To control stability and compatibility of pigment pastes

Thursday, 01. June 2000

Quelle/Publication: European Coatings Journal

Ausgabe/Issue: 6/2000

Influences of additives in water based paint formulations Jörg Schrickel, Sandra Fischer, Peter Bissinger Pigment pastes, if they are
used as a prefabricated product in the paint and lacquer production, are requested to be as universal and economical as possible. To
meet this goal, it is necessary to know how additives effect the stability and compatibility of pigment pastes in paint formulations. With
this knowlegde negative effects can be minimized. Pigment pastes are important products in the fabrication of paints and lacquers [1].
Various types of pigment pastes exist as the requirements for their use differ strongly. For the use in decorative paints and lacquers
as well as for industrial paints a broad compatibility is essential to cover a large range of binder types and paint systems. Universal
pastes for solvent and water based systems are mainly used in decorative paints where they have to cover the whole range of
different paint formulations. Specific pastes, formulated with either grinding resins [2] or high performance dispersing agents, are
used in industrial paints. There, the use of grinding resins often prevents a high compatibility due to incompatibilities with the binder
used in the lacquer. The fact that a broad compatibility is necessary for the wide use of pigment pastes in different paint systems
leads to an increased sensitivity of the pastes from influences of other formulation ingredients. The type and quantity of wetting and
dispersing agent which is used in the production of the pigment paste can influence the conditions in the paint formulation. The
wetting and dispersing agents which are used in the base paint can influence the stability of the paste if the quantity of the wetting
agent in the paste (or in the paint) is not sufficient. Defoamers can strongly influence the stability of the paste due to their properties
to absorb surfactant molecules. Polyurethane thickeners can exhibit a positive influence on the stability of pigment pastes in tinting
systems due to their ? surfactant like ? hydrophobic-hydrophilic character. Even fillers like kaolins can improve the pigment stability in
certain paint formulations. In this lecture influences of additives on the stability and compatibility of pigment pastes in paint systems
are studied. The behaviour of defoamers, wetting agents and PUR thickeners in tinting systems are displayed. Types of pigment
pastes and their formulation Pigment pastes, if they are used as a prefabricated product in the paint and lacquer production, are
requested to be as universal and economical as possible. The requirements however, are very specific, depending on the paint
system and application. A differentiation can be made in pigment pastes which are based on grinding resins and others, in which
dispersing and wetting agents are used as principle grinding agents. In the first case the grinding resin provides strong wetting
properties and dispersing agents have only to be added in smaller quantities to support the dispersion. Due to various binder types
used in industrial paints incompatibilities can limit the use of grinding resins. Resin free pigment pastes generally show a better
compatibility with respect to the binder which is used in the paint formulation. As universal pastes they are mainly used in solvent and
water based decorative paints. In order to meet rising requirements concerning quality and environmental concerns, specific pastes
have to be developed. With polymeric dispersing agents these objective can be obtained. The applications in which pigment pastes
are used also determine the formulation of a paste. Pigment pastes for architectural coatings, with less requirements of compatibility
towards the binder, may be formulated with a relatively low quantity of a wetting dispersing agent. Anti-settling or thickening agents
can be used to adjust consistancy and stability of the paste if they do not influence gloss and colour strength significantly. Industrial
coatings [3], require a much better dispersion and quality of the paste. Here, the colour development, gloss, haze gloss and chemical
and mechanical resistance are the most important factors in order to obtain a perfect quality of the applied film [4]. The pigment
pastes for industrial use therefore require high quality dispersing agents and mainly higher dosages than pastes which are used in
architectural coatings. A resin free paste requires a higher content of dispersant In the preparation of pigment pastes with a grinding
resin a good stability of the paste is obtained by the high molecular resin which has sufficient wetting properties. Further wetting and
dispersing agents only have to be added in lower quantities in order to obtain an even better dispersion and stabilisation. The use of
thickening or anti-settling agents is dispensable. However, the compatibility of the grinding resin with the resin of the paint limits the
use ofe these pastes. A resin free paste requires a higher content of dispersant. This dispersant demand [5] in order to cover the
whole surface of the pigment, is determined by the type and size of the pigment surface. This minimum dosage of dispersant is often
not enough to obtain a stable paste. The necessary quantity of dispersant to obtain a stable paste can exceed in this case the
dispersant demand strongly. In additon to rising quality requirements, ecological aspects actually lead to the development of new,
APEO [6] and solvent free pigment pastes bades on polymeric dispersing agents. Results and Discussion Defoamers effect the
stability of pigment pastes Defoamers in water based paints can exhibit strong influences on pigment pastes due to their surfactant
absorbing character. This is especially pronounced in cases, where the quantity of wetting agent in a paste is rather low and/or where
a strong defoamer has already absorbed wetting agents from the base paint. The influence of defoamers on the stability of pigment
pastes in paint formulations is studied with the tinting of a white interior wall paint of high pvc with a conventional, commercially
available pigment paste of iron oxide black. The base paint is prepared in this experiment without defoamers. Different types of
defoamers with variations in their hydrophobic properties and chemical composition are added then to the paint. The defoamer and
the paste are incorporated during 5 minutes by stirring at 1000 rpm. To 100 g of paint 3.0 g of pigment paste is added together with
0.2 g of defoamer. Defoamer 1 and defoamer 2 are strongly unpolar, hydrophobic defoamers, based on highly purified paraffinic oils.
Defoamer 3 contains an emulsifier in addition to the paraffinic oils. The hydrophobicity and polarity of the polysiloxane defoamer 4 is
controlled by the modifications of the silicone chains. After application of 200 µm paint on degreased glass plates a rub out test is
carried out. After drying the colour strength for the rubbed and unrubbed surfaces is determined. Values are reported in Table 1. All
defoamers containing samples show a reduction of colour strength In Figure 1 a comparison of the colour strength values of rubbed
and unrubbed parts are displayed in function of the defoamer. The colour strength of the unrubbed part of the sample without
defoamer (100%) serves as reference for the comparison with different defoamer types. The influence of the defoamer on the colour
strength values of the applied films is significant. In comparison to the reference, all defoamers containing samples show a reduction
of colour strength. The values of colour strength with defoamer range from 46.7 to 94.6 for the unrubbed parts and from 49 to 108 for
the rubbed parts. Although defoamer 1, 2 and 3 consist of paraffinic white oil as principle active substance there is a big difference in
the influences they exhibit. Defoamer 3, which in comparison to the defoamers 1 and 2 contains additionaly a nonionic emulsifier, has
a much lower influence on the colour strength. However, the initial value of the reference cannot be reached. The lowest influence is

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 observed with defoamer 4, which is a modified polysiloxane defoamer. As already observed before in other occasions, this defoamer
type in general shows the lowest influence on the stability of pigment pastes in paint formulations. Defoamers 2, 3 and 4 lead to the
flocculation of the black pigment. The rubbed sufaces are darker (more intense) as the unrubbed surfaces. Flocculantes and
agglomerates have been destroyed mechanically upon rubbing. In contrast, the rubbed surface in the sample of defoamer 1 turns
brighter. This means, that mainly the titanium dioxide was flocculated in this case. The best: Mixing wetting agent and defoamer
before adding to the paint Defoamers act as ?absorber? of wetting agents and therefore can influence the stability of pigment pastes.
As a result flocculation occurs upon tinting a base paint with pigment pastes. The emulsifer containing defoamer 3 shows in
comparison with the emulsifier free defoamers 1 and 2 less influence on the stability of the pigment dispersion. In order to reduce the
influence of the defoamer the above displayed experiment was modified in such a way that a wetting agent was added together with
the defoamer. The type of wetting agent and the way of addition to the paint was modified. For all trials defoamer 1 was used due to
the strong destabilsation effect on the coloured pigment as well as on titanium dioxid in the previous experiment. Paint and pastes are
the same as mentioned above. The wetting agents which are used in this trials to modify the defoamer behaviour, are nonionic glycol
esters (wetting agents 1 to 3) and a modified sulfosuccinate (wetting agent 4). Each defoamer and wetting agent was introduced in
three different ways: a) mixing wetting agent and defoamer before adding to the paint, b) addition of the defoamer to the paint first,
then stirring for one minute and subsequent addition of the wetting agent, then stirring for four minutes, c) addition of the wetting
agent to the paint first, then stirring for one minute and subsequent addition of the defoamer, then stirring for four minutes. In Table 2
the colour strength values of the applied samples are displayed in function of the way of incorporation and wetting agent. As
comparison the values of the colour strength of the samples without defoamer (reference) and with defoamer 1 from the previous
experiment are also given. The unrubbed part of the sample without defoamer was again taken as reference at 100%. In Figure 2 the
colour strength values of the rubbed and unrubbed parts of the samples containing different wetting agents, are displayed. Trial No 1
is the reference and No 2 the defoamer application without wetting agent from the previous experiment. As can be seen immediately
from Figure 2 the wetting agents 1 and 3 have a positive influence in order to avoid stability problems of the paste (trials No 3 and 9).
In these cases the values for the unrubbed parts are like the reference value and the rubbed parts are even more intense compared
to the reference. In these two examples, flocculation of the pigments caused by the defoamer can be reduced by the use of a wetting
agent. The nature of the wetting agents is of subordinate importance: independent from the incorporation method wetting agents 2
and 4 do not exhibits improvements. The way of incorporation of the wetting agent is important. The high colour strength values with
wetting agents 1 and 3 can only be obtained, if the wetting agent and the defoamer are mixed together before addition to the paint
(incorporation method a). In the case of the incorporation methods b and c, in which one additive is added to the paint before the
other one, no significant difference is observed Incorporation method c with previous addition of the wetting agent leads to somewhat
better results than method b. The wetting agent only influences the relation of colour strength between rubbed and unrubbed parts
Independent from the chemical nature of the wetting agent is also the behaviour, whether the black or the white pigments flocculate
and therefore a higher or lower colour strength of the unrubbed surfaces compared to the rubbed surfaces are obtained. Here again
the way of incorporation of the wetting agent is more influent. As can be seen from Figure 2, in all incorporation methods ?a? the
colour strength of the rubbed parts is more intense, independent from the wetting agent. The higher colour strength values of the
rubbed parts indicate a flocculation of the pigments of the pigment paste. In contrast, all trials following incorporation method ?b? lead
to lower colour strength values of the rubbed surfaces. In this case the titanium dioxide pigments are more flocculated than the
coloured pigments. This flocculation is subsequently eliminated by rubbing, resulting thus in a lower colour strength of the rubbed
part. Incorporation method ?c? also leads to lower colour strength values of the rubbed parts. Only in trial No 8 the results are
contrarily, indicating, that also coloured pigments are flocculated. PU thickeners stabilize pigment pastes Polyurethane thickeners
consist of a hydrophobic-hydrophilic-hydrophobic structure. Due to hydrophobic-hydrophobic interactions associative PU thickeners
can interact with hydrophobic surfaces of pigments, obtaining thus an immobilisation (stabilisation) of the pigment in the paint system
[7]. Due to their hydrophobic-hydrophilic structure PU thickeners additionally can act surfactant-like. In order to examine the
influences of PU thickeners on the flocculation stability of pigments a pigment paste of an organic pigment was added to an interior
wall paint which contained only cellulosic ethers (MHEC 6000 mPas) as thickeners and no defoamer. Two pigment pastes were
prepared, one with a minimum stabilisation of the pigments and one with an optimum stabilisation. Paste A contains Heliogen green
pigment ?L 8730? with 15% of a polymeric dispersing agent calculated on the pigment. The pigment paste is stable to sedimentation
but contains only the minimum dispersant quantity which is necessary to cover completely the pigment surface. Paste B contains
35% dispersant on pigment and is stable and compatible with all paint formulations. The further ingredients are listed in table 3. The
pastes are added in 1.72 g quantity to 100 g of paint. This corresponds to 0.5% pigment solid in the paint. Four different trials are
carried out in order to investigate the influence of the thickener. In a first trial the paste was added to a paint sample which did not
contain neither defoamer nor PU thickener. In a second trial the paste was added to a sample which contained only defoamer
(defoamer 1 from the previous trials). The third sample only contained PU thickener, without defoamer and in the fourth sample both,
defoamer and PU thickener were present. The paint samples were applied on glass plates and one part of the surface was rubbed.
After drying colour strength and rub-out were determined. If paste A with 15% dispersant on pigment is added to the paint which does
not contain neither defoamer nor PU thickener, low colour strength and high rub-out values are obtained (Table 4). In the second
sample containing defoamer, the colour strength decreases slightly compared to the previous application, and the rub out increases,
indicating the flocculation of the green pigment. This changes significantly when the PU thickener is added to this paint (without
defoamer). A strong increase in colour strength and a strong reduction of the rub out can be observed. The influence of the PU
thickener results in an additonal stabilisation on the paste, which is prepared with the minimum dispersant quantity. If now defoamer 1
is added with the PU thickener, the thickener can maintain its stabilising effect. The destabilising effect of the defoamer is
suppressed, which is indicate in the small change of the rub out values. In Table 5 the colour strength and rub out values for the
samples with paste B, containing the optimum stabilisation of 35% dispersant on pigment, are displayed. The results change in the
case of the pigment paste B, which is sufficiently stabilised by dispersing agents from the beginning. The colour strength is
significantly higher and is not influenced any more by the addition of the PU thickener. The rub out values are considerably lower with
paste B. Using perfectly stabilised pigment pastes the influence of additives from the base paint can be minimised. Results at a
glance # The compatibility and stability of pigment pastes can be influenced by additives of the paint forumulations. # Defoamers act
as surfactant absorbers. This can lead to destabilisation effects on the pigment dispersions. # The choice of the right defoamer can
prevent problems in the forumulation of paints and lacquers, which are prepared using pigment pastes. # Wetting agents can control
the compatibility of defoamers. # Apart from adjusting rheological properties PU thickeners can stabilise pigments and reduce rub out
effects. # For the successful use of pigment pastes in the production of paints and lacquers-apart from the formulation of the paste ?

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 the careful choice of additives for the base paints is of crucial importance. [4 tables and 2 figures, please see tiff or pdf-file]
LIFELINES Dr. Jörg Schrickel, born in 1963, studied chemistry at the University of Münster where he obtained his degree in
organometallic chemistry. He gained his Ph. D. at the Max-Planck-Institut for radiation chemistry in Mülheim/Ruhr in organometallic
photochemistry. After a two years post-doctoral stage at the University of Zaragoza/Spain he joined Münzing Chemie GmbH in 1996
where he works as Sales and Marketing Manager. Sandra Fischer obtained a degree in Coatings Technology in Stuttgart. From 1995
to 1997 she worked as a technical manager in the product evaluation and customer service for metal pigments in printing inks at
Eckart Werke/Nürnberg. In 1998 she joined Münzing Chemie GmbH where she is responsible for technical customer service and
product development. Peter Bissinger obtained his degree in Coatings Technology in Stuttgart. He joined Münzing Chemie GmbH in
1992. As head of the technical service department he is responsible for customer service and product development. References [1]
Brock, Groteklaes, Mischke, Lehrbuch der Lacktechnologie, Vincentz Verlag, Hannover, (1998) [2] M. Dalton, R. Krause, P. Braun,
Ink World 3, (1997), 3, p. 64 [3] W. Herbst, H. Hunger, Industrial Organic Pigments, Verlag Chemie, Weinheim (1993) [4] L.-J. Calbo,
Handbook of Coatings Additives, Marcel Dekker, New York (1992) [5] W. Heilen, G. Feldmann-Krane, S. Silber; ECJ (1995) 10, p.
712 [6] J. H. Bielmann, FARBE&LACK (1996) 4, p. 91 [7] J. Schrickel, Pitture e Vernici, (1999), 5

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