Dispersant Technologies for Improved Economy Paints

Lidaris San Miguel Rivera, Caroline Hinson, Sandy Umphrey, Trevor Ewers, Tom Kalantar, Ant Van Dyk,
Mark Langille

The Dow Chemical Company, Dow Coating Materials Additives R&D, Midland-Michigan, Collegeville-
Pennsylvania, USA

ABSTRACT

High pigment volume concentration (PVC), or economy, paints constitute about half of the
volume of waterborne architectural coatings used globally, and are particularly important in
Asian Pacific (AP), Latin American (LA), and European, Middle Eastern and African (EMEA)
markets. In LA this market corresponds to 30-35% of the architectural market of 2.3 billion
liters.1 These paints are predominantly composed of more economical extenders to reduce
costs using small amounts of binder and TiO2. As a result, high PVC paints generally suffer
from poor wash resistance, durability and wet hiding. There is a need in this market to lower the
formulation cost while maintaining or improving film properties such as wash resistance, opacity,
and color acceptance, and others. Dispersants play a key role in high PVC formulations to help
disperse and stabilize pigments and extenders along with influencing many coating properties.
Typically, low cost polyacid dispersants are used in this market segment. However, premium
dispersants have been found to improve many coating properties including hiding, wash
resistance, and scrub resistance. Premium hydrophobic copolymer dispersants provide the
formulator with additional latitude to vary the extender package (particle sizes and extender
types), and the PVC, to provide cost effective more sustainable solutions to performance
targets. This work focuses on the development of a new dispersant to provide improved
washability in high PVC formulations. An 80% PVC styrene-acrylic paint with a cellulose ether
thickener was used as a screening formulation. New dispersant compositions with an improved
washability performance were identified. We have explored how dispersant composition affects
key coating performance properties in this high PVC formulation space. An analysis of these
results is presented and we discuss how dispersant interactions with the formulation can be
selected to maximize cost effective opacity, wash and scrub resistance performance.

INTRODUCTION
High pigment volume concentration (PVC), or economy, paints constitute half of the volume of
waterborne architectural coatings globally, primarily concentrated in the Asia Pacific (AP), Latin
American (LA), and European, Middle Eastern and Africa (EMEA) markets. In LA this market
corresponds to 30-35% of the architectural market of 2.3 billion liters. These paints are
predominantly composed of more economical extenders and pigments, using very little binder
and TiO2 to reduce cost as these are more expensive components. As a result, high PVC
paints generally suffer from poor durability and low wet hiding. Formulators often assume that
the best way to make the lowest cost paint is to use the lowest cost ingredients. We believe
that an alternative approach to low cost paint is to optimize the total cost of the formulation
rather than each individual ingredient. Using higher quality/more efficient raw materials may

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allow formulators to use lower amounts of high cost raw materials in their paint (i.e. binder, TiO2)
to deliver a lower total formulated cost with equal or improved performance.

Typically, low cost polyacid homopolymer dispersants have been used in this market segment.
However, premium dispersants have been shown to improve many coating properties including
color acceptance, hiding, and water resistance properties. Substituting the cheaper polyacid
dispersants with premium dispersants may allow for improved film properties at an equal or
lower formulation cost to meet market needs. The added expense from the dispersant
substitution can be offset by slightly increasing PVC level to reduce the more expensive binder
content. Premium hydrophobic copolymer dispersants provide the formulator with additional
latitude to vary the extender package (particle sizes and extender types) and the PVC with more
cost effective solutions to performance targets. This work focuses on the development of a new
dispersant with improved washability in high PVC formulations. An 80% PVC styrene-acrylic
paint with cellulose ether thickener was used as a screening formulation. New dispersant
compositions with improved washability performance were identified. We have explored how
dispersant composition affects key coating performance properties in this high PVC formulation
space. An analysis of these results is presented and we discuss how dispersant interactions
with the formulation can be selected to optimize cost effective opacity, wash and scrub
resistance performance.

EXPERIMENTAL PROCEDURES

Synthesis
The experimental dispersants for this study were synthesized and prepared as solutions or
dispersions in water.

Paint Formulation
The letdown for all paints was made in a single large batch. The water, Natrosol cellulose ether,
and AMP-95 neutralizing amine were mixed for 45 minutes to completely dissolve the Natrosol
cellulose ether and form a uniformly smooth solution. The remaining letdown ingredients were
added and mixed. Paints were made by dispersing the pigments, combining with letdown and
then mixing. The pH and KU of the paints were measured after completion and after 24 hours
equilibration time. The screening formulation is an 80 PVC styrene-acrylic paint with cellulose
ether thickener (see Figure 1).

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 Figure 1. Screening formulation.
GRIND mass (g)
Iceberg calcined clay 18.24
Ti-Pure R-706 TiO2 4.54
Mistron 353 talc 11.50
Omyacarb 3 CaCO3 41.39
Water ~32.32
Dispersant (0.35% on pigment) ~.75
Foamaster NXZ defoamer 0.23
Total 108.98
Letdown - Premix
Water 32.13
Natrosol 250 HBR cellulose ether 0.83
AMP-95 neutralizing amine 0.15
Foamaster NXZ defoamer 0.23
Texanol ester alcohol 1.53
Propylene Glycol 0.77
PRIMAL AS-380 Emulsion 16.10
Total 51.73
Grand Total 160.71
Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow

Washability Test
The washability test method was based on ASTM D4248 with adaptations to LA and AP
national paint tests and customer methods. The method differs from wet abrasive scrub
resistance methods ASTM D2486 and ISO 11998 in replacing an abrasive media with a
surfactant solution to better represent cleaning interior wall paints with detergent. The coatings
were drawn down on Leneta vinyl scrub charts using a two inch wide six mil Bird Bar with the
configuration shown in Figure 2. The drawdowns on both ends are sacrificial coatings and only
the three middle drawdowns are used for the washability data. Three charts were coated for
each dispersant sample resulting in 9 individual data points (per dispersant). The charts were
dried for 7 days and then subjected to the washability test using a Gardner Scrub Machine (see
Figure 3). The first and second cut through were both recorded and the latter was used for the
sample analysis. The washability test was performed using a 0.5% Nacconal 90G surfactant
solution and a Hog Bristle Brush (BYK, item 8111). After securing the dried panel and
positioning the brush in the holder, 20 mL of surfactant solution was evenly distributed over the
scrub area. Every 400 cycles five mL of surfactant solution was added to the scrub area. The
instrument was started and the panel observed for Fail Point 1 (first cut through): a three

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millimeter wide breakthrough in the coating indicated by seeing the black scrub chart and Fail
Point 2 (second cut through): a complete breakthrough the width of the coating as indicated by a
black line across the coating for each of the three test coatings on three panels per paint.

Figure 2. Schematic representation of a washability test drawdown chart.

Figure 3. Washability test instrument setup. Front view (left), top view (right).

RESULTS AND DISCUSSION

The first set of samples discussed here includes three control samples at different dispersant
loading levels of 0.35%, 1%, and 2% based on pigment. These controls were selected to
represent a polyacid dispersant (A1) and two hydrophobic dispersants (H1-A1 and H2-A2) with
different hydrophobe type. Table 1 shows the dispersants descriptions and abbreviations for all
the dispersant used in this study. The data collected for the three controls including delta KU,
contrast ratio, and washability (second cut through) is included in Table 2. All formulations show
stable KU after 24 hrs and compatibility issues were not observed independently of the

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dispersant used or the dispersant loading level. The contrast ratio was fairly constant across all
samples included in the first set.

Table 1. Dispersant descriptions and abbreviations.

dispersant description abbreviation set #
hydrophobic copolymer 1-acid type 1 H1-A1 1,2,3
hydrophobic copolymer 2-acid type 1 H2-A1 1,3
hydrophobic copolymer-acid type 2 H-A2 2,3
hydrophobic copolymer-acid type 3 H-A3 2
polyacid-acid type 1 A1 1,2,3
polyacid-acid type 2 A2 2
polyacid-acid type 3 A3 2
polyacid-acid type 1 & 2 A1&2 2
hydrophilic copolymer-acid type 1 HP-A1 2

Table 2. Delta KU, contrast ratio, and washability data for control samples.

nd
Contrast 2 Cut St.dev
Disp. Delta nd
dispersant Ratio through 2 Cut
level KU
Average Average through
0.35% 0.5 95.91 793 94
H1-A1 1% 1.1 96.75 748 16
2% -0.1 96.79 792 60
0.35% -0.2 96.66 570 37
A1 1% -0.4 96.67 667 70
2% -1.1 96.39 634 28
0.35% 0.4 96.96 659 22
H2-A1 1% -2.1 96.49 645 19
2% -1.9 96.64 585 18

JMP statistical analysis software was used to analyze the second cut through data and
determine differences among samples. Figure 4 shows the washability data for hydrophobic
copolymer 1-acid type 1 (H1-A1), hydrophobic copolymer-acid type 1 (H2-A1), and polyacid-
acid type 1 (A1) at 0.35% (top), 1% (middle), and 2% (bottom) dispersant loadings. In this case,
the three different dispersants are plotted together at 0.35%, 1%, and 2% dispersant loading. At
both the 0.35% and 2% levels, differentiation between all control dispersants is observed;
however, the observed trends are different. When the dispersant loading level is 0.35% the H1-
A1 dispersant shows the better washability behavior followed by H2-A1 dispersant and A1

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dispersant shows the worst performance. At 2% loading the H1-A1 dispersant still shows the
best performance but A1 dispersant takes the second place and H2-A1 dispersant shows the
lowest value for washability cycles. When 1% of dispersant based on pigment is used no
differentiation is observed for H2-A1 and A1 dispersants. Based on these results, it was decided
to use 0.35% dispersant loading in the rest of the scouting effort because differentiation can be
seen among all three dispersants and this loading level is commonly used in economy paint
formulations. The bottom line is that regardless of the level of dispersant used (within the range
of the experiment), H1-A1 dispersant consistently outperformed H2-A1 and A1 dispersants. This
could be attributed to the composition of the H1-A1 dispersant and the structure of the H1
hydrophobe which may provide better compatibility with the binder resulting in a stronger film. In
general the hydrophobic dispersant seems to have a better washability performance than
polyacids. This can be attributed to their ability to reduce water uptake, causing less swelling of
the film and minimizing the film mechanical strength loss. Upon washing of the film the
hydrophobic dispersant reduces the rate of extender particle removal from the film, which
creates a less abrasive media relative to polyacids, causing less damage to the film as it is
washed due to lower rate of removal of the film.

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Figure 4. Washability data for H1-A1, H2-A1, A1 at 0.35% (top), 1% (middle), and 2%
(bottom) dispersant loadings.

900
850

Second Cut through

800
750
700
650
600
550
500
H1-A1 (0.35%) H2-A1 (0.35%) A1 (0.35%)

900
850
Second Cut through

800
750
700
650
600
550
500
H1-A1 (1%) H2-A1 (1%) A1 (1%)

900
850
Second Cut through

800
750
700
650
600
550
500
H1-A1 (2%) H2-A1 (2%) A1 (2%)

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The second set of samples represents a diverse group of dispersants containing polyacids,
hydrophilic copolymer and hydrophobic copolymers. Representations of different acid types are
included for polyacids and hydrophobic copolymer to assess their effect on the washability
performance. Table 3 shows the delta KU, contrast ratio, and washability data for the second
set of materials studied here. As observed for the control samples discussed above, all the
formulations in this set exhibited good stability as evidenced by small delta KU differences. The
contrast ratio was fairly constant across all samples except for the hydrophilic copolymer-acid
type1 (HP-A1) dispersant which shows a lower value (see Table 3). This could be attributed to
lower adsorption to pigments and less effective electrosteric stabilization, which could possibly
be improved with a higher dispersant loading but at the expense of water resistance and
washability.

Table 3. Delta KU, contrast ratio and washability data for experimental dispersants
control samples in the second set at 0.35% dispersant loading level.
nd nd
2 Cut St.dev 2
Contrast Ratio
dispersant Delta KU through Cut
Average
Average through
A1 0.7 96.76 654 62
A2 -2.3 96.76 626 45
A3 -0.3 96.91 666 17
A1&2 -0.5 96.67 593 19
HP-A1 -0.5 96.02 581 8
H1-A1 -0.3 96.66 715 22
H-A2 -0.6 96.91 858 58
H-A3 -2 96.94 697 15

Figure 5 shows the washability data for the second set of experimental dispersants and control
samples. At first glance, looking at Figure 5 it can be observed that the hydrophobic dispersant
outperformed the polyacids and the hydrophilic copolymer. No statistical differentiation was
observed for polyacid dispersants containing acid type 1, 2, and 3. However, when acid type 1
and 2 was combined in the same dispersant, the washability performance was negatively
affected. HP-A1 dispersant shows slightly lower washability performance than polyacids. A clear
differentiation in washability performance is observed among the hydrophobic dispersants. Both
H1-A1 and hydrophobic copolymer-acid 3 (H-A3) dispersants have similar washability behavior
and a clear improvement in washability is observed for hydrophobic copolymer-acid type 2 (H-
A2) dispersant. This improvement can be attributed to the presence of acid type 2 potentially

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giving this material more absorption to the pigment particles than acid type 1 and 3. The
improved absorption combined with the hydrophobic character could result in a more uniform
and denser film resulting in an improvement in washability. However, when acid type 2 is
incorporated in a polyacid the washability improvement is not observed (see Figure 5, A2 and
A1&2). The advantage of incorporating acid type 2 is only observed when it is incorporated with
other hydrophobic monomers. It is important to note that these materials were tested at 0.35%
dispersant loading level (based on dry pigment) and this might not be the ideal dispersant use
level for all the dispersants in this study. Therefore further improvement could be expected by
optimizing the dispersant use level.

Figure 5. Washability data for the second set of dispersants.

950

900

850
Second Cut Through

800

750

700

650

600

550

500
A1 A2 A3 A1&2 HP-A1 H1-A1 H-A2 H-A3

The third set of samples is composed of the leading candidate in washability improvement (H-
A2) and control samples at different dispersant loading levels. Table 4 shows the delta KU,
contrast ratio, and washability data for the third set of samples studied here. As observed for
the first two sets, small delta KU values were measured after 24 hours indicating the preparation
of stable formulations over this period. However, the contrast ratio for this set present a
correlation with the washability data (shown in Figure 6). In general, as the contrast ratio
increases the washability performance is improved. As mentioned before, this could be more
evidence of the formation of a more uniform and denser film with better mechanical properties
resulting in an improvement in washability.

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Table 4. Delta KU, contrast ratio and washability data for H-A2 and control samples in the
third set at different dispersant loading level.

nd nd
Contrast Ratio 2 Cut through St.dev 2 Cut
dispersant Delta KU
Average Average through

A1 (0.35%) -0.5 96.72 607 13

A1 (2%) -0.2 96.65 598 32
H2-A1 (0.35%) -1.5 96.73 693 21
H2-A1 (2%) -0.9 96.59 557 33
H1-A1 (0.35%) -1 96.52 791 36
H1-A1 (2%) -1.1 96.73 802 50
H-A2 (0.35%) -0.6 96.91 858 58
H-A2 (1%) -1.1 96.92 1036 30
H-A2 (2%) -0.7 96.94 1328 119

Figure 6. Contrast ratio average in function of 2nd cut through average for the third set of
dispersants.

97.0
Constract Ratio Average

96.9

96.8

96.7

96.6

96.5

96.4
500 700 900 1100 1300 1500
2nd Cut Through Average

The washability data for the third set of experimental dispersants and control samples is shown
in Figure 7. In this set the dispersant loading level was varied to understand the effect on
washability performance. The performance of A1 was independent of the dispersant loading
level used here (0.35% and 2%, on dry pigment). The same trend was observed for the H1-A1
dispersant. However, both H2-A1 and H-A2 show a dependency in performance with the
dispersant use level. For the H2-A1 dispersant the washability performance is negatively

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affected when the dispersant loading level is increased from 0.35% to 2%. This is in full
agreement with the data collected for the control set samples (set 1). Conversely, the
performance of the H-A2 dispersant is improved as the dispersant loading level in increased.
The washability performance increases from an average of 858 cycles (2nd cut through) to 1326
cycles. For this material, the increased dispersant level results in a clear performance boost
relative to the other hydrophobic dispersant and polyacid control samples. This performance
benefit can be attributed to the presence of acid type 2 giving this material stronger absorption
to the pigment particles combined with the hydrophobic character of the dispersant.

Figure 7. Washability data for the third set of dispersants at different dispersant loading
level.

1500
1400
1300
Second Cut Through

1200
1100
1000
900
800
700
600
500
A1 A1 H2-A1 H2-A1 H1-A1 H1-A1 H-A2 H-A2 H-A2
(0.35%) (2%) (0.35%) (2%) (0.35%) (2%) (0.35%) (1%) (2%)

CONCLUSIONS
1. H1-A1 (hydrophobic copolymer 1-acid type 1) dispersant functions as a high performing
dispersant in high PVC formulations. Its performance in this formulation space exceeds
that of other control samples.
2. H-A2 (hydrophobic copolymer-acid type 2) dispersant shows superior performance to
H1-A1 dispersants in this high PVC formulation space.
3. The performance of H-A2 dispersant is dependent on dispersant use level. Higher use
level resulted in further improvement in performance. The advantage of incorporating
acid type 2 is only observed when is incorporated with other hydrophobic monomers.
4. This performance benefit can be attributed to the presence of acid type 2 giving this
material stronger absorption to the pigment particles, combined with the hydrophobic

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 character, resulting in a more uniform and denser film with the ability to reduce water
uptake, causing less swelling of the film, and minimizing the film mechanical strength
loss.
5. A high performance dispersant such as H-A2 has been shown to improve film properties
such as washability and contrast ratio in an economy paint formulation. It should also
give the formulator the option to reduce total formulated cost by taking advantage of the
improved film properties contributed by the dispersant to increase PVC by reducing the
level of more expensive materials such as the binder or TiO2 while retaining comparable
paint performance to the control formulation.

ACKNOWLEDGMENTS
The authors would like to thank Dan Saucy, Rob Fletcher, Art Leman, and Al Maurice for
valuable discussion.

1.(a) New Report Studies South American Paint Industry. PCI Magazine 2014, (June 1, 2014); (b)
Thurston, C., Latin American Paint and Coatings Market Rebounds, Investments Follow Strong Demand
Coatings World 2013, (June 2013); (c) Bangert, C.; Detiveaux, S., STATE OF THE GLOBAL COATINGS
INDUSTRY: 2013 and Beyond. Jct Coatingstech 2013, 10 (3), 48-52.

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