Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 05/2007
Seite/Page: 144
Optimal dispersion
Latex/pigment composite particles improve waterborne
paints.
The quality of paint is to a large degree dependent on the
quality of the pigment particles dispersion. Latex particles
containing a new proprietary acrylic monomer capable of
superior binding to pigment surfaces show a significant
increase in the dispersion of TiO2 particles throughout the
dry film. This leads to a considerable improvement in key
paint performance properties.
Marie Bleuzen*, William J. Rosano, Gary R. Larson, Leo J.
Procopio.
* Corresponding Author. Contact: Dr. Marie Bleuzen, Rohm
and Haas, European Laboratories, 371 rue L. van
Beethoven, B.P. 249, 06905 Sophia Antipolis Cedex,
France, Tel. +33 4 93 95 53 60, mbleuzen@rohmhaas.com
The performance and appearance of pigmented waterborne
coatings strongly depend on the degree to which the various
pigments and polymer particles are dispersed throughout
the dried film [1-4]. The ideal state of dispersion is usually
reached when all particles are reduced to and remain as
non-flocculated primary particles.
Polymer particles, pigments and fillers that are not optimally
dispersed can adversely affect the ability of the coating to
provide an adequate barrier to electrolytes, water or gases,
as well as the mechanical properties such as tensile
strength, elongation, scrub resistance, and also optical
properties, for example hiding power and gloss. In addition,
poorly-dispersed pigments and fillers can affect the ability to
add colourant as well as the paint's colour stability under the
applied shear forces that occur during application by
brushing or spraying.
Increasing the latex-pigment interaction
When pigments such as TiO2 are well-dispersed, important
properties such as hiding, film gloss, colour and the
effectiveness of the coating as a barrier are maximised. A
way to provide an optimised pigment distribution is to form
polymer-pigment composite latex particles in the aqueous
phase, by effectively increasing the interaction between
individual TiO2 and latex particles. During the drying process
and film formation, this association can prevent TiO2
particles from agglomerating, avoiding negative impacts on
the performance.
A new approach to achieve such composites is offered by
using a newly developed, proprietary latex particle
containing a specialty monomer ("SM"). The SM contains
groups capable of binding to the pigment surface, which
significantly improve pigment association, allowing for a
more uniform pigment distribution and therefore enhancing
coatings performance properties as well as optimising
pigment usage.
Experimental tests show a range of improvements in
property performance such as better binding capacity in
paints above cPVC (critical pigment volume concentration).
Thus, scrub resistance and hiding power values typical for
conventional systems are achieved at up to 20% less binder
usage and up to 15% less TiO2 usage. Alternatively,
significant gains in scrub resistance and opacity occur at
equal binder and TiO2 usage.
In paints formulated below cPVC, significant improvement
occurs in stain-blocking and stain resistance, metal
adhesion, corrosion resistance, film gloss and efflorescence
resistance. The new technology is designed for high quality,
low-VOC, low odour interior wall paints as well as those for
exterior applications, thanks to its pure acrylic composition.
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Experimental design
The synthesis of emulsion polymers was based on standard
emulsion polymerization techniques found in the literature
[5,6]. The bulk compositions of the polymers were based on
combinations of acrylic or acrylic-styrene monomers and a
carboxylic functional monomer ("CFM") (control
composition) or a specialty monomer (SM). Latex particle
diameters were in the range from 100nm to 300nm, with
glass transition temperatures of about 35C unless noted
otherwise. The non-volatile content of the polymers was
about 40% by weight or greater. The polymer compositions
tested differed in the degree of hydrophobic character where
composition A was more hydrophobic (higher styrene
content) than composition B.
Emulsion polymers were formulated into screening
formulations using exterior grades of TiO2. All paints were
prepared from dry-powder pigments and extenders.
Film gloss was measured on coatings cast onto
phosphate-treated, cold-rolled steel whereas corrosion
resistance was determined on blast-cleaned, hot-rolled
steel. Paints were applied with a drawdown bar to give
about 3 mils (75m) of dry film. Coatings were allowed to
cure at 25C and ~55% RH for approximately two weeks
prior to testing.
Homogeneous pigment dispersion helps gloss
Table 1 compares the film gloss of paints based on
copolymer compositions containing either the CFM or the
SM. The data show that the gloss increased significantly in
both compositions when CFM was replaced with the SM.
The data also show that the level of gloss attained with the
SM in both polymer compositions was approximately the
same, whereas composition A was slightly higher. The
cause for the gloss increase is thought to result from better
dry-film morphology. Gloss retention of paints based on
composition B was close to 100% for both monomer types
for exposure times of about 1000 hours (UV-A/water
condensation). The paint based on composition A retained
ca 100% of its initial gloss when the polymer composition
included the SM while the CFM based paint gloss dropped.
Since neither the SM or CFM are expected to affect the
response of the polymer to UV light, the observed gloss
drop of the CFM based polymer of composition A may be
related to differences in film swelling during the
condensation cycle of the test.
Table 2 shows the improvement in film gloss of binders
based on the SM extended to lower TiO2 loadings. The SM
containing binder showed a much less rapid gloss decrease
with increasing pigment loading (e.g. only about 10 units in
20 degree gloss at 11 PVC) compared to the CFM
containing binder. The data show that, as the PVC
approached zero, film gloss for both paints approached the
same gloss values.
Field emission scanning electron microscopy (FE-SEM) of
cross sections of dried films (Figure 1) show that the TiO2
distribution of the paint based on the SM modified latex was
far more uniform compared to the paint based on the CFM
modified latex. Atomic force microscopy (AFM) scans
(images not provided here) were consistent with the
FE-SEM images, showing that paints based on the SM
modified latex had a more uniform TiO2 distribution relative
to CFM latex based coatings. In addition, surface roughness
(Ra) values, calculated from the AFM image data, were 24
and 29 for the SM and CFM based coatings, respectively.
The smoother surface of the SM based coating (smaller Ra)
 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 05/2007
Seite/Page: 144
is consistent with its higher film gloss.
Improved hiding power
A further consequence of a more uniform TiO2 distribution
using SM functional polymers is increased hiding power.
Table 3 shows the contrast ratios calculated from
Y-reflectance readings for paints formulated at 11 and 18
PVC. As can be seen, the SM containing binder gave higher
contrast ratios compared to CFM for both PVCs. In fact, the
contrast ratio of SM based paints at 11 PVC was about the
same as the CFM based paint at 18 PVC, suggesting a
potential reduction of TiO2.
Enhanced corrosion resistance properties
The effect of monomer type on the ability of the coating to
protect metal surfaces from corrosion during salt-fog
exposure significantly improved when the CFM was
replaced by the SM in both polymer compositions. Table 4
shows only a few blisters formed after a two-week, salt-fog
exposure of paints based on the SM containing polymer in
contrast to the dense blister formation on paints based on
CFM binder.
The reduction of blister formation for the SM containing
coating was consistent with improved film-barrier properties
as measured by EIS (electrical impedance spectroscopy)
[7]. Figure 2 compares the calculated coating resistance of
CFM and SM functional compositions as a function of
exposure time to the NaCl solution. The results show the
resistance (Rc) of the CFM based coating dropped by about
two orders of magnitude after about 20 minutes of exposure.
On the other hand, the resistance of the SM based coating
remained high and unchanged showing better barrier
properties compared to the CFM system.
Higher abrasion resistance
Polymers made with the new specialty monomer showed
improved abrasive scrub resistance over the conventional
CFM counterparts. Table 5 compares the mass loss after
200 scrub cycles of above critical PVC paints based on
all-acrylic polymers. The data show the CFM based paint
had a film-thickness loss of about 43m while the SM based
paint lost about 30m. In addition to the data shown here,
improved abrasive scrub resistance was also observed in
paints formulated above and below critical PVC.
Superior encapsulation
The inclusion of the new SM in polymer emulsions results in
the pigment particles being better encapsulated by the
emulsion particles. Table 6 shows the calculated amount of
latex adsorbed onto the TiO2 for polymer compositions A
and B - 25% to ca 40% for the SM containing compositions
and 0% to ca 8% for CFM compositions.
Assuming a latex particle size of 130 nm, the amount of
latex needed to completely cover the TiO2 (230 nm)
surfaces, with ca 210 parts by weight TiO2 is calculated to
be about 30%. This suggests that the association of the
latex onto the pigment surfaces was near saturation for the
particles considered here, although the actual distribution of
latex around the pigment is unknown. For example the latex
may not necessarily be arranged in a monolayer, as this
simple calculation might imply.
Adsorption of latex onto the TiO2 surfaces in the wet paint is
consistent with dry-film SEM scans which show the TiO2
was more evenly spaced for the SM based polymer
compared to the CFM polymer. The samples based on the
SM functional polymer show TiO2 particles covered on the
sides and tops with latex particles (Figure 3). That the
coverage of latex particles appears to be less than expected
is probably due to sample preparation procedures.
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Latex particles containing a specialty monomer provided
waterborne coatings with significant improvements in film
gloss, corrosion control, hiding and scrub resistance over
the corresponding CFM containing analogues with no
increase in the total formulation cost. Alternatively,
formulators can, by using lower quantities of binder and
pigment, optimise the formulation cost with no loss in
performance.
References
[1] T. C. Patton, "Paint Flow and Pigment Dispersion", 2nd
Ed., John Wiley and Sons, 1979.
[2] S. J. Paul, "Surface Coatings-Science and Technology",
John Wiley and Sons, 1985.
[3] C. H. Hare, "Protective Coatings - Fundamentals of
Chemistry and Composition", SSPC: The Society for
Protective Coatings, 1998.
[4] G. Larson, L. Procopio and W. Rosano, 2001
Proceedings of the International Waterborne, High Solids
and Powder Coatings Symposium.
[5] I. Piirma, "Emulsion Polymerization", Academic Press,
1982.
[6] R. G. Gilbert, Emulsion Polymerization - A Mechanistic
Approach", academic Press Limited 1995.
[7] L. G .S .Gray and B. Appleman, SSPC 2002 Proceedings.
Results at a glance
- A new binder technology based on a latex-pigment
composite formation results in an optimized dispersion of
the pigment particles in water-based paints.
- The impact of these acrylic-based, latex-polymer binders is
due to a proprietary specialty monomer containing groups
that significantly enhance the interaction between the
polymer and inorganic particles.
- The pigment particles are better encapsulated by the
emulsion particles.
- Significant improvements in many properties are achieved.
- Formulators are able to choose: either get a wide range of
performance improvements with no cost penalty, or optimize
the formulation cost with no loss in performance
- The new binder technology is designed for high quality,
low-VOC, low odour interior wall paints, as well as exterior
applications, thanks for its pure acrylic composition.
The authors:
> William J. Rosano, received a Ph.D. from the Ohio State
University in physical chemistry. He has worked at Rohm
and Haas Company at Spring House Technical Center for
20 years. He works in the development of waterborne
polymers, cross-linking chemistries and additives for the
construction and industrial coatings industries.
> Dr. Marie Bleuzen received her Doctorate in Chemistry
from the University of Poitiers. In November 1991 she joined
Rohm and Haas in their European Laboratories in Sophia
Antipolis, Valbonne in Southern France. In January 2000
she moved to the architectural coatings segment and is
responsible for the development of new binders and
additives for the European market.
> Gary R. Larson earned his BSc in chemistry from Western
Michigan University in 1972 and a MA in chemistry in 1977.
Currently he is working at Rohm and Haas Company at their
Spring House Pennsylvania research laboratory on
waterborne protective coatings for metal and maintenance
coatings.
> Dr. Leo J. Procopio received his Ph.D. in inorganic
chemistry from the University of Pennsylvania. He joined
Rohm and Haas Company at their Spring House, PA
 Quelle/Publication: European Coatings Journal
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Seite/Page: 144

research laboratories in 1991. He is currently a group leader

in the architectural and functional coatings technical service
department at Rohm and Haas.

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 Quelle/Publication: European Coatings Journal
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Figure 1: FE-SEM of dried 18 PVC TiO2 paints cast one on top of the other, based on
composition A using CFM (top half of image) and SM (lower half of image).

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Figure 2: Coating resistance (Rc) as a function of exposure time to a 5% NaCl solution

as derived from EIS spectra of SM (red trace) and CFM (blue trace) based polymers
formulated in white gloss paints.

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Figure 3: FE-SEM (magnification 50,000) of diluted blends of TiO2 and latex particles
based on polymer composition A. The image on the left was based on the
SM-containing latex while the image on the right was based on a CFM-containing latex.
The image on the left shows latex absorbed around the TiO2 particles.

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