3.

CHEMICAL TYPES
OF THICKENING AGENTS
The chemistry of the many types of thickening agents is extremely large. Only a brief overview
is given in this section.

1. Starch and its derivatives

2. Derivatives of plant seeds (galactomannans)
3. Derivatives of seaweeds (alginate)
4. Viscous emulsions
5. Synthetic polymer thickeners

1. Starch and its derivatives

Native starch is a naturally occurring polymer and abundant in many plat products, and
naturally was the first thickener examined in detail by the textile printer. Because of the

CH2OH CH2OH CH2OH CH2OH

H O H H O H H O H H OH
H H H H
OH H OH H OH H OH H
HO OH O O O

H OH H OH H OH H OH

amylose

H OH H OH H OH

OH H O OH H O OH H O

H O H H O H H O H
CH2OH CH2 CH2OH

O
H
HO H O
OH H
H CH2OH
H
O
H
HO H O
OH H
H CH2OH
H

n
amylopectin
requirement for "boiling" and the amount required to achieve viscosity they are little used
unless they have further chemical treatment. The derivatives are still in use.

Starch is a homopolymer of glucose (D-glucopyranosyl) units, with most of the units

joined by α-D-(1 4) linkages. Most starches contain 20-30% of the linear chain polymer,
known as amylose ( see Figure ), together with an irregularly branched material, amylopectin.
Amylopectins have an α-D-(1 6) branch for each 15-30 glucose units. So-called waxy
starches contain little or no amylose. Separation can be achieved by fractional solution or
precipitation.

Advantages of starch thickeners: giving high colour yields

Disadvantages of starch thickeners: poor levelness and worse washing-off

Starch ethers

CH2 - O - CH2COONa
H O H
H
O OH H O

H OH

Carboxymethyl ether of starch

These are produced, in the presence of alkali (sodium hydroxide), by reaction with one or other
of monochloracetic acid, ethylene oxide, dimethyl sulphate. They readily produce cold soluble
products with good printing properties and colour yield although the "handle" of the final print
can be "harsh" under certain circumstances, particularly if H.T. steamed or given a bake
fixation. Normally, used in admixture with sodium alginate for vat dye printing by the two-
stage method (flash-age), or as a component of a blend product for polyester printing (by H. T.
steam fixation) where the starch ether can increase colour yield.

Typical product is "Solvitose C5" (Avebe Starches, Holland).

2. Derivatives of plant seeds (galactomannans)

General name for a related range of thickening agents based on the seeds of leguminous plants.
The main products of this group are:
Locust Bean Gum - although often quoted as a component of a thickener, its recent price
increases has virtually eliminated it as a textile print thickener
 Guar Gum - by far the most popular of the galactomannan products used

CH2OH
HO O H
H
OH H
H
H OH

CH2 H H
H O
O H
H OH OH
O OH OH H
H H
O
H H CH2OH
m
n

D-galacto - mannoglycans
m=1 - guaran
m=3 - carubin

M M M M M M
M - mannose
G G
G - galactose
. carubin ó

M M M M M M

G G G

. guaran

Although the cold-water dispersibility is a major advantage, attention must be paid to

the technique used for dispersion to avoid the formation of lumps. The hydration of the powder
should not be faster than the rate of surface wetting.

Typical products include "Indalca" PA3/R (Cesalpinia, Italy), "Polyprint" S82C (Polygal,
Switzerland). Normally, used for acid dye printing on polyamide, protein fibres, carpet
printing, blended with other thickeners for polyester printing, vat dye printing (both "all-in" for
discharge printing and blended with starch ether for 2-stage (flash ageing)).
3. Derivatives of seaweeds (alginate)
Derivatives of seaweeds by extraction of the alginic acid and treatment with sodium carbonate
to produce sodium alginate. They are important for reactive dye printing because of the
absence of primary hydroxyl groups and the repulsion of the dye anions by the ionised
carboxyl groups under alkaline conditions. They are available in a range of molecular weights
which produce grades ranging from "low viscosity" (high solid) to high viscosity (low solids).
Sodium alginates have become very important for print-paste thickening because of
their ready solubility, even after high-temperature fixation treatments.

COOH H H COOH H H
H O H O OH
H O OH OH H O OH OH
OH OH H O OH OH H
OH O O H
H H COOH H H COOH
n
alginic acid

They are used for reactive dye printing, vat dye printing by the two-stage method (flash ageing)
in admixture with starch ether and as a component of many polyester thickeners.

Typical products include, Manutex F, Manutex RS (Kelco), Lamitex L10 (Protan Ltd,
Norway).

Selection of a thickeners
Thickeners vary in both solid content and, what is most important to the textile printer, their
behaviour whilst actually being used in the printing process ( see Fig.T-3 and T-4 ).
1. Low solid grades - high viscosity (Manutex RS types)
More pseudoplastic, more sensitive to velocity gradient
2. High solid grades - low viscosity (Manutex F types)
Less sensitive to velocity gradient (D)
 η RS η
F

F
RS
conc % D
Fig.T-3: Viscosity vs concentration Fig.T-4: Flow curves

Manutex RS - for hydrophilic fibres

Manutex F - for hydrophobic fibres, less shear sensitive than Manutex RS

4. Viscous emulsions
Oil and water do mix, if enough energy is used to break up one component of the mixture into
small droplets, dispersed in the other component. Such simple emulsions are unstable, but their
stability and ease of preparation can be considerably increased by the incorporation of a
surface-active emulsifier. The nature of the emulsifier and the ratio of the two immiscible
liquids determine which liquid will be dispersed (the disperse phase) in the other (the outer,
continuous phase)
The emulsifier forms a film between the two liquids, reducing interfacial tension. Each
molecule of emulsifier contains a region that is hydrophilic and another that is hydrophobic
(lipophilic), and it is the balance between the dominance of these regions that determines its
relative solubility in oil and in water. This hydrophile-lipophile balance (HLB) has been
evaluated for many surface-active agents and expressed in a standard manner, over the range of
1 to 40. Experience has shown that compounds with HLB values of 3-6 stabilize water-in-oil
(W/O) emulsions and those with values of 8-18 are effective for oil-in-water (O/W) emulsions.

By using the petroleum distillate fraction (b.p.150-2000C) known as white spirit, water and
emulsifier we can prepare O/W emulsions suitable for pigment pastes. Nowadays these
emulsions are not used from ecological point of view.

5. Synthetic polymer thickeners

Synthetic thickeners are used in pigment printing systems. Environmental protection measures
on the use of emulsions, have encouraged the development of synthetic agents.
In general, these thickener are based on co-polymers of acrylic acid (e.g. methacrylic acid,
ethyl acrylate) which in water give low viscosity dispersions (the molecules are randomly
coiled). On adding alkali, the carboxyl acid groups are ionised, which causes the polymer
chains to extend by mutual repulsion with consequent increase in viscosity. FigureT-5 gives a
schematic interpretation of this change from randomly coiled to chain extension (viscosity
increase) with alkali addition.

Fig. T-5: Chain straightening of polyacrylic acid on addition of alcali

CH2 CH CH2 CH

COONH4 COONH4
n
H 2O

CH2 CH CH2 CH

CO CO

O-NH4+ O-NH4+ n

Fig.T-6: Ionisation of amonium salt of polyacrylic acid

Synthetic thickeners like polyacrylic acid (PAA - see Fig.T-6) exhibit pseudoplastic
rheology or shear thinning, which means that the formulation undergoes a large change in
viscosity under stress but recovers instantaneously on removal of stress to almost the original
viscosity. Synthetic thickeners are efficient at only 1-3 % concentration level while
approximately 10% of a natural thickener is needed to give the required viscosity in the print
paste. Other advantages of synthetic thickeners include rapid make-up since they require no
waiting for hydration to occur, sharp print boundaries, and controlled penetration which usually
provides greater colour value and levelness.
One problem with traditional PAA thickeners is sensitivity to electrolytes. A high
pigment concentration may cause a large decrease in viscosity of the required viscosity.
Traditional PAA thickeners sometimes exhibit difficulty in wash off after fixation of the print.
New innovation and technology in synthetic printers solved most of these above limitations.

Typical products include:

ALCOPRINT PT-RV - co-polymer of acrylic acid (Ciba)
LUTEXAL HIT - co-polymer of maleinic acid (BASF)
ACRACONZ F (Bayer)
LAMBICOL L91/S (LAMBERTI)