpene resin is prepared, at least in part,
from limon ene. In another aspe ct, the sele cted terpene resin is
prepared, at least in part, from a carene. Each of these terpenes
may be obtained from various commercial suppliers, e.g.,
Aldrich Chemical (Milwaukee, Wis.), Arizona Chemical
Company (Jacksonville , Fla.), Millennium Specialty Chemi•
cals (Jacksonville , Fla.), International Flavors and Fr agrances
(f ormerly Bush Boake Allen in Jacksonville, Fla.), or DRT
(Les Derives Resiniques et Terpeniques of Dax, France) or by
transf ormations such as the isomerization of a -pinene to
dipentene or of 1\-3-carene to 1\-2-carene or the pyrolysis of
� -pinene to myrcene. n-Pinene, � -pinene, 1\-3-carene and
dipentene are often ultimately obtained from trees, particu•
larly pine trees. Limonene can be obtained from the citrus
processing industry.
In one aspect, the resin is the cationic polymerization prod•
uct ofa terpene, e.g., it may be prepared by cationic polymer-
ization of resin-grade � -terpene, monomer, limonene mono•
mer, or a mixture of the two monomers. Cationic
polymerization of terpenes may be achieved by treating the
terpene with a Lewis acid catalyst . More specifically, cata•
lysts that may be used include aluminum chloride (AICl3 ) and
boron trifluoride (BF3) and their derivatives (e.g., their ether•
ates or other solvated form); as well as acidic clays, antimony
4
halides, stron g protic acids such as hydrofluoric acid and
sulfuric acid, and titanium tetrachloride. The catalysts may be
removed f rom the resin by any number of processes known to
those skilled in the art. The terpene resins, so produced, may
be further subje cted to treatment at elevated temperature to
distill away solvent and remove co-products, and thereby
achieve a desired softening point for the resin.
A preferred-terpene from which to prepare a terpene resin
10 is � -pinene. � -pinene monomer is commonly obtained by
distillation of crude sulfate turpentine, which is a by-product
ofthe paper industry. Resin-grade �
-pinene is generally about
80% by weight �
-pinene with much of the remainder being
15
a-pinene. Higher purity grades of � -pinene, such as the so-
called aroma-chemical grade thereof, which is greater than
90% by weight � -pinene, may also be used in preparing the
terpene resins. See, e.g., U.S. Pat. No. 4,487,901 for disclo•
20
sure directed to making � -pinene resin. The resin may also be
prepared from a-pinene (see, e.g., U.S. Pat. Nos. 4,113,653
and 4,057,682).
Other preferred terpenes are lim onene and dipentene.
Limonene may be obtained as a byproduct of the citrus indus•
25 try. Dipentene obtained by pyrolysis or catalytic cracking of
a -pinene (i.e ., racemic limonene) may also be used in pre•
paring the terpene resins.
The terpene resin may comprise, in addition to the residues
from the above terpenes, the residues ofvarious non-terpenic
30
unsaturated compounds, particularly unsaturated hydrocar•
bons, e.g., olefins and dienes. Examples thereof include, but
are not limited to: isobutylene, diisobutylene, 1-alkenes (e.g.,
1-octadecene), 2-alkenes, trisubstituted alkenes, vinylcyclo•
hexene, as well as piperylene and dicyclopentadiene streams
35
obtained from steam cracking of petroleum distillates. The
latter streams generally include piperylene, isoprene, 2-me•
thyl-2-butene, 2-m ethyl-1- butene, cyclopentene, an acyclic
pentene, cyclopentadiene, and dicyclopentadiene. See, e.g.,
U.S. Pat. Nos. 6,121,392 and 3,959,238 for disclosure
40
directed to resins made from � -pinene and various unsatur-
ated hydrocarbons.
An exemplary terpene-hydrocarbon resin contains from 65
to 35 percent by weight of polymeric units derived from
45 dicyclopentadiene and from 35 to 65 percent by weight of
polymeric units derived from � -pinene. In one aspect, the
molar ratio of the dicyclopentadiene to beta-pinene in the
polymerization reaction starting materials ranges from about
1:2 to about 2: 1. The polymerization reaction between dicy•
50 clopentadiene and � -pinene may be a thermal (i.e. no catalyst
is employed) or catalyzed (i.e., conducted in the presence of
a catalyst, e.g., an acid catalyst). Examples of acid catalysts
that may be used include Bronsted acid and Lewis acid-type
catalysts, such as H2 S0 4 , HCI, H3 P0 4 ; metal halides such
as
55
BF 3 , BCl 3 , AICl 3 , A!Br3 , SnC14 , ZnCl 2 , SbCl 3 as well as
the etherates thereof . In the catalyzed polymerization
process, the amount of catalyst may range from about 0.1 to
about 20 weight percent of catalyst based on the total
weight of reac• tants to be polymerized. The polymerization
60
reaction may be
carried out neat (without solvent) at or above the melting
points of the reactants, or can be carried out in the presence of
a solvent. The reaction pressure may vary and range from
about one atmosphere to about 10 0 atmospheres with a pres•
65
sure of from about two atmospheres to about ten atmospheres
being pref erred. The reaction temperature may range from
about 0-10 0° C. A reaction time of about 1- 8 hours is gener•
ally sufficient to achieve a desired molecular weight distribu•
tion of f rom about 550 to about 55,000 (weight average
molecular weight), and a sof tening point ranging from about
 US 7,452,941
5 B2
100 to about 170° C. Other limonene-containing hydrocarbon
resins include those described in U.S. Pat. Nos. 6,357,499 and
6,228,944.
Suitable terpene resins that may be used in the above•
disclosed process of the present invention in clude, but are not
limited to, commercially-available terpene resins sold by the
Arizona Chemical Company (Jacksonville, Fla.) designated
as SYLVARES® terpener esins M-1115, B-115, 7100, 7115,
7125, 1085, 1100, 1115, 1125, andA-25.
Terpene-vinylaromatic resins (also known as aromatic
modified terpene resins) that may be used f or the above•
disclosed process of the present invention, may be prepared
by acid catalyzed polymerization, in a suitable solvent, using
any of the above-mentioned terpenes with a vinylaromatic
monomer. Lewis acid catalysts, including A1Cl3 and BF 3 or
their derivatives, may be use d. Acid ic clays,
antimony
halides, stron g protic acids such as hydrofluoric and sulfuric
acid, and titanium tetrachloride, may also be used. The viny•
laromatic monomers that may be used in clude, but are not
limited to: styrene, indene, methylstyrenes, and para-alkyl•
styrenes, includin g mixtures thereof . These resins may be
post-treated with iod ine or by way of other decolorizing pro•
cesses. Some spe cific examples of t erpene-vin ylarom atic res•
ins, suitable for use in the above-disclosed process of the
present invention, are products designated as SYLVARES®
ZT 10 5LT and 510 0 resins, sold by the Arizona Chemical
Company (Jacksonville, Fla.).
Terpene-phenol resins that may be used for the above•
disclosed process of the present invention ("the terpene-phe•
nol resins") may be prepared by acid catalyzed polymeriza•
tion, in a suit able solvent, of any of the above-mentioned
terpenes with phenol and/or a derivative thereof . This chem•
istry is well known in the art. See, e.g., U.S. Pat. Nos. 5,723,
566 and 5,844,063. Lewis acids, includin g but not limited to
boron trifluoride and derivatives or complexes thereof , and
strong protic acids such as those listed above, may be use d.
The phenolic portion of the terpene phenol resin may be, e.g.,
phenol it self , or substituted phenols such as, for example,
monosubstituted phenol includin g monoalkylsubstituted
phenol, disubstituted phenol includin g dialkylsubstituted
phenol, trisubstituted phenol includin g trialkylsubstituted
phenol, and a naphthalene compound having a hydroxyl sub•
stituent attached to the ring.
Non-terpene olefins and die nes that may be used in addi•
tion to the terpenes for preparing the terpene-phenol resins,
include those listed above f or the terpene resins. For inst ance,
residues of the following non-terpene olefins and diolefins
may be present in the terpene-phenolic resin: vin ylarom atics
such as styrene, indene, cr-methylstyrene, divinylbenzene, a
divinylbenzene with one or more alkyl groups, isobutylene,
diisobutylene, a I- alkene, a 2-alkene, a trisubstituted alk ene,
vinylcyclohexane, piperylene, isoprene, 2-methyl-2-butene,
2-methyl-1-butene, cyclopentene, an acyclic pentene, cyclo•
pentadiene, dicyclopentadiene, and alkylaromatic styrenes.
Some specific examples ofterpene-phenol resins, suitable
for use in the above-disclosed process of the present inven•
tion, are commercial products designated as SYLVARES®
TP 300, 2040, 2040 HM, 2019, 7042 and3523 resins, sold by
Arizona Chemical Company (Jacksonville, Fla.).
Some hydrocarbon resins useful in the preparation of sur-
factants of the present invention may have little or no terpene•
derived residues. For example, CS unsaturated hydrocarbons
may be used to prepare suitable hydrocarbon resins. Such
resins may be prepared by cationic polymerization of pip•
erylene streams, obtained by steam cracking of petroleum
distillates. While the composition of these streams is quite
variable, they generally include cis- and trans-piperylenes,
6
isoprene, 2-methyl-2-butene, 2-methyl-1-butene, cyclopen•
tenc, acyclic pentanes, cyclopentadiene and dicyclopentadi•
ene.
Olefinic monomers may be co-reacted with the CS unsat•
urated hydrocarbons present in such streams. Examples
include 1-alkenes such as isobutylene and diisobutylene,
vinylaromatic monomers such as styrene, terpenes such as
those mentioned above, and mixtures thereof. Also, olefins
such as 2-methyl-2-butene may be added to such streams to
increase the amount of the corresponding olefin already
10 present therein. Catalysts that may be used include Lewis
acids such as AlCl3, BF3 and derivatives thereof.
Another type ofthe hydrocarbon resin that may be utilized
to prepare a surfact ant accordin g to the present invention is
prepared using thermal polymerization of streams rich in
15 dicyclopentadiene, including it s isomers and derivatives.
Additionally, these monomers may be thermally co-polymer•
ized with a mixture of vin ylarom atic monomers, such as those
listed previously, as well as with pure styrene or pure alkyl
styrenes, such as those mentioned above. The hydrocarbon
20 resins may be used as prepared, or may be partially or com•
pletely hydrogenated. However completely or substantially
hydrogenated hydrocarbon resins are not pref erred because
they can be more difficult to react to for m an adduct. In one
aspect of the invention, the hydrocarbon resin contains unsat•
25 uration, i.e., contains double and/or triple carbon -carbon•
bonds. In another aspect of the invention the hydrocarbon
resin has not undergone a hydrogenation treatment prior to
reaction with an a,�-unsaturated carboxylic acid or anhy-
dride or ester.
30 Some of the processes that may be used to prepare
the above-described terpene, terpene-phenol, terpene-
vin ylaro• matic and hydrocarbon resins, are described in
the Kir k• Othmer Encyclopedia of Chemical Technology,
Fourth Edi• tion, Volume 13, pp. 717-743, John Wiley &
35 Sons, New York, N.Y .
The selected hydrocarbon resin is reacted with an a,�•
unsaturated carboxylic acid, or anhydride or ester thereof, to
provide a carbonyl-containing resin, also referred to herein as
40 an adduct. As used herein, "a,�-unsaturated carboxylic acid"
ref ers to compounds that have the structure (R 1 )(R 2)C= C
(R3 )- C(= 0 )- 0 H where each of R 1, R2 and R3 is selected
from hydrogen, halogen and organic groups. Thus, an a,�•
unsaturated carboxylic acid has at least one double bond
45 between adjacent carbon atoms, wherein at least one ofthese
carbon atoms is bonded to a carboxyl group. The term "a,�•
unsaturated carboxylic anhydride" simply refers to the anhy•
drides thereof , which may be mixed anhydrides (i.e., formed
from two dif ferent carboxylic acids) or may be homogeneous
50 anhydrides (i.e., formed f rom two molecules having the same
structure), or may be internal anhydrides (i.e., one molecule
has two carboxylic acid groups, and those two groups react
together to form an anhydride, e.g., maleic anhydride).
Grafting unsaturated acids and anhydrides onto resins
55
using a thermal condensation process is described in, for
example , U.S. Pat. Nos. 3,379,663 and 3,953,407. Free radi•
cal graftin g has also been disclosed in U.S. Pat. Nos. 3,279,
925; 3,005,800; and 3,161,620. Either of these approaches
may be utilized to prepare an adduct in the process of
60
the present invention. The graf ting reaction may be carried
out without solvent at a temperature ranging from 170° C. to
240° C. Alternatively, a solvent may be used. Excess,
unreacted acid or anhydride may be removed by, for
example, distilla• tion. Reaction time may vary from 2-24
65
hours.
In one particular embodiment of the process of the present
invention, the a,�-unsaturated carboxylic acid is maleic acid,
and the a,�-unsaturated carboxylic anhydride is maleic anhy-
 US 7,452,941 B2
7 8
dride. Other a,�-unsaturated carboxylic acids and anhydrides
thereof that may be used for the adduct-forming reaction
include, but are not limited to, fumaric, citraconic and
ita•
conic acids and their respective anhydrides. Furthermore,
esters ofan a,�-unsaturated carboxylic acids may be used for
the adduct-forming reaction. In general, about 1-30 wt% of
the a,�-unsaturated carboxylic acid is reacted with the resin,
based on the total weight of a,�-unsaturated carboxylic acid
and resin. For instance, when maleic anhydride is used for the
adduct-f orming react ion, about 1-30 parts of maleic anhy-
dride are reacted with 10 0 parts of resin. In various aspects of
the invention, the residue from the a,�-unsaturated carboxy-
lie acid or anhydride or ester thereof constitutes at least 3 wt
%, or at least 4 wt %, or at least 5 wt %, or at least 6 wt%, or
at least 7 wt% of the weight of the adduct. When the residue
from the a,�-unsaturated carboxylic acid or anhydride or
ester thereof constitutes less than about 3-4 wt% of the adduct
weight, the subsequently-f ormed surf actant may not have
enough hydrophilic character to function as a surfactant.
Thus, in various additional aspects, the residue from the a,�•
unsaturated carboxylic acid or anhydride or ester thereofthat
is present in the adduct constitutes 3-30 w t% of the adduct
weight, or3 -25 wt% , or3 -20w t %, or 3-15 wt% , or 3-10 wt
%, or 4-25 wt%, or 4-20 wt% , or 4-15 wt% , or 4-10 wt% ,
or 5-25 wt% , or 5-20w t %, or 5-15 wt%, or 5-l Ow t %, each
percent value based on the total weight of adduct. Such
weight measurements can be made by measuring the weight
of the st arting material hydrocarbon resin , and then weighing
the product adduct. The difference is attributed to the weight
contributed by the residue from the a,�-unsaturated carboxy-
lie acid or anhydride or ester thereof. When this difference is
too small, the adduct does not have the desired surfactancy
characteristics.
In a pref erred embodiment, a terpene resin is reacted with
maleic anhydride to provide an adduct, and this adduct is
reacted so as to incorporate poly(alkylene oxide) groups. For
inst ance , the adduct may be reacted with alkylene oxide, e.g.,
ethylene oxide, and thereby form poly(alkylene oxide)
directly on the adduct . Alternatively, the poly(alkylene oxide)
may be formed separately, and then reacted with the adduct .
Methods for reacting alkylene oxide with a carboxylic acid
group so as to convert the acid into the correspondin g poly
(alkylene oxide) ester, and methods for reacting poly(alky•
lene oxide) with a carboxylic acid group, are both well known
in the art.
For example, in one aspect the invention , the adduct may be
subsequently reacted with a reactive polyalkylene polyol or
an alkylene oxide (collectively, PAO) to provide the surfac•
tant. When the adduct is prepared using an a,�-unsaturated
carboxylic acid or anhydride thereof, then the reaction with
hydroxyl-terminated PAO is an esterification reaction. When
an esterofthe a, � -unsaturated carboxylic acid or anhydride is
used to prepare the adduct, then reaction with hydroxyl•
terminated PAO is a transesterification reaction.
As used herein, PAO refers to an essentially linear polymer
("chain polymer") having a molecular weight ranging from
1,000-20,000 that contains repetitive alkylene ether groups.
An alkylene ether group is represented by - R---0- where
"R" represents a C1 -C6 alkylene group and "O" represents
oxygen, where the PAO has repetitive - R---0- groups,
denoted (- R---0- )n, where R is independently selected at
each occurrence. A preferred alkylene group is a C 2 alkylene
group, i.e., an ethylene group- The PAO has at least one
carboxyl-reactive group, e.g., a hydroxyl or amino group. In
one aspect, the PAO has two carboxyl-reactive groups,
where
in a preferred embodiment both of these carboxyl-
reactive groups are hydroxyl groups. Two or more different
PAOs may
be reacted with the adduct, where these PAOs may dif fer in
various ways, e.g., compositionally in that one PAO may
contain more ethylene oxide residues than another PAO, or by
molecular weight in that one PAO may have a larger average
5 (either number average or weight average) molecular weight
than another PAO.
In one specific embodiment, the PAO is polyethylene gly-
col (herein af ter, "PEG"). In a related embodiment, the
molecular weight of the PEG ranges f rom 1,000 to 20,000.
10 The molecular weight of the PEG, in another related embodi•
ment, ranges f rom 2,000t o 8,000. In a preferred embodiment,
the PAO has two hydroxyl groups, one of which reacts with
the adduct , and the other of which is available for further
functional group modification as discussed below.
15 The amount of PAO reacted with the adduct may range
from about 0.8 to 1.8 equivalents of hydroxyl per equivalent
of carboxyl group present in the adduct . The temperature at
which the adduct is reacted with the PAO may range from
about 240° C. to 290° C. A more narrow temperature range of
20 from 240° C. to 265° C. may be used instead. In one embodi•
ment, the reaction between the adduct and PAO is carried out
until an acid number of 25 or less is reach ed, while in another
embodiment the reaction is carried out until an acid number of
less than 5 is reached. Thus, in one aspect, the surfactant has
25 an acid number of less then 25, while in another aspect the
surf act ant has an acid number of less than 5. In another aspect
surfact ant has an acid number within the range of 5 and 25.
Furthermore, while not required, a catalyst may be used for
the above esterification reaction between the PAO and the
30 resin adduct. Catalysts that may be used include, but are not
limited to, acids such as phosphoric, hypophosphorus and
sulfuric acids; alkylsulf onic and arylsulf onic acids; and
oxides, hydroxides and carboxylates of Group I and Group II
elements (alkaline and alkaline earth).
35 The present invention, in another representative embodi-
ment, is directed to a process for preparing a surfact ant that
comprises formin g an adduct and reacting that adduct with
PAO, as described above, and then modif yin g the surf actant
by means of phosphorylation or sulf ation to provide a f unc-
40 tionalized surf actant. In a preferred embodiment, the reaction
between the adduct and the PAC) provides a surf act ant mol•
ecule that has a plurality of polyalkylene polyol chains, such
as PEG chains, grafted to the adduct backbone. Many of the
plurality of chains terminate with a hydroxyl group. Thus, at
45 the sites of the hydroxyl groups, the chains may be function•
alized to yield surfact ants having dif ferent properties,
depending upon the pendent functionality imparted thereto.
Imparting pendent functionality to the surfactant by sulfa•
tion may be accomplished using sulfur trioxide (S03), oleum,
50 or acetyl sulf ate. The formation of sulf on ates is also possible
when there are double bonds present in the surf act ant adduct
backbone or polyalkylene polyol chains pendent therefrom.
Imparting pendent functionality to the surf actant by phospho•
rylation of the hydroxyl-terminated chains may be accom-
plished using reactants that in clude, but are not lim ited to,
55 phosphorus pentoxide (P 2 0 5 ) , phosphorus trichloride (PC13 ) ,
polyphosphoric acid, and phosphorus oxychloride (POC13).
Thus, in various aspects, the present invention is directed to
a surfactant prepared by reacting a resin with an a,�-unsat-
60 urated carboxylic acid or ester or anhydride to thereby form
an adduct; optionally reacting the adduct with a poly(alkyle•
neoxide) (PAO) to provide a surfactant; and optionally treat•
ing the surfactant under sulfation or phosphorylation condi-
tions to provide a modified surfactant.
65 In one aspect of the invention, the surfactant is isolated
prior to being used as a surfactant, i.e., it is isolated and/or
purified prior to being combined with water. Thus, the
inven-
 US 7,452,941
9 B2
tion provides, in one aspect, surfactant that is anhydrous at
room temperature and pressure. This isolated surfactant can
then be added to other compositions, e.g., tackifier resins, to
provide an aqueous dispersion of the tackifier. Thus, in one
aspect, the adduce is provided in isolated form, while in
another aspect the surfactant is provided in isolated form,
each at room temperature and pressure. In one aspect, "iso•
lated form" means free from water.
The present invention, in yet further aspects, is directed to
compositions comprising a surfactant as described herein and 10
a tackifier resin, and to aqueous dispersions comprising these
two components. As used herein, "tackifier resin" refers to a
resin that enhances the adhesive properties of an
adhesive formulation . Such adhesive properties in clude,
without limi• tation, tackiness, peel-resistance and ease of 15
surf ace wettin g. Suitable tackifier resins include the terpene,
terpene-h ydro• carbon , terpene-phenol, and hydrocarbon
resins described pr eviously. Another suitable tackifier resin
is a rosin ester tackifier resin.
Compositions of the present invention, comprising a dis• 20
closed surf actant and a tackifier resin, may be prepared by
melting the tackifier resin, then adding the surf actant and
mixing it with the resin by stirring. Aqueous dispersions of
surf actant/tackifier resin may be prepared by adding hot water
to the melted tackifier resin having the surfactant mixed there• 25
with. The hot water may be added to first form a water-in -oil
emulsion. More water is then added to bring about an inver•
sion to an oil-in-water emulsion and, then, to provide the
aqueous dispersion having a desired solids content. The
emulsion is then cooled to a temperature of 50 ° C. or less, and, 30
if needed, biocides may be added.
Some spe cific examples of t ackifier resin/surfactant com•
binations that are present in the disclosed compositions and
aqueous dispersions of the present invention in clude: (1)
rosin ester tackifier resin/terpene-vinylaromatic resin-MA• 35
PEG surf actant; (2) rosin ester tackifier resin/terpene-phenol
resin-MA-PEG surf actant; (3) rosin ester tackifier resin/viny•
laromatic-m od ified hydrocarbon resin -MA-PEG; (4) terpene
tackifier resin/terpene resin-MA-PEG surf actant; (5) terpene
tackifier resin/hydrocarbon resin-MA-PEG surfact ant; (6) 40
terpene-vin y!arom atic tackifier resin/terpene-viny!aromatic
resin-MA-PEG surf actant; (7) terpene-vinylaromatic tack i•
fier resin/vinylarom atic-m odified hydrocarbon resin-MA•
PEG surfact ant; (8) terpene-phenol tackifier resin/terpene•
phenol resin-MA-PEG surfact ant; (9) hydrocarbon tackifier 45
resin/terpene-MA-PEG; (10 ) hydrocarbon tackifier resin/hy•
drocarbon resin-MA-PEG surf act ant; (11) aromatic-modi•
fied hydrocarbon tackifier resin/terpene-viny!arom atic resin•
MA-PEG surf act ant; (12) aromatic-mod ified hydrocarbon
tackifier resin/vinylaromatic-modified hydrocarbon resin- 50
MA-PEG surfact ant. Each of these combinations is a separate
aspect of the present invention, where "MA" indicates that
maleic anhydride was reacted with the indicated resin to form
the adduct, and PEG indicates that a polyethylene glycol
molecule was reacted with the indicated adduct. In each of
55
these separate aspects, the criteria as set forth above, e.g.,
acid number, extent of adduction as measured in weight
percent, molecular weight of the PEG, ctc., may be used to
tion.
further characterize the products and processes of the present
inven•
An exemplary aqueous dispersion that is suitable for use in
waterborne adhesives may have a solids content ranging from
50-60% or from 55-60%, a pH ranging from 4-9 or 6-8; a
viscosity that is less than 8000 cps or less than 1500 cps or less
than 10 00 cps (Br ookfield #5/20 rpm or# 3/ 50 rpm); a particle
size of less than 2 µm or less than 1 µm; and a mechanical
stability sufficient to pass industry screening tests related to
10
pumping, formulating operations, and the like. Further, the
aqueous dispersions of the present invention may comprise,
in addition to a disclosed surfactant, a co-surfactant that may
be anionic, nonionic or polymeric.
The present invention, in another aspect, is directed to an
adhesive composition comprising a tackifier resin, a polymer
latex, water, and at least one of: a surfactant prepared by
reacting a resin with an a,�-unsaturated carboxylic acid or
esteror anhydride to thereby form an adduct; optionally react-
ing the adduct with a poly(alkyleneoxide) (PAO) to provide a
surf act ant; optionally treating the surfactant under sulf ation
or phosphorylation conditions to provide a modified surfac•
tant.
The adhesive compositions may be prepared by blending
an aqueous tackifier dispersion of the present invention with
a natural or synthetic polymer latex or blend of latexes,
according to techniques well known to those of skill in the art.
Suitable polymer latexes include aqueous suspensions of
natural rubber or synthetic elastomers. The latter elast omeric
polymers in clude, but are not limited to, acrylic polymers
derived from 2-ethylhexyl acrylate, butyl acrylate, methyl
methacrylate, methacrylic acid, and acrylic acid; polystyrene,
a styrene-butadiene copolymer; a polymer derived from a
vinyl acetate such as ethylene vinyl acetate; polychloroprene;
an acrylon itrile-butadiene copolymer.
In a further aspect, the present invention is directed to a
pressure sensitive adhesive overlay, prepared by applying a
layer of a disclosed adhesive composition to a surface of
a substrate, serving as an adhesive carrier, and drying the
layer. As used herein , the term "overlay" ref ers to any
substrate having a layer of adhesive material applied to at
le ast a portion of its surf ace ("first surf ace") and, thereby,
adapted to be adhesively applied to a surface of another
substrate ("se cond surf ace ") by bringing the first and second
surfaces into con- tact under pressure.
A subst antial portion of the commercial production of
waterborne adhesives is used f or the manuf acture of pressure
sensitive adhesives (PSAs) for adhesive overlays such as
labe ls, tapes, decorative appliques, and the like. Suitable sub-
strates servin g as adhesive carriers may be prepared using
non-woven material such as, f or example, paper, plastic,
metal or f oam; or may be prepared using woven material,
such as, f or example, woven cotton or woven synthetic poly•
mers. Some examples of the latter are polyethylene, polypro-
pylene, polyvinyl chloride, polyester, and polyamide.
The following examples are provided for the purpose of
illustration, not limitation.
EXAMPLES
Example 1
Preparation of an Adduct by Reacting Maleic
Anhydride with a Terpene-Vinylaromatic Resin
A four-neck, 1 L round-bottom flask was charged with 450
grams Sylvares® ZTl 05LTterpene-viny!aromatic resin (Ari•
zona Chemical Company, Jacksonville, Fla.) and heated to
150° C. under 2 LPM nitrogen purge. When the resin had
60 melted and was sufficiently fluid, stirring was started at about
250 rpm. To the stirred resin was added 50.0 grams ofmaleic
anhydride. The contents of the flask were placed under a
nitrogen atmosphere, and heated to 200° C. The agitation was
incr eased to 300 rpm . The reaction mass was stirred for 16.5
65 hours at 200° C., then heated to 250° C. over about 5.5 hours.
A sample was analyzed showin g 97 .1 % conversion of the
maleic anhydride. The temperature was lowered to 200° C.,
 US 7,452,941 B2
11
and the contents of the flask were sparged with nitrogen to
remove the unreacted maleic anhydride until the acid value of
a water-e xtract (equal weight to sample) was 0.3. The con•
tents of the flask were disch arged. Analysis of the adduct
showed 6.54% maleic anhydride adducted by weight.
Example 2
Preparation of Resin Dispersion Surfactant by
Reacting the Adduct of Example 1 with Polyethylene
Glycol
A 1 L, four-neck round-bottom flask equipped with a
paddle stir sh aft, nitrogen inlet and thermocouple was
charged with 10 0.0 grams of the adduct from example 1 and
143.2 grams of polyethylene glycol having an average
molecular weight of 2000 ("PEG 2000", Aldrich Chemical
Com pany, Milwaukee, Wis.). The contents of the flask were
heated, under 1 LPM nitrogen purge. Stirring was started
when the contents were molten and sufficiently fluid. When
the temperature reached 219° C., 0.54 grams of 7 5% ph os•
phoric acid was charged and the flask placed under a nitrogen
atmosphere, and heated to 250° C. The reaction mass was
stirred at this temperature for 20 hours. A sample of reaction
mass had an acid number of 1.4. The contents of the
flask were-cooled to 157° C. and discharged.
Example 3
Dispersion of a Rosin Ester Tackifier Resin With the
Surfactant of Example 2
A 1.5 L resin flask was charged with 300.0 grams of Syl•
vares® RE-85 (Arizona Chemical Com pany, Jacksonville,
Fla.) and 18 .0 grams of surf act ant from example 2. The con•
tents were heated under a 2 LPM nitrogen sweep to 98° C.
Stirring was st arted, and the flask was placed under a nitrogen
blanket. A solution of 2.1 grams of 50% potassium hydroxide
in 47 grams distilled water was prepared and heated to 80° C.
When the temperature of tackifier resin-surfact ant blend was
112° C., the hot potassium hydroxide solution was added to
produce first a water-in-oil dispersion , which inverted to an
oil-in-water dispersion. The temperature of this dispersion
was brought to 97° C., and 160 grams of hot distilled water
was added over 18 minutes. The resulting diluted dispersion
was cooled to 59° C., and some biocide was added. After
cooling further to 50 ° C., the dispersion was analyzed for a pH
of 9.5.A sample of the dispersion was adjusted to a pH of 7.5
and 58.8% solids and a mean particle size of 0.84 microns.
All of the above U.S. patents, U.S. patent application pub•
lications, U.S. patent applications, for eign patents, foreign
patent applications and non-patent publications ref erred to in
this spe cification and/or listed in the Application Data Sh eet,
are incorporated herein by reference, in their entirety.
From the for egoing it will be appreciated that, although
specific embodiments of the invention have been described
herein f or purposes of illustration, various modifications may
be made without deviating from the spirit and scope of
the invention. Accor dingly, the invention is not limited
except as by the appended claims.
The invention claimed is:
1. A process for preparing a surfactant comprising: reacting
an a, �-unsaturated carboxylic acid or anhydride, or an ester
thereof, with a resin comprising hydrocarbon monomeric
residues, to provide an adduct; and reacting the adduct with
either alkylene oxide or a carboxyl-reactive poly(alkylene
oxide) to provide the surfactant, wherein the resin is selected
12
from the group consisting of a terpene-phenol resin, a ter•
pene-hydrocarbon resin, and a terpene-vinylaromatic resin
wherein the resin comprises at least one residue selected from
the group consisting of residues of o-pinene, � -pinene,
limonene, dipentene, � -phellandrene, 1\-3-carene, and 1\-2-
carene, wherein the resin further comprises at least one resi•
due selected f rom the group consisting of r esidues of isobu•
tylene, I- alk ene, 2-alkene, a trisubstituted alkene, and
vinylcyclobexene.
10 2. A process for preparing a surfactant comprising; reacting
an a, � -unsaturated carboxylic acid or anhydride, or an ester
thereof, with a resin comprising hydrocarbon monomeric
residues, to provide an adduct; and reacting the adduct with
15 either alkylene oxide or an carboxyl-reactive poly(alkylene
oxide) to provide the surfactant, wherein the resin is selected
from the group consisting of a terpene-phenol resin, a ter•
pene-hydrocarbon resin, and a terpene-vinylaromatic resin
wherein the resin comprises at least one residue selected
20 from
the group consisting of residues of o-pinene, � -pinene,
limonene, dipentene, � -phellandrene, 1\-3-carene, and 1\-2-
carene wherein the resin further comprises at least one residue
selected from the group consisting of residues of piperylene,
25 isoprene, 2-methyl-2-butene, 2-methyl-1-butene, cyclopen•
tenc, an acyclic pentene, cyclopentadiene, and dicyclopenta-
diene.
3. A process for preparing a surfactant comprising: reacting
an a, � -unsaturated carboxylic acid or anhydride, or an ester
30
thereof , with a resin comprising hydrocarbon monomeric
residues, to provide an adduct ; and reacting the adduct with
either alkylene oxide or a carboxyl-reactive poly(alkylene
oxide) to provide the surfact ant, wherein the resin is selected
35 from the group consisting of a terpene-phenol resin, a ter•
pene-hydrocarbon resin, and a terpene-vinylaromatic resin,
wherein the resin comprises at le ast one residue selected from
the group consisting of residues of piperylene, isoprene,
2-methyl-2-butene, 2-methyl-1-butene, cyclopentene, an
40 acyclic pentene, cyclopentadiene, and dicyclopentadiene.
4. A process for preparing a surfactant comprising: reacting
an a, � -unsaturated carboxylic acid or anhydride, or an ester
thereof, with a resin comprising hydrocarbon monomeric
residues, to provide an adduct; and reacting the adduct with
45
either alkylene oxide or a carboxyl-reactive poly(alkylene
oxide) to provide the surfactant, wherein the resin is selected
from the group consisting of a terpene-phenol resin, a ter-
pene-hydrocarbon resin, and a terpene-hydrocarbon resin,
50
and a terpene-vinylaromatic resin, wherein the adduct is
reacted with poly(ethylene glycol) or a mixture of more than
one poly(ethylene glycol).
5. A process for preparing a surfactant comprising: reacting
an a, � -unsaturated carboxylic acid or anhydride, or an ester
55
thereof, with a resin comprising hydrocarbon monomeric
residues, to provide an adduct; and reacting the adduct with
either alkylene oxide or a carboxyl-reactive poly(alkylene
oxide) to provide the surfactant, wherein the resin is selected
from the group consisting of a terpene-phenol resin, a ter•
60
pene-hydrocarbon resin, and a terpene-vinylaromatic resin,
wherein the adduct in reacted with ethylene oxide.
6. A composition comprising the surfact ant of any of
claims 1, 2, 3, 4, and 5 and a tackifier resin.
7. An aqueous dispersion comprising water and the com•
65
position of claim 6.
8. An adhesive composition comprising the surfactant of
any of claims 1, 2, 3, 4, and 5, a tackifier resin, a polymer
latex, and water.
9. A pressure sensitive adhesive overlay prepared by apply•
ing a layer of the adhesive composition of claim 8 to a surface
of a substrate, and drying the layer.
 US 7,452,941
13 B2
10. An adhesive composition comprising the surf act ant of
any of claims 1, 2, 3, 4, and 5.
11. A process f or preparing a surfact ant comprisin g: react•
ing an .alph a .. . beta-unsaturated carboxylic acid or anhy•
dride, or an ester thereof , with a resin comprising hydrocar•
bon monomeric residues, to provide an adduct; and reactin g
the adduct with either alkylene oxide or a carboxyl-reactive
poly(alkylene oxide) to provide the surf act ant, wherein the
resin is a terpene-phenol resin and comprises at least one
residue select ed from the group consisting of residues
of .alpha.-pinene, .beta.-pinene. .delt a.-3-carene and
limonene.
12. The process of claim 11 wherein the terpene-phenol
resin further comprises at least one residue selected from
the
14
group consisting of residues of styrene, indene, .alph a.-me•
thylstyrene, an alky!arom atic styrene, divin ylbe nzene, a divi•
nylbenzene with one or more alkyl groups, isobutylene,
diisobutylene, a I- alkene, a 2-alkene, a trisubstituted alk ene,
vinylcyclohexene, piperylene, isoprene 2-methyl-2-butene,
2-methyl-1-butene, cyclopentene, an acylic pentene, cyclo•
pentadiene, and dicyclopentadiene.
13. The process of claim 11 wherein the phenol is selected
from the group consisting of phenol, a mono substituted phe•
10
nol, a disubstituted phenol, a trisubstituted phenol and a
hydroxyl-substituted naphthalene compound.
* * * * *
 I III IIIIII Illllllllllllllllllllllllllllllllllllllllll111111111111111111
US009023929B2

c12) United States Patent (IO) Patent No.: US 9,023,929 B2

Aarts et al. (45) Date of Patent: May 5, 2015

(54) TACKIFIER DISPERSION 5,030,388 A * 7/1991 Martino et al. ...............

56 0/ 12 7
(75) Inventors: Patrick Peter Mario Aar t s, Elsloo 5,552,519 A 9/19 96 Hemmings et al.
6,274,657 Bl * 8/2001 Geoghegan et al. ..........
(NL); Lodewijk Johannes 52 4/ 270
Hubertus Houben, Eijsden (NL); 6,464,764 Bl 10 /2002 Lichtenberg et al.
John Hazen, Spaubeek (NL) 2001/ 00217 37 Al * 9/2001 Hazen et al . ..................
52 4/ 30 0
(73) Assignee: Lawter, Inc., Chicago, IL 2003/0092829 Al 5/ 2003 Klauck et al.
(U S) 2003/0212201 Al * 11/ 2003 Hazen et al. ..........
( *) Notice : Subject to any disclaim er, the term 52 4/ 845 FOREIGN PATENT
of t his patent is extended or adju sted 2004/0158003 DOCUMENTS
Al 8/2004 Ruckel et al.
EP
2004/0171727 Al 0258753
* A2 Winters
9/2004 9/1988et al. ................
under 35 1172395 Al 1/2002
EP
524/270
U.S.C. 154(b) by 921 days. GB 785474 10/1957
(21) Appl. No.: 11/053,682 GB 1600933 10/1981
GB 2137212 A 10/1984
(22) Filed: Feb.9 ,2 005 SU 1098930 A 6/1948
SU 1098930 A 6/1984
(65) Prior Publication Data WO WO 8/1994
WO 94/18 260 10/1994
US 2005/0203228 Sep. 15, WO WO 8/1999
Al 2005 * cited by 94/24221
WO
Related U.S. Application Data
examiner 99/39886
(60) Provisional application No. 60/543,913 , filed on Primary Examiner - Michael Pepitone
Fe b. (74) Attorney, Agent, or Firm - Foley & Lardner,
13, 2004. LLP
(51) Int. Cl.
(57) ABSTRACT
COSKS/10 (2006.0 1
BOJF 17/36 ) The in vention relates to a tackifier dispe rsion
(52) U.S. Cl. (2006.0 1 com prising a resinous material and an emulsifie r, the
CPC ) COSK 5/10 (2013.01) emulsifier being obtainable by a method com prisin g
(58) Field of Classification Search pr ovid in g an e ster of one or more fatty acids containing at
CPC C08K 5/09; C08K 5/10; C08K least two con ju gated double bonds, reacting the ester with
5/103; C08K 67/025; a die nophile containing an acid or anhydride group, to
USPC C08K 67/08 form an intermediate product A, and, reacting the
524/77, 270, 306, 881, 501, 539, intermediate product A with one or more poly• alkylene
See application601,
file for complete search glycols. The inve ntion also relates to a method for the
history. 524/604, 878; production of a tackifier dispe rsion , its use as a tackifie r,
(56) References Cited 530/216 and an adhesive composition comprising the tackifier
disper• sion . The invention further relates to an em ulsifier,
U.S. PATENT
DOCUMENTS a method of producing the same and its use for
4,477,613 A * 10 /19 84 Evans et al. 524/77 emulsifying resinous materials.
4,670,504 A * 6/1987 Cardenas et 524/504 43 Claims, No Drawings
al
 US 9,023,929 B2
1 2
TACKIFIER DISPERSION
This application claims priority from U.S. Provisional
Application No. 60/543,913, filed on Feb. 13, 2004.
The present invention relates to a tackifier dispersion com•
prising an emulsifier, a process for the production of the same,
its use as a tackifier, and an adhesive composition comprising
the tackifier dispersion . The invention also relates to an emul•
sifier, a method of producing the same and its use for emul-
sif ying resinous materials.
BACKGROUND
Many types of adhesive formulations, especially pressure
sensitive adhesives based on synthetic polymers, such as
acrylic polymers and styrenic block -copolymers, usually
need some kind of t ack ifier in the formulation. The tackifier
improves the adhesive properties such as tackiness, peel•
resistance and ease of surface wetting. The tack of an adhesive
enables it to f orm an immediate bond between contacted
surfaces when they are brought together.
Tackifiers are generally based on resins, tackifier resins,
which can be considered as high viscosity solvents f or a base
polymer in a f ormulation . A tackifier should be seen as a
material which relates to a specific material or group of mate•
rials that it tackifies.
Various resinous materials have been suggested as tackifier
resins for synthetic polymers. Examples of materials sug•
gested include rosin, disproportionated rosin, rosin esters
such as glycerol esters of rosin and pentaerythritol esters of
rosin, aliphatic hydrocarbon resins, aromatic petroleum res•
ins, DCPD resins, terpene resins, terpene/phenol resins and
cumarone/indene resins.
Tackifier resins for pressure sensitive adhesives are usually
based on rosin and/or derivatives thereof or hydrocarbon res•
ins. Rosin is a natural resinous product mainly consisting of
rosin acids. Typical rosin acids are, f or example , abietic acid
and levopimaric acid. The dif ference between the rosin acids
is mainly the number and position of the double bonds. Rosin
may be classified due to the species of the tree from which it
originates such as Chinese, Indonesian, and Brazilian rosin
and/or to the production process from which it originates such
as gum rosin, wood rosin or tall oil rosin.
Hydrocarbon resins are generally low-molecular weight
aliphatic or aromatic polymers typically having a weight
average molecular weight of 500-3000. Common aliphatic
hydrocarbon resins are resins derived from so called C5 feed
streams and common aromatic hydrocarbon resins are
derived from C 9 feed streams. These feed streams originate
from the oil cracking industry.
In aqueous adhesive compositions it is common to in clude
the tackifier resin in the form of an aqueous dispersion. In
order to make a dispersion from a resinous material such as
rosin or hydrocarbon resin, a surf act ant is needed acting as an
emulsifier. In the case of rosin and hydrocarbon resins, the
aqueous dispersion is usually made by first melting the rosin
or hydrocarbon resin and then addin g a surfact ant and water
to form a dispersion in which the rosin/resin is the dispersed
phase and water the continuous phase.
Many different surfactants are known in the art such as
alkyl sulphonates, fatty alcohol sulphates, and phosphate
esters. However, the use of these types of surfactants may
result in an adhesive, when dried, being hygroscopic which
may result in an unwanted whitening of the adhesive film.
Also, the cohesive strength ofan adhesive bond and mechani-
cal stability of the tackifier resin dispersion can be quite low.
U.S. Pat. No. 5,552,519 discloses a surfactant derived from
a rosin ester.
US 2003/0092829 discloses a binder based on a reaction
product of soybean oil, maleic anhydride and a polyethylene
glycol oflow molecular weight.
U.S. Pat. No. 6,464, 764. discloses a wood protective agent
comprising binder made from e.g. linseed oil and sm all
amounts of m aleic acid and polyethylene glycol.
WO 94/18260 discloses a water soluble and air-drying
10 resin having an iodine value of between 50 and 150 . The resin
comprises subst antially units of : A. a monoether of a poly•
ethylene glycol having 5-100 ethylene oxide units per mol•
ecule, and B. the reaction product of : Bl ) one or more unsat•
urated f atty acids or one or more polyalcohol(s) esterified
15 with unsaturated f atty acids with 82) an alpha, beta-ethyleni•
cally unsaturated carboxyl compound wherein the molar ratio
of A :B is from about 0.2:1 to about 4:1.
GB 785474 discloses a process f or the production of con•
densation products, comprising condensing a polyalkylene
20 oxide or a derivative thereof , which oxide or derivative pos•
sesses in addition to a lipoph ilic group at le ast one free
hydroxyl group and has a molecular weight of at least 10 00,
at an elevated temperature with a polybasic carboxylic acid
which contains at least three carboxyl groups and at least one
25 lipophilic group.
US 2004/0158003 discloses a process for preparing a sur•
factant comprising: reacting an a,�-unsaturated carboxylic
acid or anhydride, or an ester thereof, with a resin comprising
hydrocarbon monomeric residues, to provide an adduct ; and
30 reacting the adduct with either alkylen oxide or a carboxyl•
reactive poly (alkylen oxide) to provide the surfactant.
Important properties for a tackifier dispersion are its foam
behaviour, solids content/viscosity balance, mechanical sta•
bility, wetting properties, and shelf life.
35 Smaller rosin/resin particles in the tackifier dispersion will,
generally, give better stability which means longer shelf lif e.
Thus, there is still a need for a tackifier dispersion which
gives an improved water-resistance of a dried adhesive when
used in adhesive compositions compared to traditional sur-
40 factants. There is also a need of providing a tackifier disper•
sion fulfilling the requirements listed above.
It is accordingly an object of the present invention to pro•
vide a tackifier dispersion with high st or age stability, good
mechanical st ability and low foaming characteristics, and
45 which only gives low loss in cohesive strength when formu•
lated in to adhesive compositions. It is a further obje ct of the
present invention to provide an emulsifier that can be pro•
duced in a process only requiring few steps.
50 THE INVENTION
The objects of the present invention are achieved by a
tackifier dispersion comprising a certain emulsifier. The
invention also relates to a process for the production of a
55 tackifier dispersion, a method of producing an emulsifier, an
emulsifier, use of the emulsifier, use of the tackifier disper-
sion, and an adhesive composition comprising the tackifier
dispersion . It has surprisingly been found that tackifier dis•
persions comprising the emulsifier give very sm all particle
60 sizes of dispersed resinous material and can be made with
high solids contents. Also, tackifier dispersions com prising
the emulsifier have excellent st or age st ability and mechanical
stability. Furthermore, adhesive compositions comprising the
tackifier dispersion have high water resistance, excellent
65 cohesion, high adhesion, and good wetting properties.
One aspect of the invention concerns a process for the
production of a tackifier dispersion comprising dispersing a
 US 9,023,929
3 B2
resinous material in an aqueous phase in the presence of an
emulsifier, the emulsifier being obtainable by a method com•
prising providing an ester of one or more fatty acids contain•
ing at least two conjugated double bonds, reacting the ester
with a dienophile containing an acid or anhydride group, to 5
form an intermediate product A, and, reacting the intermedi•
ate product A with one or more polyalkylene glycols.
A further aspect of the invention concerns a tackifier dis•
persion comprising a resinous material and an emulsifier, the
emulsifier is being obtainable by a method as defined above. 10
The emulsifier can thus be a reaction product of one or more
polyalkylene glycols with an intermediate product A formed
by a reaction between an ester of one or more fatty acids
containing at le ast two conju gated double bonds with a dieno•
phile containing an acid or anhydride group.
Still a further aspect ofthe invention concerns the use ofan
emulsifier as defined above for dispersing a resinous material.
Another aspect of the invention concerns a process for the
production of an emulsifier comprising providing an ester of
one or more fatty acids containing at least two conjugated 20
double bonds, reacting the ester with a dienophile containing
an acid or anhydride group, to form an intermediate product
A, and, reacting the intermediate product A with one or more
polyalkylene glycols having an average molecular weight,
determined by hydroxyl number analysis, of more than 650. 25
Still another aspect of the invention concerns an emulsifier
obtainable by the process as described above. The emulsifier
can thus be a reaction product of one or more polyalkylene
glycols having a number average molecular weight of more
than 650 with an intermediate product A formed by a reaction 30
between an ester of one or more fatty acids containing at least
two conjugated double bonds with a dienophile containing an
acid or anhydride group.
The ester of one or more f atty acids suitably has an iodine
number of more than about 60, preferably more than about 35
10 0, most pr ef erably more than about 140 g iodin e per 10 0 g
of ester. The ester is suitably an ester of one or more f atty acids
and an alcohol. The alcohol is suitably a C 1 -C 10 mono-, di- or
trio! or a higher polyol, preferably a C1 -C6 mono-, di- or triol,
more pref erably a glycerol or ethylene glycol, most pr ef er- 40
ably glycerol. The ester is pref erably a glycol mono- or diester
of one or more f atty acids or a mono-, di- or a triglyceride of
one or more f atty acids, most pr ef erably a triglyceride of one
or more fatty acids. Suitable glycol mono- or diesters of one
or more f atty acids include any which contains two conju- 45
gated double bonds such as ethylene glycol linolenate and
ethylene glycol linolate. Suitable triglycerides of one or more
fatty acids include vegetable oils and some animal oils of
which , f or example , can be mentioned sardin e oil, linseed oil,
tung oil, walnut oil, soybe an oil, safflower oil, sunflower oil, 50
sesame oil, cottonseed oil, com oil, rapeseed oil, peanut oil,
crambe oil, castor oil, olive oil, canola oil, grapeseed oil, and
sesame oil, pr ef erably used are sardine oil, linseed oil, tung
oil, walnut oil, soybean oil, safflower oil, and sunflower oil.
Pref erably, the triglyceride is selected from the group of l in- 55
seed oil, soybean oil, and sunflower oil.
It is to be understood that the esters of one or more fatty
acids ref erred to herein do not in clude esters that might have
been f ormed from im purities of f atty acids in rosin when
making rosin esters.
Suitable dienophiles containing an acid or anhydride group
include alpha-beta ethylenically unsaturated carboxylic acids
and anhydrides thereof which may be sele cted from mono-,
di- and polybasic ethylenically unsaturated carboxylic acids
and anhydrides thereof as well as mixtures of two or more 65
ethylenicallyu nsaturated carboxylic acids or anhydrides. The
ethylenically unsaturated carboxylic acid is suitably an alpha-
4
beta unsaturated C3-C4- mono- or dicarboxylic acid and may
be selected from acrylic acid, crotonic acid, sorbic acid,
maleic acid, methylmaleic acid, ethylmaleic acid, propylma-
leic acid, butylmaleic acid, fumaric acid, and structurally
similar ones, and also anhydrides thereof. Suitably, the eth•
ylenically unsaturated carboxylic acids are dibasic acids or
anhydrides thereof , pref erably maleic acid , maleic anhydride,
and fumaric acid, most pref erably maleic anhydride.
The one or more polyalkylene glycols suitably belong to
the group of C 2-C 5 polyalkylene glycols, such as polyethyl•
ene glycol and polypropylene glycol. End-capped polyalky•
lene glycols such as C 2-C 5 polyalkylene glycol mono alkyl
ethers, wherein alkyl suitably is C1 -C5 alkyl, preferably
C1 -C4 alkyl such as methoxy polyethylene glycol and butoxy
15 polyethylene glycol, are particularly preferred. Most prefer•
ably, at least one of the one or more polyalkylene glycols is
polyethylene glycol. The average molecular weight of the
polyalkylene glycol, determined by hydroxyl number analy-
sis, is suitably from about 500 to about 12000 and preferably
more than 650. Preferably the molecular weight is from
about
1000 to about 8000, most preferably from about 1500 to about
5000. It is also suitable to use a mixture of one polyalkylene
glycol of higher molecular weight with another with a lower
molecular weight. In such cases the one or more polyalkylene
glycols are may be a mixture of a polyalkylene glycol having
an average molecular weight, determined by hydroxyl num-
ber analysis, of suitably f rom about 500 to about 2500, pr ef•
erably from about 10 00 to about 2000, with a polyalkylene
glycol having an average molecular weight of suitably f rom
about 3000 to about 50 00, preferably from about 3500 to
about 4500.
The weight ratio of the ester of one or more f atty acids to
the dienophile is suitably f rom about 0.5:1 to about 20:1,
pref erably from about 1: 1 to about 10 : 1, more preferably
from about 1: 1 to about 8: 1, most preferably f rom about 4: 1 to
about 8: 1.
The reaction of the ester of one or more f atty acids with the
dienophile suit ably f orms a Diels-Alder adduct f rom an
unsaturation in the dienophile and the conjugated double
bonds in the f atty acid part of the ester and thus introd uce s one
or more acid and/or anhydride groups therein . The resultin g
intermediate product A pref erably has an iod ine number f rom
about Ot o about 10 0, more preferably from about 10 to about
80, most preferably from about 10 to about 70 g iodine per
100 g ofA.
The reaction of the ester of one or more f atty acids with the
dienophile suitably takes place in a reaction mixture at a
temperature of f rom about 160 to about 260° C., preferably
from about 180 to about 230° C., most pref erably from about
190 to about 220° C.
The one or more acid and/or anhydride groups in interme•
diate product A introduced by the Diels-Alder reaction con•
stitute grafts for further reaction with the hydroxyl group in
the one or more polyalkylene glycols. The weight ratio inter•
mediate product A to total amount of the one or more poly•
alkylene glycols, is suitably from about 0.05:1 to about 5:1,
pref erably f rom about 0.08: 1 to about 1: 1, more preferably
from about 0.1:1 to about 0.5:1, most pref erably from about
0.1:1 to about 0.4:1. The resulting emulsifier preferably has
60
an iodin e number f rom about Oto about 20, more preferably
from about 2 to about 17 , most pr ef erably from about 5 to
about 15 g iod ine per 10 0 g of prod uct . The number average
molecular weight of the emulsifier is pref erably from about
2000 to about 19000, more pr ef erably from about 4000 to
about 12000, most pref erably f rom about 6000 to about 7000.
In one embodiment the emulsifier is a mixture of at least one
component having a molecular weight from about 7000 to
 US 9,023,929 B2
5 6
11000, at least one component having a molecular weight
from about 3000 to about 6500 and at least one component
having a molecular weight from about 300 to about 1000.
The reaction of the intermediate product A with the one or
more polyalkylene glycols suit ably takes place at a tempera•
ture of f rom about 160 to about 300° C., preferably from
about 190 to about 260° C. The optimal temperature may
depend on which polyalkylene glycol that is used.
The resinous material is suitably a hydrocarbon resin or a
rosin, or a mixture thereof . Suitable hydrocarbon resins 10
include aliphatic or aromatic hydrocarbon resins derived
from respectively C5 feed streams and C 9 feed streams,
DCPD resins, terpene resins, terpene/phenol resins and
cumarone/indene resins. The resinous material is pr ef erably a
rosin. The rosin comprises rosin acids which are mainly a 15
mixture of C 20 monobasic carboxylic acids containing a
phenanthrene skeleton. The rosin can be an unmodified or a
modified rosin. There are many dif ferent ways of modif ying
rosin. The rosin can be partially f ortified or esterified. Pref •
erably, the rosin is a glycerol, pentaerythritol or triethylene
20
glycol ester of a rosin acid. The rosin can be treated with
paraformaldehyde in the presence of paratoluene sulph onic
acid to inhibit crystallization or it can be st abilized by dispro•
portionation which involves transf erring hydrogen atoms
from one molecule of abietic acid to another. This is suitably
carried out by heating rosin at from about 10 0° C. to about 25
300° C. in the presence of a disproportion ation
catalyst . Examples of disproportionation catalysts are:
supported or non supported metals such as palladium, nickel
and platinum iodine, iodides such as iron iodide, sulph ur
dioxide and sul• phides such as iron sulphide. The 30
catalyst is suitably employed in an amount of from about
0.1 % to about 5% by weight on the basis of the amount of
rosin employed. The disproportionated rosin prepared in
the above manner has pr ef erably a content of abietic acid
of not more than about 5% by weight. Rosins partially 35
saponified with sodium or potas• sium hydroxide or with a
volatile base (e.g. ammonia or a lower amine such as
triethanolamine) are also usef ul. The tackifier dispersion
according to the invention can com prise any of the above
40
described rosins or mixtures thereof .
When preparing the tackifier dispersion according to the
invention, the resinous material is suitably first melted and the
emulsifier is added, suitably as a melted substance or as
present in an aqueous solution . The aqueous solution is pre•
ferred in continuous dispersing processes, while the melted 45
subst ance is pref erred in batch dispersing processes. The
emulsifier is added so as to be present in the tackifier disper•
sion in an amount of suit ably f rom about 2 to about 15% by
weight, based on the weight of resinous material, preferably
from about 5 to about 8% by weight. Sufficient hot water, 50
suit ably f rom about 5 to about 15% by weight, based on the
weight of resinous material, is stirred in to f orm a
creamy water in oil emulsion . Upon dilution with water,
suit ably in an amount of f rom about 10 to about 35% by
55
weight, based on the weight of resinous material, preferably
from about 15 to about 30% by weight, most pref erably from
about 20 to about
25%, the emulsion inverts to provide a stable oil in water
emulsion. The dispersion is suit ably further diluted with
60
water until the desired solids content is reached. If required,
conventional anionic emulsifiers (surfactants) can be incor•
porated into the tackifier dispersion. Such typical anionic
emulsifiers in clude alkyl aryl sulphon ates, such as sodium or
ammonium alkyl benzene sulph onates, f atty alcohol sul•
65
phates, e.g. sodium lauryl sulphate, phosphate esters, e.g.
sodium salt s of mono- and di-esters of orthophosphoric acid,
esters of sulph osuccinic acid, sod ium salts of sulphated
monoglycerides and sulphonates or sulphosuccinates of alkyl
phenol polyoxyalkylene oxide condensates or of polyoxy•
alkylene oxide condensates, e.g. the ammonium salt of non•
ylphenol polyethylene oxide sulphonic acid.
The solids content, i.e. the dry content ofresinous material
and emulsifier, in the tackifier dispersion is suitably at least
about 20% by weight up to the maximum content achievable,
preferably at least about 50% by weight, most preferably at
least about 55% by weight.
The mean particle diameter D5 0 of the resinous material in
the tackifier dispersion, where D 50 means the mean particle
diameter for the 50 weight% fraction ofthe particles starting
from the smallest particles, is suitably less than about 1
micron, preferably less than about 0.7 microns, more prefer-
ably less than about 0.5 microns, most preferably less than
about 0.45 microns. The mean particle diameter D90 of the
resinous material in the tackifier dispersion, where D90 means
the mean particle diameter for the 90 weight% fraction ofthe
particles starting from the smallest particles, is suitably less
than about 2 microns, preferably less than about 1.5 microns,
most preferably less than about 1 micron.
The viscosity ofthe tackifier dispersion is suitably adapted
to the specific use but is suitably, measured as Brookfield
(spindle 3@50 rpm) at 20° C., from about 100 to about 1200
mPa·s, preferably from about 200 to about 700 mPa·s, most
preferably from about 300 to about 500 mPa·s.
The tackifier dispersion according to the invention pref er•
ably has a storage stability (shelf lif e) of at least about six
months and will suitably demonstrate no substantial separa-
tion, coagulation or deposition. It is also pref erred that the
dispersion is low foaming and have good mechanical stability
during pumping, transportation and mixing, as well as low
foaming and good stability when formulated in an adhesive
composition and during coating of the adhesive composition.
The tackifier dispersion according to the invention is suit•
ably used as a tackifier in compositions comprising polymers,
preferably in adhesive compositions.
The invention further relates to an aqueous adhesive com-
position comprising one or more polymers and the tackifier
dispersion according to the invention . Pref erably, the aqueous
adhesive composition is a pressure sensitive adhesive (PSA)
composition. The aqueous adhesive composition suitably
comprises from about 60 to about 90 weight% of a synthetic
polymer latex or natural rubber latex, and from about 10 to
about 40 weight% of the tackifier dispersion. Suitable poly•
mers in the aqueous adhesive composition are natural and
synthetic rubbers such as polychloroprene rubber, styrene•
butadiene rubbers, SIS block copolymers, SBS block copoly-
mers, VAE (vinylacetate ethylene copolymers), nitrile rub•
bers and polyisobutylene rubbers, acrylate polymers, acrylic
polymers such as acrylic esters and methacrylate polymers or
mixtures thereof . Pref erred polymers used in the aqueous
adhesive composition accordin g to the invention are acrylic
polymers and/or acrylic ester copolymers. Other compounds
known to the person skilled in the art may also be included in
the aqueous adhesive composition exemplified by wetting
agents, biocides, plasticisers, st abilisers, antioxidants, fillers,
colouring agent and the like. The amounts of polymers/co-
polymers and other compounds contained in the adhesive
compositions are not critical and may vary so as to give the
pref erred properties of the adhesive com position . The com•
pounds can be in any physical state guided by the state of the
adhesive composition such as dispersed in an aqueous phase,
liquid or solid.
The invention will now be illustrated by means of the
following examples, which, however, should not be inter-
 US 9,023,929 B2
7 8
preted as limiting the scope of the invention. Parts and per• EXAMPLES 6-7
centages mean parts by weight and percentages by weight,
unless otherwise specified. Two further tackifier dispersions were made according to
the same procedure as in example 5 but using the reaction
EXAMPLE 1 5 products of examples 3 and 4 respectively.
Some properties of the tackifier dispersions according to
1000 g (83 weight%) oflinseed oil, having an iodine value examples 5-7 are summarised in table 1.A comparison is also
of 178 was heated to 180° C. 200 g (17 weight%) of maleic made with a tackifier dispersion produced accor din g to teach•
anhydride was gradually added, the reaction mixture being ings of U.S. Pat No. 5,552,519.
kept under agitation. The reaction mixture was then heated 10
to TABLE 1
200° C. which was maintained for 6 hours. The water soluble
Viscosity,
acid value (AV[ws]) was determined and if AV[ws]<2 mg Brookfield
KOH/g, then the spe cification was considered reached. If Particle size, [spindle 3 @ 50
15
AV[ws] >2 mg KOHIg, then the reaction mixture was allowed rpm, Solid s content Dsc/Doo 20° C.]
to react for another hour after which the water soluble acid (we ight% ) (mic rons) (mPa s)
value was again checked. The procedure was repeated until Exa mple 5 50 .0 0.38/0.49 250
the spe cification was reach ed. The final water soluble acid Exa mple 6 50 .3 0.32/0.51 420
value (AV[ws]) was 1.03 mg KOH/g, the acid value (AV) was 20
Exa mple 7 55.6 0.35/ 0.54 200
C omparison 55.2 0.55/ 0.87 290
85.3 mg KOH/g and the viscosity 760 mPa·s (Brookfield
spindle 3@50 rpm, 20° C.)
EXAMPLE2 It is concluded that tackifier dispersions according to the
present invention have smaller particle sizes than a high-
220 g (16 weight %) of the reaction product of example 1 25 performance prior art dispersion. In particular, in Example 7,
was mixed with 1200 g (84 weight%) of polyethylene glycol very high solids content is combined with small particle sizes.
PEG 4000. The temperature was kept at 250° C. for 20 hours. Stability tests were also made, both in terms of shelf lif e
The acid value (AV) of the reaction product was 4.6 testing, mechanical stability tests by rheometer, cone and
mg KOH/g. plate setup and high speed stirring stability test. The rheom-
30 eter test is made by measuring the normal force build-up in a
EXAMPLE3 cone and plate setup. Increase in normal force is indicative of
onset of breakdown. The high speed stirring test is made by
Example 1 was repeated giving a reaction product having a high speed stirring equipment (Hamilton Beach). The test
final water soluble acid value (AV[ws]) of 0.74 mg KOH/g mixture is stirred at high speed (3000 rpm) until coagulum is
and an acid value (AV) of the maleated linseed oil of 84.6 mg 35 formed. Time of breakdown is recorded.
KOH/g. 180 g (15 weight% ) of this reaction product was A foam f ormation test was also performed as follows: the
mixed with 252 g (21 weight%) of polyethylene glycol PEG tackifier dispersion is stirred at high spe ed (3000 rpm) for one
1500 and 768 g (64 weight%) of polyethylene glycol PEG minute. The foam created is measured and expressed as rela•
4000. The temperature was kept at 200° C. for 20 hours. The tive volume (%) increase compared to starting volume.
product had an acid value (AV) of 5.3 mg KOH/g. 40 The results are summarised in table 2.

EXAMPLE4 TABLE2
St a bility test St a bility
216 g (18 weight%) ofthe same reaction productoflinseed test
oil and maleic anhydride made in example 3 was mixed 45 Sh elf (rhe ology, cone (high spe e d
with Foa m lif e and plate) mixing)
Dispersion acc. to
984 g (82 weight %) of butoxy polyethylene glycol (with formation
example 5
average molecular weight of 4000 g/mol). The temperature (the invention)
>6 >900 s >20m in 50%
Dispersion based on
was kept at 200° C. for 20 hours. The product had an acid months
50 alkyl phosphate
value (AV) of 7.5 mg KOH/g. emulsifier
EXAMPLES >6 - 50 s - 4m in 12 0%
months

A tackifier dispersion was made by warming 1600 g of
glycerol rosin ester (softening point of82.8 and an acid
value
of 13.1 mg KOH/g), in a pot to 120° C. When molten 40 g of
tri-ethanol amine (TEA) was added, while stirring the rosin,
followed by addition of 64 g of the reaction product of
example 2 and 80 g (29 weight% aq. solution) of a conven•
ml hotanionic
tional (90° C.) water (RhodapexA
surfactant was added toB20obtain
from the inversion
Rhodia). 200
followed by addition of 400 ml hot (90° C.) dilution water.
The dispersion is further diluted by addition of 110 0 ml cold
water (30° C.) to obtain a stable dispersion. The particle size
D50 /D 9 0 which means the maximum particle size for 50 and
90 weight % respectively of the particles was 0.38/0.49
microns, the viscosity 250 mPas (Brookfield spin dle 3@50
rpm, 20° C.), the solids content 50.0 weight% .
It is concluded that a tackifier dispersion according to the
invention has excellent storage stability, shear stability, and
foaming behaviour.
55
EXAMPLE 8
Three adhesive compositions, each comprising between 25
60 and 30 weight% (by dry weight) of the tackifier dispersion
prepared in example 5, were made by blending the tackifier
dispersion with each of three dif ferent acrylate based polymer
products respectively (Acron al® V215 from BASF,
Robond™ PS7596 from Rohm&Haas Co, and Flexcryl®
65 1625 from Air Products). The adhesives were coated to sili•
cone release liners and then dried at 90° C. for 3 minutes to
obtain a coat weight each of20±1 g/m", before laminating
to
 US 9,023,929 B2
9 10
80 g/rrr' plain paper face stock and then covered with release
paper. The lamin ates were conditioned at 50 % relative
humidity at room temperature (23 ° C.) be fore assessing their
adhesive properties.
Three further adhesive compositions were made in the
same way but using a tackifier dispersion according to the
disclosure of U.S. Pat. No. 5,552,519.
The resistance to shear (FINAT test method FTM-8), loop
tack (FINAT test method FTM-9) when glued on various
substrates and peel 90° (FINAT test method FTM-2) were
tested for 25 mm strips of the adhesive samples.
The results are summarised in table 3.
5. The tackifier of claim 1, wherein the ester of one or more
fatty acids has an iodine number of more than about 60.
6. The tackifier ofclaim 1, wherein the ester ofone or more
fatty acids is a triglyceride of one or more fatty acids.
7. The tackifier of claim 6, wherein the triglyceride is
linseed oil, soybean oil or sunflower oil.
8. The tackifier of claim 1, wherein the die nophile is an
alpha-beta ethylenically unsaturated carboxylic acid or anhy•
10 dride.
9. The tackifier of claim 8, wherein the dienophile is maleic
acid, maleic anhydride or fumaric acid.

TABLE3
Amount
tack ifier Loo12 Tack Peel 90°
Resist ance
st ee l hdpe card hdpe
(we ight to she a r ca rd
Sa mple Polymer %) (h) (N) (N ) (N) (N)
1 (the invention) Acronal ® 30 14 17.0
(N) 12.5 5.4 5.5
4.0
V215
2 (c ompa ra tive) Acronal ® 30 11 15.5 9.9 5.7 5.4
4.3
V215
3 (the invention) RobondT M 30 18 .7 14 .5 7.4 6.6
4.1
PS7596
4 (c ompa ra tive) RobondT M 30 19 .8 14 .9 7.6 6.7
4.6
PS7596
5 (the invention) Flexcryl ® 25 39
1625
6 (c ompa ra tive) Flexcryl ® 25 19 10. The tackifier of claim 1, wherein the one or more
It is concluded that an adhesive
1625
composition comprising
the tackifier dispersion according to the present invention has polyalkylene glycols are C 2-C 5 polyalkylene glycols or
better cohesion (measured as shear stability) than an adhesive C2-C5 polyalkylene glycol mono alkyl ethers.
composition comprising the ref erence tackifier dispersion. 35 11. The tackifier of claim 1, wherein the one or more
The adhesion results (measured as Loop Tack and Peel Adhe• polyalkylene glycols are a mixture of a polyalkylene glycol
sion) are in average equivalent to the high-performing refer• having an average molecular weight, determined by hydroxyl
ence tackifier dispersion. number analysis, from about 500 to about 2500, with a poly•
alkylene glycol having an average molecular weight from
The invention claimed is: 40 3000 to 5000.
1. A tackifier dispersion comprising: 12. The tackifier of claim 1, wherein at least one ofthe one
a resinous material; or more polyalkylene glycols is a polyethylene glycol.
an emulsifier; 13. The tackifier of claim 1, wherein at le ast one of the one
wherein: or more polyalkylene glycols is a methoxy polyethylene gly-
the resinous material is a hydrocarbon resin or a rosin, or 45 col or a butoxy polyethylene glycol.
a mixture of any two or more thereof; 14. The tackifier of claim 1, wherein the emulsifier has an
the emulsifier comprises a reaction product of an inter• iodine number f rom about Ot o about 20 g iod ine per 100 g of
mediate product A with one or more polyalkylene emulsifier.
glycols, said intermediate product A being a reaction 15. The tackifier of claim 1, wherein the resinous material
product of an ester of one or more f atty acids contain- 50 is a hydrocarbon resin.
in g at least two conju gated double bonds and a dieno• 16. The tackifier of claim 1, wherein the resinous material
phile containing an acid or anhydride group; rs a rosm.
the one or more polyalkylene glycols have a number 17. The tackifier of claim 1, wherein the emulsifier is
average molecular weight from 3000 to 8000; and present in an amount f rom about 5 to about 8% by weight,
the emulsifier has a number average molecular 55 based on the weight of r esinous material.
weight of about 4000 to about 12,000. 18. The tackifier of claim 1, having a solids content of at
2. The tackifier of claim 1, wherein a weight ratio of inter• least 50% by weight.
mediate product A to the one or more polyalkylene glycols, 19. An emulsifier comprising:
based on total amount of the intermediate product A and the a reaction product ofan intermediate product A with one
one or more polyalkylene glycols, is f rom about 0.05:1 to 60 or more polyalkylene glycols, said intermediate
about 5: 1. product A being a reaction product of an ester of one or
3. The tackifier of claim 1, wherein a weight ratio of the more fatty acids containing at least two conjugated
ester of one or more f atty acids to the dienophile is less than double bonds and a dienophile, the dienophile
about 25:1. comprising an acid or anhydride group;
4. The tackifier of claim 1, wherein a weight ratio of the 65 wherein:
ester of one or more fatty acids to the dienophile is from about the one or more polyalkylene glycols have a
1: 1 to about 8: 1. number average molecular weight from 3000 to 8000;
and
 US 9,023,929 B2
11
wherein:
the emulsifier has a number average molecular weight
of about 4000 to about 12,000.
20. The emulsifier of claim 19, wherein a weight ratio the
intermediate product A to the one or more polyalkylene gly•
cols, based on total amount of the intermediate product A and
the one or more polyalkylene glycols, is f rom about 0.05: 1 to
about 5: 1.
21. The emulsifier of claim 19, wherein a weight ratio of
the ester of one or more fatty acids to the dienophile is less 10
than about 25:1.
22. The emulsifier of claim 19, wherein a weight ratio of
the ester of one or more fatty acids to the dienophile is from
about 1: 1 to about 8: 1.
23. The emulsifier of claim 19, wherein the ester of one or 15
more fatty acids has an iodine number ofmore than about 60.
24. The emulsifier of claim 19, wherein the ester of one or
more fatty acids is a triglyceride of one or more fatty acids.
25. The emulsifier of claim 24, wherein the triglyceride is
linseed oil, soybean oil or sunflower oil.
26. The emulsifier of claim 19, wherein the dienophile is an
alpha-beta ethylenically unsaturated carboxylic acid or anhy•
dride.
27. The emulsifier of claim 19, wherein the dienophile is
maleic acid, maleic anhydride or fumaric acid.
28. The emulsifier of claim 19, wherein the one or more
polyalkylene glycols are C 2 -C 5 polyalkylene glycols
or
C 2-C 5 polyalkylene glycol mono alkyl ethers.
29. The emulsifier of claim 19, wherein the one or more 30 ester ofone or more fatty acids to the dienophile is from
polyalkylene glycols are a mixture of a polyalkylene glycol
having an average molecular weight, determined by hydroxyl
number analysis, from about 500 to about 2500, with a poly•
alkylene glycol having a number average molecular weight
from 3000 to 5000.
30. The emulsifier of claim 19, wherein at least one of the
one or more polyalkylene glycols is a polyethylene glycol.
31. The emulsifier of claim 19, wherein at least one of the
one or more polyalkylene glycols is a methoxy polyethylene
glycol or a butoxy polyethylene glycol.
32. The emulsifier of claim 19, wherein the emulsifier has
an iodine number from about Oto about 20 g iodine per 100 g
of emulsifier.
33. A process for the production of a tackifier dispersion,
the process comprising:
dispersing a resinous material in an aqueous phase in the
presence of an emulsifier;
wherein:
the resinous material is a hydrocarbon resin or a rosin,
or a mixture of any two or more thereof;
the emulsifier being obtainable by a method comprising:
providing an ester of one or more fatty acids contain•
ing at least two conjugated double bonds;
reacting the ester of one or more f atty acids with
a dienophile containing an acid or anhydride 55
group to form an intermediate product A; and
reacting the intermediate product A with one or more
polyalkylene glycols;
wherein:
the one or more polyalkylene glycols have a num• 60 from
ber average molecular weight of 3000 to 8000;
and
the emulsifier has a number average molecular
weight of about 4000 to about 12,000.
12
34. The process of claim 33, wherein a weight ratio the
intermediate product A to the one or more polyalkylene gly•
cols, based on total amount of the intermediate product A and
the one or more polyalkylene glycols, is from about 0.05: 1 to
about 5: 1.
35. The process of claim 33, wherein a weight ratio of the
ester ofone or more fatty acids to the dienophile is from
about
1: 1 to about 8: 1.
36. A process for the production of an emulsifier, the pro•
cess comprising:
providing an ester of one or more fatty acids containing at
least two conjugated double bonds;
reacting the ester with a dienophile containing an acid or
anhydride group to form an intermediate product A;
reacting the intermediate product A with one or more
poly•
alkylene glycols having a number average
20 molecular weight of more than 3000; and
wherein:
the emulsifier has a number average molecular weight
of about 4000 to about 12,000.
37. The process of claim 36, wherein a weight ratio inter•
25
mediateproductA to one or more polyalkylene glycols, based
on total amount of the intermediate product A and the one or
more polyalkylene glycols, is from about 0.05:1 to about 5:1.
38. The process of claim 36, wherein a weight ratio of the
about
1: 1 to about 8: 1.
39. A composition comprising:
one or more polymers; and
35 a tackifier dispersion;
wherein:
said tackifier dispersion comprises:
a resinous material; and
an emulsifier comprising a reaction product of an
40
intermediate product A with one or more polyalky•
lene glycols;
the resinous material is a hydrocarbon resin or a rosin,
or a mixture of any two or more thereof;
45 said intermediate product A comprising:
a reaction product of an ester of one or more fatty
acids containing at least two conjugated
double bonds;and
a dienophile containing an acid or anhydride group;
50 the one or more polyalkylene glycols have a number
average molecular weight of 3000 to 8000; and
the emulsifier has a number average molecular weight
of about 4000 to about 12,000.
40. The tackifier of claim 1, wherein the one or more
polyalkylene glycols have an average molecular weight from
3500 to 4500.
41. The emulsifier of claim 19, wherein the one or more
polyalkylene glycols have an average molecular weight
3500 to 4500.
42. The process of claim 33, wherein the one or more
polyalkylene glycols have an average molecular weight
from
3500 to 4500.
43. The composition of claim 39, wherein the one or more
polyalkylene glycols have an average molecular weight from
3500 to 4500.
* * * * *
 I III IIIIII Illllllllllllllllllllllllllllllllllllllllll111111111111111111
US009988565B2

c12) United States Patent (IO) Patent No.: US 9,988,565 B2

Pernecker et al. (45) Date of Jun.5,2018
Patent:
(54) ROSIN ESTER TACKIFIERS FOR 4,260,550 A 4/19 81 Armstrong et al.
PRESSURE-SENSITIVE ADHESIVES 4,477,613 A 10 /19 84 Evans et al.
4,643,848 A 2/19 87 Thomas et al.
(71) Applicant: ARIZONA CHEMICAL COMPANY, 4,751,025 A 6/19 88 Olechowski et al.
4,758,379 A 7/19 88 Johnson, Jr.
LLC, Jacksonville, FL (US) 5,504,129 A 4/19 96 Dandreaux et al.
5,504,152 A 4/19 96 Schluenz et al.
(72) Inventors: Tibor Pernecker, Pooler, GA (US); 5,552,519 A * 9/19 96 Hemmings ......... B01Fl 7 /0028
Christopher J Holmes, Pooler, GA 156/327
(US); Leigh E Quinlan, Pooler, GA 5,559,206 A 9/19 96 Williams
(US) 5,691,405 A 11/ 1997 Huffer
5,830,992 A 11/ 1998 Whalen
(73) Assignee: Arizona Chemical Company, LLC, 5,969,092 A 10 /1999 Karvo
Jacksonville, FL (US) 6,034,168 A 3/2000 Wang
6,171,385 Bl 1/ 2001 Rurlaender et al.
6,274,657 Bl 8/2001 Geoghegan et al.
( *) Notice: Subject to any disclaimer, the term ofthis 6,444,022 Bl 9/2002 Krishnan et al.
patent is extended or adjusted under 6,900,274 B2 5/2005 Ruckel et al.
35 7,452,941 B2 11/ 2008 Ruckel et al.
U.S.C. 154(b) by O days. days. 7,994,106 B2 8/2011 Nelson et al.
(21) Appl. No.: 14/ 781,140 2003/0198773 Al 10 /2003 Miekka et al.
2004/0143065 Al 7/2004 Holub et al.
(22) PCT Filed: Jun. 14, 2014 2005/0203228 Al 9/2005 Aarts et al.
2007/0135542 Al 6/2007 Boonstra et al.
(86) PCT No.: PCT/US2014/000146 2008/0020957 Al * 1/ 2008 Nelson .................... C08L 93/04
508/449
§ 371 (c)(l), 2011/ 0034669 Al 2/2011 Dallavia
(2) Date: Sep. 29, 2015 2011/ 0213120 Al 9/2011 Astrologes et al.
FOREIGN PATENT DOCUMENTS
(87) PCT Pub. No.: W0 2014/ 200567 CN 101443426 A 5/2009
CN 102039099 B 6/2013
PCT Pub. Date: Dec. 18, 2014 EP 1878429 Al 1/2008
(65) Prior Publication Data
OTHER PUBLICATIONS
US 2016/0122607 Al May 5, 2016
International Search Report and Written Opinion dated Sep. 2, 2014
Related U.S. Application Data as issued in PCT/US2014-000146 filed Jun. 14, 2014.
(60) Provisional application No. 61/835,373, filed on Jun.
14, 2013. * cited by examiner

(51) Int. Cl.

Primary Examiner - Arrie L Reuther
C09J (2006.01)
19 3/ 04 (2014.0 1) (74) Attorney, Agent, or Firm - Samantha Page; Cantor
C09D 11/00 (2006.01) Colburn LLP
C09J 7104 (2006.01)
C09J (2006.01)
(57) ABSTRACT
10 7 / 00 (2006.01)
C09J 133/08 (2006.01) Water-dispersible adducted rosin esters, a process for mak•
(52) G09F 3/10 ing them, and their use in aqueous tackifier dispersions f or
C08L 93/04 C09J 193/04 (2013.01); C08L 93/04 pressure-sensitive adhesives are disclosed. Reaction of a
(2013.01); C09D 11/00 (2013.01); C09J 71045
U.S. Cl. rosin with a polyol gives a rosin ester intermediate, which is
CPC (2013.01); C09J 107/00 (2013.01); C09J then reacted with a dienophile to produce an adducted rosin
133/08 (2013.01); G09F 3/10 (2013.01); C09J ester. The adducted rosin ester is further esterified with a
2203/334 (2013.01); C09J 2400/283 polyethylene glycol having an Mw<700 to produce the
(2013.01); C09J 2407/00 (2013.01); C09J water-d ispersible adducted rosin ester. Esterification with
2433/00 (2013.01); C09J 2453/00 (2013.01);
the low-mole cular-weight PEG imparts good water dispers•
C09J 2493/00 (2013.01)
ibility to the adducted rosin ester while maintaining com•
(58) Field of Classification Search patibility with other tackifier components. Combination of
CPC C09J 193/04 the aqueous tackifier dispersions with polymer emulsions,
See application file for complete search history. particularly acrylics, gives pressure-sensitive adhesives that
deliver good loop tack and peel properties compared with
(56) References Cited
commercial alternatives, even when the coat weight is
U.S. PATENT DOCUMENTS reduced by 20%.

1,696,337 A 12 /1928 Symmes

4,201,701 A 5/ 1980 Coney 13 Claims, No Drawings
 US 9,988,565
1 B2
ROSIN ESTER TACKIFIERS FOR
PRESSURE-SENSITIVE ADHESIVES
FIELD OF THE INVENTION
The invention relates to rosin ester tackifiers useful in the
production of pressure-sensitive adhesives.
BACKGROUND OF THE INVENTION
Rosin esters, i.e., esters of rosin and polyols, have been
known for almost a century (see, e.g., U.S. Pat. No. 1,696,
337) and are widely used as tackifiers for packaging and
pressure-sensitive adhesives.
The simple st rosin esters are made by reacting a rosin
acid, which may be disproportion ated, with one or more
polyols such as glycerol, pentaerythritol, and diethylene
glycol. Improvements relate to ways to make rosin esters
with low color or low odor. For examples, see U.S. Pat. Nos.
4,477,613; 4,758,379; 5,504,152; 5,830,992; and 5,969,092.
In another common approach, a rosin acid is first heated
with an enophile such as an unsaturated dicarboxylic acid or
anhydride (e.g., maleic anhydride or fumaric acid) to form
an adduct by an ene reaction or a Diels-Alder reaction. Acid
groups in the adduct are then esterified by reaction with a
polyol (e.g., glycerol, pentaerythritol). For examples of rosin
esters made this way, see U.S. Pat. Nos. 4,201, 701; 4,643,
848; 5,559,206; 5,691,405; 6,171,385; and 7,994,106, and
U.S. Pat. Appl. Pub!. No. 2011/0213120.
Occasion ally, a one-pot approach is used in which a rosin
acid, polyol, and unsaturated diacid or anhydride are heated
together. This usually in volves principally esterification
rather than formation of an adducted resin (see, e.g., U.S.
Pat. No. 4,201,701) .
In yet another approach, a rosin ester is made in the usual
way be reacting a rosin acid and a polyol or mixture of
polyols. In a second step, an adducted resin is then made by
heating the rosin ester with an unsaturated diacid or anhy•
dride. Usually, the acid groups are then modified to enhance
water solubility or water dispersability. For examples, see
U.S. Pat. Nos. 4,751,025 and 5,504,129.
Rosin esters have been used to make surfactants or
emulsifiers. For inst ance , U.S. Pat. No. 4,260,550 teaches to
form an adduct f rom rosin and maleic anhydride, followed
by esterification with polyethylene glycol, 6000 mo!. wt.
(see Examples VIII-X). The PEG-m odified rosin ester is
used as a surfactant for making a hair care product. In
another example, U.S. Pat. No. 6,274,657 teaches the prepa•
ration of a surfact ant by reacting rosin or dimerized rosin
with polyethylene glycol, 8000 mo!. wt. The surfactant is
combined with rosin ester tackifiers to make st able aqueous
dispersions. In U.S. Pat. Nos. 6,900,274 and 7,452,941, a
surf act ant is made by reacting maleic anhydride with a
terpene or hydrocarbon resin to f orm an adduct , which is
further reacted with polyethylene glycol, 2000 mo!. wt. This
surf act ant is also useful f or making st able aqueous dispe r•
sions comprising rosin ester tackifiers. U.S. Pat. Appl. Pub!.
No. 2007/0135542 describes emulsifiers made by reacting a
rosin with polyethylene glycol, followed by reaction with
polyphosphoric acid. The resulting water-d ispersible prod-
uct is combined with tackifiers to give aqueous dispersion s
useful for pressure-sensitive adhesives.
In another variation on the surfactant theme, U.S. Pat. No.
5,552,519 teaches to prepare rosin ester surf actants in three
steps. In one aspect , a rosin is first esterified with a polyol
(e.g., glycerol) to an acid value of le ss than 30 mg KOH/g.
The rosin ester is then grafted with an unsaturated dicar-
2
boxylic acid or anhydride. The grafted rosin ester is esteri•
fied with polyethylene glycol having a weight-average
molecular weight (Mw) of 4000 to 16000. This material is
used as a surfactant for creating an aqueous dispersion of
a rosin ester based on rosin and pentaerythritol. The
dispersion is combined with a tackifier and an acrylic
polymer, and this mixture is used to make a pressure-
sensitive adhesive.
Improved tackifiers are needed, particularly ones useful in
10 pressure-sensitive adhesives prepared from aqueous disper-
sions. In particular, the industry needs tackifiers than can be
combined with acrylic emulsions to give adhesives having
good loop tack and peel properties. Pref erably, the tackifiers
could be made using conventional, economical startin g
15 materials, conventional equipment, and ordin ary process
steps. Ideally, the tackifiers could reduce reliance on surfac•
tants and deliver desirable adhesive properties while reduc•
ing coat weight by 10 -20% or more.
SUMMARY OF THE INVENTION
20
In one aspect, our invention relates to a water-dispersible,
water insoluble adducted rosin ester and a process for
making it. A rosin is reacted with a polyol to give a rosin
ester intermediate, which is then reacted with a dienophile to
25 produce an adducted rosin ester. The adducted rosin ester is
further esterified with a polyethylene glycol to produce the
water-d ispersible water insoluble adducted rosin ester. The
polyethylene glycol has a weight-average molecular weight
less than 700.
30 The invention in cludes aqueous tackifier dispersions com•
prising water, a surfactant, and the adducted rosin ester. The
aqueous tackifier dispersions are prepared by combining
components under high-shear conditions. Also included are
pressure-sensitive adhesives comprising a polymer emulsion
35 and the inventive tackifier dispersions, as well as laminates
used in label making. The lamin ates comprise a release liner,
a layer of inventive adhesive coated on a surface of
the release liner, and a f ace stock laminated to the
adhesive• coated release liner.
40 Although adducted rosin esters are of ten difficult to
disperse in water, we surprisingly found that esterification of
adducted rosin esters with low-mole cular-weight PEG
imparts good water insolubility and dispersibility to the
adducted rosin ester while maintaining compatibility with
45 other tackifier components used in the production of aque•
ous dispersions. The aqueous tackifier dispersions can be
combined with polymer resins, particularly acrylics, to give
pressure-sensitive adhesives that deliver good loop tack and
peel properties compared with commercial alternatives,
50 even when the coat weight is reduced by 20%. Be cause
equivalent performance can be achieved at lower coat
weights, formulators can choose to reduce cost by using less
adhesive or to enhance performance at traditional coat
weights.
55
DETAILED DESCRIPTION OF THE
INVENTION
The invention relates to water insoluble and water-dis•
60 persible adducted rosin esters and a process for making
them. In a first step, a rosin is reacted with a polyol to give
a rosin ester intermediate.
Rosins suitable for use have carboxylic acid functionality
and multiple carbocyclic rings. Structurally, pref erred rosins
65 (also called "rosin acids") include mono-carboxylic acids
with the general formula C19 H2 9 COOH, with a nucleus of
three fused six-carbon rings and comprise double bonds that
 US 9,988,565
3 B2
vary m number and location . Examples of rosin
acids include abietic acid, neoabietic acid , dehydroabietic
acid, pimaric acid, levopimaric acid, sandaracopimaric acid,
isopimaric acid and palustric acid.
The rosin may be used in isolated form, or as part of a
composition which may comprise a plurality of rosin acids.
In particular, rosin may be used as a source of rosin acid.
Rosin is a hydrocarbon secretion of many plants, particu•
larly conif erous trees such as Pinus palustris and Pinus
caribaea. Natural rosin typically consists of a mixture of
seven or eight rosin acids, and other minor components.
Rosin is commercially available and can be obtained from
pine trees by distillation of oleoresin (gum rosin being the
residue of distillation), by extraction of pine stumps (wood
rosin) or by fract ionation of tall oil (tall oil rosin). Any type
of rosin may be used, including tall oil rosin , gum rosin and
wood rosin . In one embodiment, tall oil rosin is used be cause
of it s availability. Examples of suit able commercially avail•
able rosins include tall oil rosins (e.g. Sylvaros® 85, Syl•
varos® 90 or Sylvaros® 95 from Arizona Chemical). For
further examples of suitable rosins, see U.S. Pat. No. 7,994,
106 and U.S. Pat. Apple Pub!. No. 2011/0034669, the
teachings of which are incorporated herein by reference.
A polyol is reacted with the rosin. Suitable polyols have
two or more hydroxyl groups available for f ormin g esters
with the carboxylic acid groups of the rosin. Pref erred
polyols have an average hydroxyl functionality within the
range of 2 to 6. Pref erred polyols are aliphatic and have 3 to
30 carbon atoms. In one embod iment, the polyols have a
boiling point greater than 240° C. at atmospheric pressure.
Suitable polyols include, for example , glycerin, pe ntaeryth•
ritol, trimethylolethane, trimethylolpropane, ethylene gly•
col, propylene glycol, diethylene glycol, triethylene glycol,
tetraethylene glycol, 1,3-propanediol, 2-methyl-1,3-pro-
panediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclo-
hexanedimethanol, diglycerol, dipentaerythritol, mannitol,
sorbitol, hexitol, and the like, and mixtures thereof . Particu•
larly pr ef erred polyols include glycerin, pentaerythritol,
trimethylolethane, trimethylolpropane, diethylene glycol,
dipentaerythritol, sorbitol, and the like, and mixtures
thereof . For further examples of suit able polyols, see U.S.
Pat. Nos. 4,643,848 and 4,758,379, and U.S. Pat. Appl. Pub!.
No. 2011/ 0213120, the teachings of which are in corporated
herein by ref erence.
The reaction of the polyol and rosin to make the rosin
ester intermediate may be uncatalyzed or it may be per•
formed in the presence of an acidic or basic
catalyst . Suitable catalysts for the process in clude, for
example, mineral acids (e.g., sulf uric acid, phosphoric
acid), organic acids (e.g., p-toluenesulf onic acid, acetic
acid), alkali metal and alkaline earth metal oxides,
hydroxides, carbonates, acetates, and the like.
In one embodiment, the rosin ester intermediate has
an acid value within the range of 40 to 60 mg KOH/g, or
from
45 to 55 mg KOH/g. The rosin ester intermediate is normally
not isolated but is used "as is" in the next reaction step. If
the acid value of the rosin ester intermediate is too low or too
high, the final resin may not disperse well enough in water
or may not be hydrophobic enough to impart good tack ifi•
cation to the adhesive.
In some cases, the rosin ester intermediate may be avail•
able commercially. Thus, in one aspect of the invention, the
rosin ester in termediate is simply purchased and used "as is"
in the production of an adducted rosin ester as described
below. Most of ten, however, commercial rosin esters will
have an acid value of <20 mg KOH/g, which is too low for
purposes of the present invention. In some cases, a com-
4
mercial rosin ester might be modified by reaction with
additional rosin or rosin and polyol to adjust the acid value
to be within the preferred range of 40 to 60 mg KOH/g for
the rosin ester intermediate. To summarize, use of a suitable
commercial rosin ester having a high acid value or modifi•
cation of a commercial rosin ester to give a rosin ester
intermediate of satisfactory acid value is considered to be
within the scope of the present invention.
In a second step, the rosin ester intermediate is reacted
10 with a dienophile to produce an adducted rosin ester.
"Adducted" means that the dienophile and rosin react and
are joined by at least one carbon-carbon sigma bond. Usu•
ally, the principal bond-forming reaction is a Diels-Alder
reaction, in which a six-membered monounsaturated ring is
15 formed from the dienophile double bond and a pair of
conjugated double bonds in the rosin.
Suitable dienophiles have a carbon-carbon double bond
that is attached to at least one ele ctron-withdrawing group
(e.g., halogen, carbonyl group, oxygen, or the like) that
20 makes the double bond electron deficient. The dienophile is
capable of forming adducts with the unsaturation present in
rosin. Suitable enophiles include a ,�-unsaturated acids,
esters, and anhydrides such as maleic anhydride,
maleic
25 acid, maleate esters and half esters, fumaric acid, f umarate
esters and half esters, it aconic acid, itaconic anhydride,
itacon ate esters and half esters, citraconic anhydride, acrylic
acid, methacrylic acid, vinyl ace tate, and the like, and
mixtures thereof .
30 In one embod iment, the dienophile is selected from
maleic anhydride, fumaric acid, itaconic acid, citraconic
anhydride, acrylic acid, methacrylic acid, vinyl acetate, and
mixtures thereof . In another embodiment, the dienophiles
are maleic anhydride, fumaric acid, and it aconic acid. In a
35 further embodiment, the dienophile is it acon ic acid. For
further examples of suitable dienophiles, see U.S. Pat. No.
4,751,025 and U.S. Pat. Appl. Pub!. No. 2005/0203228, the
teachings of which are incorporated herein by reference.
The adducted dienophile content of the water-dispersible
40 adducted rosin ester is at least 3 wt. %, or at least 5 wt. %.
In one more embodim ent, adducted rosin esters having at
least 5 wt. % of adducted maleic anhydride, fumaric acid, or
itaconic acid, or at least 5 wt. %, or at least 6 wt. %, of
adducted it aconic acid. In one aspect, the adducted rosin
45 ester comprises from 6.0 to 8.0 wt.% , or from 6.0 to 7.5 wt.
% of adducted itaconic acid.
The adducted rosin ester has an acid value within the
range of 40 to 60 mg KOH/g, more or from 45 to 55 mg
KOH/g. If the acid value of the adducted rosin ester is too
50 low or too high, the final resin may not disperse well enough
in water or may not be hydrophobic enough to impart good
tackification to the adhesive.
The adducted rosin ester has a ring-and-ball sof tening
point within the range of 60° C. to 77° C., more or from
55 65° C. to 72° C.
In a third step, the adducted rosin ester is further esterified
with a polyethylene glycol having a weight-average mole cu•
lar weight (Mw) le ss than 700. In one embodim ent, the
polyethylene glycol is then added, and the reaction mixture
60 is heated at 10 0 to 300 degrees C. until the acid number is
- 50 mg KOH/g, and the product has a Mettler sof tening
point of - 70° C. In another embodiment, the polyethylene
glycol has an Mw within the range of 200 to 400. In a further
embodiment, the polyethylene glycol has a Mw of about
65 200. The Mw is determined by any desired method. Gel
permeation chromatography is a convenient means of mea•
suring Mw. Suitable polyethylene glycols having Mw values
less than 700 are commercially available from Dow Chemi-
 US 9,988,565 B2
5 6
cal ("Carbowax™" products) and other supplie rs. Suitable
polyethylene glycols can also be synthesized f rom water or
a dial a starter, a catalyst such as KOH or a double metal
cyanide com plex, and ethylene oxide accordin g to well•
known methods.
In another embod iment, the mass ratio of polyethylene
glycol to ester is greater than 1: 1, or from 1: 1 to 1:20, or
from 1:1 to 1:15.
We found that polyethylene glycols having Mw values
above 700 are not suitable for use for making the inventive
water-d ispersible adducted rosin esters. In particular, when
the Mw exceeds about 700, the adducted rosin ester be comes
too hydrophilic (i.e., too soluble) and can no lon ger be
dispersed in water. To function as a tack ifier, the resin needs
to be dispersible in water, so it must be reasonably hydro•
phobic. The water insoluble, water-d ispersible adducted
rosin esters made as described above may have one or more
of the following properties:
Acid value: 40-55 mg KOH/g.
Ring-and-ball softening point (ASTM E28-99): 65-72° C.
Brookfield viscosity (at 100° C.): <15,000 cP.
Mw (by GPC): <2000, preferably <1500. Polydispersity
(by GPC): <3.0.
Glass transition temperature, midpoint (by DSC): 10 °
C.-20° C.
In another embod iment, the tackifier of the present inven•
tion is in soluble in water, which allows the tackifier to be
readily in corpor ated into the aqueous dispersion and pro•
vides an aqueous dispersion with lower viscosity, thus
resulting in lower dry coat weight when placed upon the
desired substrate while still maintaining the desired adhesion
properties.
In one aspect, the invention relates to aqueous disper•
sions. The dispersions comprise water, a surfactant, and a
tackifier. The tackifier comprises a water insoluble, water-
dispersible adducted rosin ester as described above.
Preferred aqueous dispersions comprise 35 to 60 wt. % of
water, 0.1 to 10 wt. % of the surfactant, and 40 to 65 wt. %
of the tackifier; more pr ef erably, the dispersions comprise 40
to 55 wt. % of water, 0.2 to 5 wt. % of the surfactant, and
45 to 60 wt. % of the tackifier.
The aqueous dispersions are pr ef erably made by a process
which comprises combining under high-shear conditions
water, the surf actant, and the tackifier comprising the water
insoluble , water-dispersible adducted rosin ester. The pro•
cess for making the aqueous dispersion can be batch, se mi•
continuous, or continuous. Combining the water, surfact ant,
and tackifier under high-shear conditions enables the nec•
essary phase inversion to give the water-dispersed tackifier.
Generally, enough water is present to allow the mixture of
surf act ant, water, and tackifier to undergo (upon combina•
tion under high-shear con ditions) a phase inversion to form
an oil-in-water dispersion (or emulsion). The amount of
water needed to invert any particular combination of tacki•
fier components and surfactants can be determined experi-
mentally by progressively increasing the amount of water
used. As the phase inversion point is approached for a
water-in-oil dispersion, the viscosity of the mixture
incr eases dramatically, then decreases rapid ly as more water
is introduced and inversion to an oil-in-water dispersion is
completed. High-shear conditions are essential f or making
the traverse. The resulting oil-in-water dispersion has low
viscosity and a continuous aqueous phase. Unlike the water•
in-oil dispe rsion, the oil-in-water dispersion can conduct a
flow of electric current. This makes it easy to determine
whether the tackifier has been successf ully dispersed m
water.
The aqueous dispersion can be produced at atmospheric
pressure or in a pressurized react or . The choice of reactor
type is within the skilled pe rson 's discretion . Generally,
when the tackifier has a relatively high softening point, it
may be desirable to use a pressurized reactor to allow a high
enough mixing temperature for successful phase inversion.
Typically, the temperature needed for phase inversion will
be at least 10 ° C. above, preferably about 20° C. above, the
sof tening point of the tackifier.
10 The tackifier may include other components in addition to
the water insoluble, water-dispe rsible adducted rosin ester.
Suitable tackifier components are known in the art, and
many are commercially available. For example, the tackifier
may further comprise polyterpenes, terpene-phenol resins,
15 aromatic-terpene resins, aromatic-terpene-phenol resins,
rosin esters, hydrocarbon resins, liquid hydrocarbon resins,
aromatic resins, and mixtures thereof . Examples include
Sylvares® terpene phenols such as Sylvares® TP 95, Syl•
vares® TP 96, Sylvares® TP 10 5, and Sylvares® TP 115.
20 Suitable polyterpenes include, for example , Sylvares® TR
series polyterpenes such as Sylvares® TR 90, Sylvares® TR
105, and Sylvares® TR 125. Suitable hydrocarbon resins
include, for example, Sylvares® SA series aromatic resins
such as Sylvares® SA 100, Sylvares® SA 120, and Sylva-
25 res® SA 140 and a-methylstyrene phenolic resins, for
example, Sylvares® 520, Sylvares® 525, and Sylvares®
540. All of the Sylvares® products noted above are products
of Arizona Chemical. Suitable tackifier components also
include dim erized rosin acids such as Dymerex™ polymer-
30 ized rosins (products of Eastman Chemical). For additional
examples of suitable tackifiers, see U.S. Pat. Nos. 6,900,274
and 7,452,941, the teachings of which are incorporated
herein by ref erence.
Not all tackifiers will be suit able f or use . The choice of
35 tackifier components will depend on many f actors, and
particularly on how easily the components can be dispersed
in water. Other f actors include the tackifier properties (soft•
ening point, equivalent weight, acid number), availability,
cost , perf ormance requirements, customer pr ef erences, and
40 the like.
In one embodiment, the tackifier comprises 10 to 50 wt.
% of a terpene-phenol resin and 50 to 90 wt. % of the water
insoluble , water-d ispersible adducted rosin est er. In another
embodiment, tackifiers comprise 20 to 40 wt. % of a
45 terpene-phenol resin and 60 to 80 wt. % of the adducted
rosin ester.
The tackifier preferably has a softening point within the
range of70° C. to 90° C., more preferably from 75° C. to 85°
C., and most preferably about 80° C. This goal is conve•
50 niently achieved by combining the water insoluble, water•
dispersible adducted rosin ester and any additional tackifier
components in the proportion needed to give the tackifier a
softening point in the targeted range.
The tackifier preferably has a viscosity at 20° C. above its
55 softening point within the range of 10,000 to 40,000 cP, or
from 15,000 to 30,000 cP, most preferably from 20,000 to
25,000 cP.
Any desired surfactant can be used for making the aque•
ous tackifier dispersions. In one embodiment, the surfactant
60 comprises an anionic surfactant, a nonionic surfactant hav•
ing an HLB value >10, or a mixture thereof.
The amount of surfactant used will depend on the nature
of the surfactant(s) and tackifier components, the tackifier
concentration, and other factors. Generally, it is used in an
65 amount of 1 to 10 wt.% of the surfactant, or from 3 to 8 wt.
%, or from 5 to 7 wt. %, based on the combined amounts of
tackifier components.
 US 9,988,565 B2
7 8
In one embod im ent, the surf act ant comprises a sulf ate
or phosphate of an ethoxylated fatty alcohol or an
ethoxylated f atty acid . In another embod im ent, the
sulf ate or phosphate has a li near or branched C8 -C 18
alkyl ch ain, or a C12 -C 16 alkyl ch ain . Generally, the
sulfate or phosphate has 1 to 60,
or 3 to 9, oxyethylene units. In another embodiment,
the sulfate or phosphate has a counterion selected from
sodium, potassium, ammonium, and calcium. Examples
of suitable anionic surfactants are the J-Phos™ and
J-SulfTM ether phosphates or ether sulf ates available
from J1 Technologies, e.g., J-Phos™ 1066, J-Phos™
4012, J-SurfTM 3257, and the like. Specialty emulsifiers
available from J1 Technologies are also suitable, such
Nonionic surfactants an HLB value >10
as J-Mulse™ 3150, J-Mulse™ 4020, J-Mulse™ 4012,
having surfactants that are relatively
nonionic (i.e ., hydrophilic), can
and the like.
also be used. Examples include polyoxyethylene (10)
cetyl ether, polyoxyethylene (12) nonylphenol ether,
(20) oleyl ether, polyoxyethylene stearyl
polyoxyethylene
(10 0) Pluronic® EO-capped PPG ether,
copolymers BASF), and the like. (products
In one em bodime nt, the surf actant is of blend of an
anionic and nonionic surf actant in which the anionic
surf act ant is the m ajo r component. In another
embodiment su rf act ants com• prise at least a 2: 1,
pref erably at least a 3: 1 weight ratio of anionic to
nonionic surf actant. In a further embod iment, anionic
surf actant in the blend is an ethoxylated f atty alcoh ol
phosphate or an ethoxylated fatty acid phosph ate.
In another embodiment, the pH of the aqueous
dispersion
is controlled within the range of 6.0 to 9.0 , or from 7 .0 to
8.5. U sually, a base such as KOH or ammon ium
hydroxide is added to the aqueous dispe rsion to
provide the desirable degree of neutraliz ation . In a
further embodim ent, aqueous ammonium hydroxide is
used for neutralization .
The aqueous dispersion pref erably has particles with
an average diameter less than 1 um, or less than 500
nm, as measured by dynamic light scatterin g or
other suitable techniq ues.
The invention includes a pressure-sensitive adhesive.
The
adhesive comprises a polymer emulsion and an
aqueous dispersion of water-d ispe rsible adducted rosin
ester prepared as described herein . In one em bodime nt,
the adhesive com• prises 1 to 40 wt. %, or 15 to 30
wt. %, of the aqueous dispe rsion . Suitable emulsions
include acrylic polymers, natural rubbe rs, st yrene-
butadiene polymers, and the like. In on e embod im ent,
acrylic polymers are used. Suitable acrylic polymers
include polymers of alkyl acrylates and methacry• lates,
especially methyl acrylate, methyl methacrylate, ethyl
acrylate, butyl acrylate, butyl methacrylate, 2-
ethylhexyl acrylate, isooctyl acrylate, acrylic acid ,
methacrylic acid, hydroxyethyl acrylate, t-butyl
acrylate, and the like. In another embod iment, acrylic
polymers are based on butyl acrylate, 2-ethylhexyl
acrylate, or mixtures thereof .
Acrylic polymers suit able for use are com mercially
avail- able . Examples include, among many oth ers,
Acronal® acrylic resins f rom BA SF, Synthebon d™
acrylic polymers from Momentive Specialty Chemicals,
Robond™ adhesives and Primal™ polymer emulsions
from Dow Chemical, N ovacryl™ polymers from
Omnova, Flexcryl™ adhesives f rom Ashland, an d
Gelva® GME series adhesives from Cytec.
In one embodiment, the tackifier has a viscosity at
room
temperature within the range of300 to 2,000 cP, or from
400 to 1,900 cP, or from 500 to 1,800 cP.
The adhesives are well-suited for the production
oflabels.
food, general purpose, home, beauty, or other
applications. The labels can be removable, semi-
permanent, or perma• nent.
Labels are conveniently produced from lamin ates.
Thus, in one aspe ct, the inve ntion relates to lamin ates
comprising a release lin er, a la ye r of inventive
adhesive coated on a surf ace of the release liner, and a
f ace stock, such as a pape r f ace stock , that is lamin ated
to the adhesive-coated release lin er. After the face stock
10
has been laminate d to the release lin er, labels are
produced from the lamin ate, normally by punching a
plurality of l a be ls of desired dimensions from the
laminate.
The invention includes a method of making labels.
15
The method comprises: (a) coating a release liner with an
inven- tive adhesive as described above; (b) applying a
face stock to the adhesive-coated release liner to
produce a laminate; and (c) producing one or more
20 labels from the laminate. In one embodiment, the labels
are produced from a paper face stock, and in another
embodiment the labels are punched from the laminate.
In one embodiment paper labels are 80 to 100-g
coated
paper having a dry coat weight within the range of 15 to
25
20 g/nr', or from 15 to 18 g/rn", or from 15 to 16
g/m 2 . In another embodim ent, the paper labels of the
in vention will have a static sh eer of at least 2 hours, or
of at le ast 3 hours. In another embod im ent, the pape r
labels will have a loop tack offL DPE within the range
30
of 1.5 to 3.0 psi, or from 2.0 to 3.0 psi. In a further
embodiment, the paper labels will have a loop tack off
glass within the range of 3 .0 to 6.0 psi, or from 4.0 to
6.0 psi. In an even further embod im ent, the paper labe ls
35
will have a loop tack off corrugated cardboard within
the range of 1.5 to 3.0 psi, or from 2.0 to 3.0 psi. Loop
tack is measured using PST C-16 , a test method published
by the Pressure Se nsitive Tape Council (15 'h edition ,
2007). A
40 typical test is described in the examples
below.
In one em bod im ent, the pape r labels will have a 90
degree peel offL DPE within the range of 1.0 to 3.0 psi,
or f rom 2.0 to 3.0 psi. In a further embodiment, the
45 paper labels will have a 90 degree peel off corrugated
cardboard within the range of 1.0 to 3.0 psi, or from 2.0
to 3.0 psi. The 90 degree peel is pe rformed according
to PSTC-14, a test method published by the Pressure
Se nsitive Tape Council.
50
The followin g examples merely illustrate the
in vention ; the skilled person will recognize many
variations that are within the spirit of the in vention and
scope of the claims. Preparation of Rosin Ester
55
Tackifier A
Tall oil rosin (1349 g) is charged to a 3-L round-
bottom
flask equipped with nitrogen inlet, mechanical stirrer,
Dean• Stark condense r, receive r, thermocouple pr obe,
60
and tem- perature controller. The rosin is he ated to
19 0° C. under nitrogen. When the rosin is molten, the
agitator is st arted to ensure unif ormit y. Pentaerythritol
(90 g) and glycerol (90 g) are then added and the
mixture is heated to 265° C. for 2 h to give a product
65 having an acid num ber of - 50 mg KOH/g. Itaconic acid
(13 5 g) is added, and the mixture is heated at
220° C. for 1 h to give an adducted product having an
acid
numbe r of - 68 mg KOH/g. Polyethylene glycol (M n
about
200, "PEG 200," 13 5 g) is then added, and the
reaction mixture is held at 220° C. until the acid
num be r is - 50 mg KOH/g, and the product has a
Mettle r softening point of
- 70 ° C. Softening point is determined using a
 US 9,988,565 B2
9 10
Preparation of Rosin Ester Tackifiers BG
Rosin ester tackifiers BG are prepared similarly using the
reactants indicated in Table 1. For tackifiers F and G, an acid
number of 45-55 mg KOH/g is targeted prior to addition of
the itaconic acid. Properties for the finished rosin ester
tackifiers appear in Table 1.
Solubility of Rosin Ester Tackifiers
The solubility of tackifier A is determined by adding 1.0
gram of tackifier A to a 250 mL beaker on a hot plate.
100 grams of water and a stir bar are added to the beaker 10
and stirred until the water starts to boil. The water is
boiled for
10 minutes while stirring. Note: The tackifier clumped
floated on the surface of the water. The tackifier is removed
and dried in an oven at 120 degrees C. for minutes. The dried 15
tackifier is then weighed on a scale to yield 0.998 grams of
tackifier A. Thus, it is concluded that tackifier A is not
soluble in water.
The solubility of a XR9003 tackifier (a high molecular
weight PEG rosin ester available from Arizona Chemical) is 20
determined by adding 1.0 gram of tackifier A to a 250 mL
beaker on a hot plate. 100 grams of water and a stir bar are
added to the beaker and stirred until the water starts to boil.
The water is boiled for 10 minutes while stirring. Note: The
solution was uniform and transparent and there is no visible
tackifier in the flask. Thus, it is concluded that 25
XR9003 tackifier is soluble in water.
Aqueous Dispersion Preparation from Tackifier A and Syl•
vares® TP 105: Atmospheric Reactor Preparation
A resin blend is prepared by combining 75 wt. % of
finished rosin ester A and 25 wt. % of Sylvares® TP 105 30
(terpene-phenol resin) and dispersing the mixture in water
using the followin g procedure: Aj a cketed 1- L glass react or
equipped with thermocouple, liquid addition port, con•
denser, and high-sh ear, Greaves-style agitator is pre-heated
to 96° C. and then charged with molten resin (250 g). 35
Agitation (250 rpm) is started, and the reactor contents are
heated to 99° C. The dispersion temperature for a particular
blend is determined based on the temperature at which the
neat resin blend's viscosity is near 20,000 cP (typically 20°
C. above the blend's softening point).
When the temperature reaches 99° C., agitation is 40
incr eased to 400 rpm. A surf act ant mixture (54.5 g of 27.5
wt. % solution) comprising J-Mulse™ 4012 emulsifier (a
product of J1 Technologies, - 1: 1 anionic/nonionic surfac•
tant ratio) and tridecyl ether phosphate (to give a 3:1
anionic/nonionic ratio) is added to the resin mixture fol• 45
lowed by enough water to cause phase inversion (32.8 g).
Upon reaching the inversion point, the resin/surfact ant mix•
ture turns white and forms a viscous gel. At or around the
phase in version point, the reactor charge is held for 20 min,
and the temperature is maintained to ensure good mixing of
the resin/surfactant mixture. More water (154 g) is then 50
added while keeping the mixture at 99° C. and the agitation
rate at about 400 rpm. When water addition is complete, the
reactor is gradually cooled to near room temperature, and the
dispersion (491.3 g) is discharged.
TABLE 1
Synthesis and Properties of Adducted Rosin Esters
A B
Wt . %
Rosin acid, R Type S (90/10) 74.94 74.94
Itaconic acid
Fumaric acid 7.50 7.50
Pentaerythritol
0 0
5.00 5.00
Particle size (Delsa Nano light scattering particle size
analyzer): 366 nm; Brookfield viscosity (spindle #3 @ 20
rpm): 750 cP; pH=6.3; total solids: 53.9%.
Paper Label Sample Preparation and PSA Testing
The aqueous dispersion described above is compounded
with an acrylic adhesive base polymer at 30% concentration.
The compounded adhesive blend is coated on release liner at
16 .0 to 16.6 g/rrr' dry adhesive coat weight using an Elcom -
eter Applicator (model 4340). The drawdowns are immedi•
ately dried in an oven at 10 2° C. for 2 min. and kept for
additional 30 min. under ambient conditions. Drawdowns
are laminated to paper f ace st ock and placed in a
const ant temperature/humidity room (75+/- 2° F., 50+/- 5%
relative humidity) for overnight conditioning.
Loop tack and 90 degree peel adhesion tests on low
density polyethylene (LDPE), glass, and recycled corru•
gated cardboard are performed using a tensile strength tester
machine. The LDPE and glass test panels are cleaned with
isopropyl alcohol bef ore testing. Laminate sample strips
(1"x6") are conditioned overnight in the constant tempera•
ture/humidity room. Sample strips used for 90° peel tests are
laminated to test panels using a roll down machine followed
by a 30-min dwell time and tested side-by-side with a
commercial adhesive used for general-purpose paper label
applications, which is applied at 20 g/m2 coat weight.
Aqueous Dispersion Preparation in PARR Reactor: General
Procedure
The reactor is charged with predetermined amounts of
molten resin. After closing the reactor, agitation is started at
350 rpm. The reactor contents are heated to the desired
temperature, which varies from batch to batch. The disper•
sion temperature for a particular blend is determined
based on the temperature at which the neat resin blend's
viscosity is near 20,000 cP (typically 20° C. above the blend
softening
point). When T 2 0 0 0 0 cP is reached, the reactor charge is
neutralized with 45% KOH solution. After 10 minutes,
surfactant solution is added and the agitation is increased to
400 rpm. The KOH and surfact ant solutions are added usin g
a high-pressure liquid pump. The inversion point is indicated
by a sudden incr ease in torque and conductivity. At this
point, the reactor contents are held for 20 minutes and the
temperature is maintain ed. After the hold time, hot water
addition is st arted. Upon completing the water addition , the
reactor charge is cooled to near room temperature. The
pressure is typically at or below 30 psi. The aqueous
dispersions shown in Table 8 utilize this procedure.
As noted earlier, Table 1 summarizes synthetic formula•
tions and physical properties for inventive water-dispersible
adducted rosin esters A-G.
Table 2 shows the effect of formulating adducted rosin
ester tackifiers AD with Acronal® V 215 acrylic emulsion at
30 wt. % tackifier. Compared with the control, which is also
used at 16 g/m2 coat weight, the inventive compositions
provide generally improved adhesive properties (loop tack
and 90 degree peel results), particularly the improved loop
tack on glass.
Resin
c D E F* G*
76.44 76.44 84.00 74.94
74.94
6.00 6.00 0 7.50
7.50
0 0 3.00 0 0
8.00 2.00 5.00 5.0 0
5.00
 US 9,988,565 B2
11 12
TABLE I-continued
Synthesis and Properties of Adducted Rosin
Esters

Re sin

A B c D E F*
Glycerol G*
PEG 400
5.00 5.00 2.00 8.0 0 5.00 5.00
PEG 200
A nox ® 20/ Irga nox ® 5.0 0
10 10 /E310 1 7.50 7.50
7.50
total 7.50 7.50 3.00 7.50
Spe cifications 0.06 0.06 0.06 0.06 0.06 0.06
Acid number, mg KOH/g 0.0 6
Gardner color, neat
Me ttle r softe ning point, ° C. 10 0.0 10 0.0 10 0.0 10 0.0 10 0.0 10 0.0
Br ook field visc os ity, cP @ 90° 10 0.0
@ 95° c.
C.
5
@ 100° 41. 5 44.2 47.7 46.9 2 34 .9 47.3
C. Mn 53.3 9
Mw 8.0 8.0 9+ 2 8- 8+
Mz 7+ 0
Mz + 1 67.8 68.4 69.9 62.6 88.2 71. 5
polydispersity 72
(Mw/Mn) 24000 35350 45200 132 25
"Target
1Blend of acidTg,
number 45-55 mg KOH/g before addition of itaconic
midpoint,
acid. AnoxC.® 20 (hindered phenolic antioxidant,
0
12 925 product 18 650
of Chemtura), 24900 7338 phenol antioxidant, product
Irganox ® 1010 (hindered 14 200
of Ciba Specialty Chemicals),
E310
and (propyl gallate). 17 900
7263 10 52 5 12 625 4350 2912 9475
10 800
TABLE 2 572 614 598 530 69 TABLE 5953
606
10 80 12 71 110 9 893Adhesives154from Adducted10Rosin 19 Esters and an Acrylic
Adbesives from Adducted Rosin 112 Esters and an Acrylic 30
6 Dispersion
Dispersion 2780 3524 2318 2019 381 2110 Control 2647
Control 7246 7498 4878 56 42 649 4046 *
* 519 8 Formulation:
Formulation: 1. 89 2.07 1. 86 1. 69 2.24 1.71
1. 86
35
adducted RE tackifier B c D
adducted RE A 16B.7 c 19 .0 D 16 .0 tackifie r dispe11. 3rsion, % 48.8
tackifier dispe rsion, g
solids 14 .4 53.6 1
14 .0
54 .4 0
13.8 14 .0
15 .7 53.57
ta ckifier
55.30 53.61 54.40 53.57 acrylic polymer dispersion 1, g 13 .2 13.25
tackifie r dispe rsion,
13 .2 acrylic polymer dispersion 2, g 13 .2 13.25
% solids
13 .2
tackifie r dispe rsion, g bas N H 40 H N H 40 H
17 .44 17.85 17.66 17 .86 tackifier/polyme r (dry:dry) 30:70 30 :7 0
e N H 40 H
Acronal ® V 215, g 30:70
tackifier/polymer 33.02 32.76 32.88 32.75 40 coat wt. (g/rrr') 18 .0 16 .2 16 .2
(dry:dry) static she ar, h 7.3 4.0 3.3 2.6
N16 H.2
40 H N H40 H N H4 0 H loop tack, LDPE, lbs. 2.1 2.2 1. 9
base N30:70
H4 0 H 30 :70 30 :70 30:70 Adhesive prope rtie s:
2.0 loop tack, glass, lbs. 4.0 4.2 3.8
coat wt. (g/rrr') 16 .1 16 .2 16 .1 16 .0 16 .3
3.8
Adhesive 45 loop tack, ca r. cardboard, lbs. 1.1 1.1 1. 0
properties :
loop tack, LDPE, lbs. 1.1
2.3 2.0 2.3 2.1 2.2 90° peel, LDPE, pli 1. 2 1.3 1. 2 1.2
loop tack, glass, lbs. 90° peel, ca r. cardboard, pli 1. 4 1.5 1. 4 1.3
loop tack, cor. 2.8 3.6 3.9 4.0 3.6 Conclusion: Except for static shear, generally equal
cardboard, lbs. 1. 5 1.3 1. 5 1. 5 1.7 perf ormance from the adducted RE
tackifie rs ve rsus control at lowe r
90° peel, LDPE, pli
1.1 1.1 1.3 1. 4 1.4 50 "Control = commercial label adhesive. coat weight.
90° peel, cor. Loop tack and 90° peel results are an average of three samples.
1. 0 1.2 1. 2 1. 0 1.1
cardboard, pli Static shear: stainless steel, 1" x 1" x 1000 g, average of three
samples.
Conclusion: Generally improve d results at same coat weight,
particularly loop tack on glass. Table 4 summarizes examples in which the water-d ispers-
55 ible adducted rosin ester (A or B) is not the only tackifier
"Control = commercial label adhesive. component. Commercially available terpene-phenol resins
Acronal ® V 215 acrylate copolymer dispersion is a product of BASF. (Sylvares® TP 95 and TP 10 5) and a dimerized rosin
Loop tack and 90° peel results are an average of three samples. (Dymerex™ rosin) are in cluded at 5 to 25 wt. % based on
60 the combined amounts of adducted rosin ester and commer-
In the Table 3 experiments, adducted rosin ester tackifiers cial tackifier. Thus, the first entry in Table 4 illustrates a
BD are used with a 50:50 blend of acrylic polymers used for tackifier mixture of 25 wt. % Sylvares® TP 95 and 7 5 wt. %
pressure-sensitive adhesives. Here, the control is formulated of adducted rosin ester A. A portion (about 18 g) of the
at 18 g/rn", and the experimental samples are formulated at resulting aqueous tackifier dispersion (53% solids) is com•
16 g/m2 . Except for static shear, the adducted rosin ester 65 bined withAcronal® V 215 acrylic emulsion (32.7 g) to give
tackifier provides generally equal performance at the lower the tackified adhesive formulation. As sh own in the table,
coat weight. the in ventive formulations perform as well as or better than
the control f ormulation at a 20% lower coat weight (16 g/m'
versus 20 g/m").
 us 9,988,565 B2
13
14
TABLE 4
Adhesives from Adducted Rosin Esters, Other Tackifiers, and an Aq:ylic Dis12ersion

Control*

Formulation:

adducted RE tackifier A A A A B B B
% Sylvares ® TP 95 B
% Sylvares ® TP 105 25 25
% Dymerex T M rosin 25 25
tackifier dispersion, % 15 15
solids tackifier dispersion, 53.14 54 .24 54 .13 53.73 58 .75 56 .33 53.62
g Acronal ® V 215, g 53.10
tackifier/polymer (dry:dry) 17 .97 17 .69 17 .7 2 17 .82 16 .68 17 .21 17 .85
17 .9 8
base
coat wt. (g/rrr') 32 .69 32.86 32 .8 4 32.78 33.55 33.18 32.76
32 .6 8
Adhesive properties :
static shear, h 30 :70 30 :7 0 30:70 30 :70 30:70 30 :70 30 :70
30:70
loop tack, LDPE,
NH 40 H NH 40 H NH 40 H NH 40 H NH 40 H NH 40 H NH 40 H NH 40 H
lbs. loop tack, glass, 19 .8 16 .3 16 .4 16 .4 16 .3 16 .3 16 .2 16 .3
lbs. 16 .3
loop tack, car. cardboard,
lbs.
90° peel, LDPE, pli 8.6 15 12 18 13 8.3 9.9 16
90° peel, car. cardboard, pli 12
Conclusion:
"Control = commercial label adhesive.
2.5 2.1 2.4 2.3 2.1 2.1 2.0 1.7
2.0
Acronal ® V 215 dispersion is a product of BASF.
Loop tack and 90° peel results are an average of 3. 4three samples.
3.7 4.2 4.0 3.7 3.6 3.5 3.6
Static shear: stainless steel, 1" x 1" x 1000 g, average of three samples.
3.7
Sylvares ® TP 95 and TP 105 are terpene-phenol1.resins,
8 1. 6 of Arizona
products 1. 9 Chemical.
1.5 1.1 1.6 1. 6 1.3
Dymerex TM polymerized rosin is a product of Eastman Chemical. 1.3
1.3 1. 4 1. 4 1.4 1. 4 1.3 1.3 1.3
1.4
1. 2 1.3 1.1 1. 2 30 1. 0 1.2 1.1 1. 2
Table 5 demonstrates that inventive water-dispersible 1. 2 esters A or F are combined with 50 wt. % of Sylvares® TP
adducted rosin esters A and B can be combined
Generally with
equal performance 95, TP
from the 10 5, or RE
adducted TP 115 , which have sof tenin g points of 95°
Sylvares® TP 10 5 at a 3:1 weight ratio to versus
tackifiers give good
control at C.,
lower10coat
5° C., and 115 ° C., respe ctively. The aqueous tackifier
weight.
adhesives with either the acrylic polymer blend or with dispersions are prepared in a pressurized reactor as
Acronal® V 215 dispersion. Note that the adhesive proper• 35 described earlier. Generally, the adducted rosin ester tacki•
ties from the inventive adducted rosin ester blends rival fiers provide equal adhesive perfor mance at a 20% reduction
those f rom the control even with a 20% reduction in coat in coat weight. The results suggest better loopt ack on glass
weight. The last entry shows that adducted rosin ester C (8:2 when terpene-phenol resins with higher softening points are
pentaerythritol to glycerin ratio) can be used alone to give an used.
adhesive that performs well at low coat weight. 40 The examples in Table 9 show the effect of varying the pH
Table 6 summarizes formulations using 75 wt. % of a and the ratio of anionic to nonionic surf actant in preparin g
water-dispersible adducted rosin ester (A, B, F, or G) with 25 tackifier dispersions from water-dispersible adducted rosin
wt.% of Sylvares® TP 10 5 in an Acronal® V 215 system.
In each case, the tackifier blend comprising the ester A. Generally, all of the f ormulations provide improved
adducted rosin ester performs as well as or better than the adhesive performance at reduced coat weight.
control at a much lower coat weight (16 g/m2 versus 19.5 or 45 Table 10 shows the effect of coat weight on
20 g/m").
adhesive properties for a series of adhesives made using 75
Table 7 shows similar results when the same resins are wt. % of adducted rosin ester A and 25 wt.% of S ylvares TP
used with 25 wt. % of Sylvares® TP 105 and the acrylic 10 5. The inventive tackifiers provide generally equal
polymer blend. perfor mance versus the control when used at lower coat
Table 8 shows the effect of increasing the sof tening point weight and higher performance than the control when used
of the tackifier blend. Water-dispersible adducted rosin at the same coat weight.
TABLE 5

Adhesives from Adducted Rosin Esters, a Terpene-Phenol Tackifier,

and
an Acrylic Dispersion
Control*

Formula tio
n:
adducted RE tackifier A A B B c
% Sylvares ® TP 10 5 25 25 25 25 0
tackifier dispersion, % solids 53.95 53.95 56.50 56.50
53.89
tackifier dispersion, g 13.90 13.22 13.44 13.73
13.91
Acronal ® V 215, g 0 26.25 0 26.56 0
acrylic polymer dispersion 1, g 13 .2 2 0 13 .38 0
13 .22 acryhc polymer dispersion 2, g 13 .2 2 0 13 .38 0
13 .22
 US 9,988,565 B2
15 16
TABLE 5-continued
Adhesives f rom Adducted Rosin Est ers, a T erpene-Phe nol
Tackifier, and
an Ac lie Dis ersion
Control
*
tackifier/polymer (dry:dry) 30 :70 30 :70 30:70 30 :7 0
base 30:70
NH 40 H NH 40 H NH 4 0 H NH 40 H NH 40 H
coat wt. (g/rrr')
20.0 16 .1 16 .3 16 .0 16 .6
Adhesive 16 .2
properties:
loop tack, LDPE,
lbs. loop tack, glass, 2.1 1.7 2.2 1. 9 1.9
lbs. 2.0
loop tack car. cardboard, lbs. 3.7 3.5 3.6 3.8 3.5 3.5
90° peel, LDPE, pli 1. 9 1. 8 1. 8 2.1 2.0
90° peel, car. cardboard, pli 1. 5
Conclusion: 1. 2 1.3 1.4 1. 5 1.3
"Control = commercial label adhesive, 1.3
1.1
Acronal ® V 215 dispersion is a product of BASF. 0.9 1. 0 1. 0 1.0
Loop tack and 90° peel results are an average 1.of0 three samples.
Sylvares ® TP 105 terpene-phenol resin is a productGenerally
of Arizona equal performance from the
Chemical.
adducted
RE tackifiers versus control at lower coat
weight.

TABLE 6
Adhesives from Adducted Rosin Esters, a Terpene -Phenol Tackifier, and an Acrylic Dispersion

C ontrol* Control*

Formulation:

adducted RE tackifier B B G G A A A
% Sylvares ® TP 105 F
tackifier dispersion, % 25 25 25 25 25 25 25
solids tackifier dispersion, 25
g Acronal ® V 215, g 52 .83 53.06 54 .56 53.01 53.44 53.63 54 .0 2
tackifier/polymer (dry:dry) 52.91
base 14 .4 5 14 .4 0 14 .11 14 .4 1 14 .33 14 .29 14 .2 1
14 .4 3
coat wt. (g/rrr')
26.10 26.13 26.32 26.13 26.18 26.20 26.2 5
Adhesive
26.11
properties:
loop tack, LDPE, 30 :70 30 :7 0 30:70 30 :70 30 :70 30:70 30 :70
lbs. loop tack, glass, 30 :7 0
lbs. NH 40 H NH 40 H NH 40 H NH 40 H NH 4 0 H NH 4 0 H NH 4 0 H NH40 H
loop tack, cor. 19 .5 16 .3 15.9 16 .2 16 .0 20.2 15.9 16 .3 16 .5
cardboard, lbs. 16 .0
90° peel, LDPE, pli
90° peel, car. cardboard, pli 1. 6 1. 4 1. 4 1.4 1. 6 2.0 1. 8 1.7 1.7
Conclusion:
"Control = commercial label adhesive. 1. 5
Acronal ® V 215 dispersion is a product of BASF.
3.2 3.5 3.7 3.2 3.5 4.2 3.6 3.6 3.4
Loop tack and 90° peel results are an average of three samples. 3. 4
Sylvares ® TP 105 terpene-phenol resin is a product of Arizona Chemical.
1. 6 1.3 1.3 1. 2 1. 2 1. 6 1.7 1.8 1.4
1. 4

1.3 1. 2 1.3
1.3 1. 5 1.4 1.3 1. 4 1.3
1.3
1.1 1. 2 TABLE
1.1
1.3 1.72 1. 2 1.1 1.0 1. 0
1.1
Generally equal pe rf orma nce f rom the adducted RE tackifiers versus control at lowe r coa t
Adhesives from Adducted Rosin Esters, a Terpene-Phenol Tackifier, and an Acrylic Dispersion
we ight.

Control* Control*

Formulation:

adducted RE tackifier B B G G A A A F
% Sylvares ® TP 105 25 25 25 25 25 25 25
tackifier dispersion, % solids 25
tackifier dispersion, g 52.83 53.06 54 .56 53.01 53.63 54 .02 54 .02
53.65
acrylic polymer dispersion, g
13.99 13.95 13.66 13.96 13.84 13.76 13.76
tackifier/polymer (dry:dry) 13.83
base
26.39 26.42 26.61 26.41 26.49 26.54 26.54
coat wt. (g/rrr') 26.50
30:70 30:70 30:70 30:70 30:70 30:70 30:70
30:70
NH 40 H NH 40 H NH 40 H NH 40 H NH 40 H NH 4 0 H NH 4 0 H NH40 H

19 .5 16 .5 16 .1 16 .0 16 .1 19 .6 16 .2 16 .3 16 .2
16 .1
 US 9,988,565
17 B2 18
TABLE 7-continued
Adhesives from Adducted Rosin Esters, a Terpene -Phenol Tackifier, and an Acrylic
Dispersion
C ontrol* Control*

Adhesive properties :

loop tack, LDPE, 1. 6 1. 5 1. 2 1.3 1.1 2.0 1.7 1.9 1. 9

lbs. loop tack, glass, 1.7
lbs. 3.2 3.5 3.9 4.0 3.1 3.9 4.0 4.7 3.7
loop tack, cor. 3.8
cardboard, lbs. 1. 6 1. 2 1.3 1.1 1. 4 1.7 1.3 1.6 1.4
1. 8
90° peel, LDPE, pli
90° peel, car. cardboard, pli 1.3 1. 4 0.9 1.3
1.3 1. 2 1. 2 1.3 1. 2
Conclusion:
"Control = commercial label adhesive. 1. 2
Loop tack and 90° peel results are an average 1.1
of three samples.
1.1 1. 0 1.1
1.1 1. 2 0.9 0.8 1. 0
Sylvares ® TP 105 terpene-phenol resin is a product of Arizona Chemical. 1.1
G enerally equal pe rf orma nc e f rom the adducted RE tackifiers versus control at lowe r coa t
we ight.
TABLE 8 TABLE 8-continued

Adhesives from Adducted Rosin Esters, a Terpene-Phenol 20 Adhesives f rom Adducted Rosin Esters, a Terpe ne -P he nol
Tackifier, Tackifie r, and an Acrylic Dispersion: PARR Reactor
and an Acrylic Dispersion: PARR Reactor Runs Runs
Control Control
Control Control * *
* * Adhesive
For mula tio properties:
n: 25
loop tack, LDPE, lbs. 2.3 2.1 2.3 1. 9
adducted RE tackifier A F F
2.2 loop tack, glass, lbs. 4.1 2.8 4.1 3.8
% Sylvares ® TP 95 50
3.7 loop tack, cor. 1.7 1. 8 1.9 1. 4
% Sylvares ® TP 105 50 1.5 cardboard, lbs.
% Sylvares ® TP 50 90° peel, LDP E, pli 1.4 1. 4 1.4 1.1
53.11 55.74 53.03 1.3
115 tackifier 30 90° peel, ca r. cardboa rd, pli 1.4 1.1 1.2 1.2
dispersion, 1. 2
17.60
% solids C onclusion: G enerally equal perf orma nce f rom
32.91 16 .99 17 .62 the adducted RE tackifiers versus
tackifier dispersion,
33.33 32.90 control at
g acrylic polymer "Control = commercial label adhesive.
30:70 lower coat weight. Better loop tack on
dispersion, g Loop tack and 90° peel results are an average of three samples.
KOH 30 :70 30 :70 Sylvares ® TP 95, TP 105, and TP glass from terpene
115 terpene-phenol -phenol
resins resins ofwith
are products Arizona
ta ck ifier/polyme r 35 Chemical. higher softening points.
20.7 16 .1
(dry:dry) 20.7 KOH KOH
base
16 .6 16 .1
coat wt. (g/rrr') TABLE 9
Adhesives f rom Adducted Rosin Esters and an Acrylic Dispe rsion: Effec t of
Surf actant
Control*

Formulation:

adducted RE ta ckifier A A A A
tackifier dispersion, % solids A
tackifier dispersion, g 54 .11 53.83
53.87 54 .15 53.47
acrylic polymer dispersion, g 17 .29 17 .36
17.35 17 .4 0 17.30
tackifier/polymer (dry:dry) 33.12 33.07
33.08 33.00 33.10
base 30:70 30:70
30:70 30:70 30:70
dispersion surfactant system NH4 0 H NH40 H
NH40 H NH40 H NH40 H
6% (3:1) J- 6% (3:1) J-
5% (3:1) J- 6% (4:1) J- 5% (4:1)
J-
pH Mulse 4012 Mulse 4012 Mulse 4012 Mulse 4012 Mulse
coat wt. (g/rrr') 4012 mixture mixture mixture mixture
Adhesive properties: mixture
7.5 8.5 8.5 8.5
loop tack, LDPE, lbs. 8.5
loop tack, glass, lbs. 20.5 16 .1 16 .6 16.2 16 .0
loop tack, cor. cardboard, 16.4
lbs.
90° peel, LDPE, pli
2.1 1. 9 2.0 1. 8 2.0
90° peel, glass, pli
1. 9
90° peel, car, cardboard, pli
4.8 5.7 5.1 4.3 4.7
Conclusion:
4.2
2.1 1. 9 2.0 2.1 2.0
1. 8
"Control = commercial label adhesive.
Loop tack and 90° peel results are an average of three
1.3 samples. 1. 4 1.5 1. 6 1.4
J-Mulse TM 4012 emulsifier is a product of J1 Technologies having -1:1 anionic/nonionic1.3 surfactant ratio;
additional anionic surfactant (tridecyl ether phosphate)
2.7 is added to3.0
give the 3:1 or 4:1
2.7ratios recited above.
2.4 2.0
2.5
1.3 1.1 1.2 1. 2 1.2
1.1
Generally equal performance from the adducted RE tackifiers
versus control at lower coat weight.
 US 9,988,565
19 B2 20
TABLE 10 3. The rosin ester dispersion composrnon of claim
1 wherein the adducted rosin ester has an acid value within
Adhesives from Adducted Rosin Esters, a Terpene -Phenol the range of 45 to 55 mg KOH/g.
Tackifier, and an Aqylic Dis12ersion: "Coat
Ladder"
4. The rosin ester dispersion composition of claim
Control* 1 wherein the adducted rosin ester has a ring-and-ball
soften• ing point within the range of 65 to 72° C.
Formulation:
5. The rosin ester dispersion composition of claim
adducted RE tackifier A A A 1 wherein the adducted rosin ester comprises at least 5 wt.
% Sylvares ® TP 105 A
25 25 25 25
% of adducted itaconic acid.
tackifier dispersion, % 10
solids tackifier dispersion, 59.39 59 .39 59.39 6. The rosin ester dispersion composition of claim 1
g 59.39 further comprising a surfactant and a tackifier.
acrylic polymer dispersion, 113.28 16 .14 16 .14
16 .14
7. The rosin ester dispersion composition of claim 6
g tackifier/polymer comprising 35 to 60 wt.% of water, 0.1 to 10 wt.% of the
(dry:dry) 237.56 33.8 6 33.86
pH
33.86 15 surfactant, and 40 to 65 wt. % of the tackifier.
coat 30 :70 30:70 30 :70 8. The rosin ester dispersion composition of claim
static wt. (g/rrr')
shear, h 30 :70
Adhesive
loop tack, LDPE, 6 wherein the tackifier further comprises a resin selected
7.0 8.6 8.6
properties:
lbs. loop tack, glass, from the group consisting of polyterpenes, terpene-phenol
8.6
lbs. 19 .8 16 .2 16 .2 17 .5 resins, aromatic-terpene resins, aromatic-terpene-phenol
loop tack, ca r. ca rdboa rd, 19 .5 20 resins, rosin esters, hydrocarbon resins, liq uid hydrocarbon
lbs.
90° peel, LDPE, pli resins, aromatic resins, and mixtures thereof .
90° peel, car. cardboard, pli 13 8.0 7.0 5.3 9. The rosin ester dispersion composition of claim
Conclusion: 4.3
6 wherein the surfactant comprises a sulf ate or phosphate
2.0 1. 9 2.1 2.2
1. 9 of an ethoxylated f atty alcohol or an ethoxylated f atty
25
"Control = commercial label adhesive. 6.2 6.1 5.8 6.1 acid.
Loop tack and 90° peel results are an average of three samples. 6.5 10. The rosin ester dispersion composition of claim 1
Sylvares ® TP 105, terpene-phenol resin, is a 2.2 2.0 Chemical.
product of Arizona 1. 8 2.2
2.2
further comprising a polymer emulsion.
The preceding examples are 1.meant 4 1. 5 as illustrations;
only 1.5 1.3 11. The rosin ester dispersion composition of claim 10
the following claims define the
1.7 wherein the polymer emulsion is selected from the group
1.1 scope 1.3 of the1.2invention.1. 4 1. 9 30
We claim: consisting of acrylic polymers, natural rubbers, and styrene-
Generally equal performance from
1. A rosin ester dispersionthecomposition comprising:
adducted RE tackifiers versus
butadiene polymers.
(a) an adducted rosin estercontrol producedwhen by:used at lower coat 12. The rosin ester dispersion composition of claim 1,
reacting a rosin with a polyol weight, toandprovide
higher performance
a rosin ester wherein the adducted rosin ester esterified with the polyeth•
intermediate; and than control when used at the same 35 ylene glycol is insoluble in water.
coat weight.
reacting the rosin ester intermediate with a dienophile 13. The rosin ester dispersion composition of claim 1,
to provide an adducted rosin ester; and wherein the polyol is sele cted from the group consisting of
(b) water; glycerin , pentaerythritol, trimethylolpropane, trimethylole•
wherein said adducted rosin ester is esterified with a thane, ethylene glycol, propylene glycol, diethylene glycol,
polyethylene glycol having a weight-average molecular 40
triethylene glycol, tetraethylene glycol, dipentaerythritol,
weight less than 700. and sorbitol 1,3-propanediol, 2-methyl-1,3-propanediol,
2. The rosin ester dispersion composition of claim 1 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimetha•
wherein the polyethylene glycol has a weight-average nol, diglycerol, dipentaerythritol, mannitol, sorbitol,
molecular weight within the range of 200 to 400. hexitol,
and mixtures thereof.

* * * * *