US 20170210931A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2017/0210931 A1
Bohling et al. (43) Pub. Date: Jul. 27, 2017
(54) VNYLACETATE BINDERS IN AN Publication Classification
ABOVE-CRITICAL PVC COATINGS
COMPOSITION (51) Int. Cl.
C09D I3/04 (2006.01)
(71) Applicants: Dow Global Technologies LLC, C09D 27/06 (2006.01)
Midland, MI (US); Rohm and Haas (52) U.S. Cl.
Company, Philadelphia, PA (US) CPC ......... C09D 131/04 (2013.01); C09D 127/06
(2013.01)
(72) Inventors: James C. Bohling, Lansdale, PA (US);
Junyu Chen, Shanghai (CN); Edwin
Nungesser, Horsham, PA (US); Zhen (57) ABSTRACT
Qian, Anhui (CN); Tao Wang,
Shanghai (CN)
The present invention is an above-critical coating composi
(21) Appl. No.: 15/329,737 tion comprising an aqueous dispersion of polymer particles,
pigment particles, and extender particles wherein the poly
(22) PCT Filed: Jul. 30, 2014 mer particles comprise from 80 to 99.8 weight percent
structural units of vinyl acetate and from 0.1 to 6 weight
(86) PCT No.: PCT/CN2O14/O83292 percent structural units of a phosphorus acid monomer. The
S 371 (c)(1), composition shows Surprisingly improved hiding with
(2) Date: Jan. 27, 2017 increased particle size of the polymer particles.
US 2017/0210931 A1 Jul. 27, 2017

VINYLACETATE BINDERS IN AN 0006. As used herein, the term “in a single phase' refers
ABOVE-CRITICAL PVC COATINGS to the fact that the polymer particles comprise one or more
COMPOSITION copolymers comprising structural units of vinyl acetate and
the phosphorus acid monomer with the described propor
BACKGROUND OF THE INVENTION tions.
0007 As used herein, the term “extender particles' refer
0001. The present invention relates to a coatings compo to inorganic materials that are used to increase the pigment
sition comprising a stable aqueous dispersion of vinyl Volume concentration of the coating composition. Extender
acetate functionalized polymer particles adsorbed to pig particles are generally distinguished from pigment particles
ment particles in an above-critical pigment Volume concen by their lower index of refraction (typically from 1.3 to 1.6
tration (PVC) paint formulation. as compared to above 2.0 for pigments). Examples of
0002 Coating formulations are complex mixtures of Suitable extenders include, calcium carbonate, clays, alumi
polymers particles (binder), pigments, extenders, and addi num silicates, silica, calcium silicates, mica, talc, and
tives. The pigment of choice in most coatings formulations nephilene syenite.
is TiO, which is effective for creating opacity, but expen 0008. As used herein, the term “structural units” refers to
sive. The expense can be mitigated somewhat by function the remnant of the recited monomer after polymerization.
alizing the binder with phosphate groups to promote adsorp For example, a structural unit of vinyl acetate is as illus
tion of the binder particles to TiO2 particles to form trated:
composites with increased spacing between the pigment
particles, thereby providing a mechanism for reducing the
levels of expensive TiO2 to achieve the same degree of
hiding.
0003) Especially attractive binders for architectural coat
ings are vinyl acetate polymers and copolymers, which are
known to have high Scrub resistance at relatively low cost. structural unit of vinyl acetate
Vinyl acetate polymers functionalized with phosphate
groups are especially desirable as film-forming polymers
due to the cost benefits provided by reduced TiO, usage. where the dotted lines represent the points of attachment of
Cost benefits of vinyl acetate based paints are further the structural unit to the polymer backbone. Preferably, the
realized in above critical PVC paint formulations, which are concentration of structural units of vinyl acetate is from 85,
widely used in spite of their relatively poor performance. It more preferably from 90 weight percent, to preferably 98
would be desirable to improve performance, particularly weight percent based on the weight of the polymer particles.
hiding (opacity), in these above-critical vinyl acetate based 0009 Examples of suitable phosphorus acid monomers
paint formulations economically. include phosphonates and dihydrogen phosphate esters of an
alcohol in which the alcohol contains or is substituted with
SUMMARY OF THE INVENTION a polymerizable vinyl or olefinic group. Preferred dihydro
gen phosphate esters are phosphates of hydroxyalkyl acry
0004. The present invention addresses a need in the art by lates and methacrylates, including phosphoethyl methacry
providing a coating composition comprising an aqueous late and phosphopropyl methacrylate, with phosphoethyl
dispersion of polymer particles, pigment particles, and methacrylate or a salt thereof being especially preferred. A
extender particles wherein the polymer particles comprise, preferred phosphonate is 2-(methacryloyloxy)ethyl phos
in a single phase and based on the weight of the polymer phonic acid or a salt thereof.
particles, from 80 to 99.8 weight percent structural units of (0010) “Phosphoethyl methacrylate” (PEM) is used herein
vinyl acetate and from 0.1 to 6 weight percent structural to refer to the following structure:
units of a phosphorus acid monomer or a salt thereof,
wherein the polymer particles have a particle size by
dynamic light scattering of from 80 nm to 500 nm, and O
wherein the coating composition has an above-critical pig O
ment volume concentration. The present invention addresses O
a need in the art by economically improving hiding in 1N1 N!
above-critical PVC vinyl acetate based paint formulations OH
YOR
without adversely impacting other desirable properties in the
coating.
where R is H or
DETAILED DESCRIPTION OF THE
INVENTION
0005. The present invention is a coating composition
comprising an aqueous dispersion of polymer particles, 1N--
pigment particles, and extender particles wherein the poly
mer particles comprise, in a single phase and based on the
weight of the polymer particles, from 80 to 99.8 weight
percent structural units of vinyl acetate and from 0.1 to 6 where the dotted line represents the point of attachment.
weight percent structural units of a phosphorus acid mono
mer or a salt thereof, wherein the polymer particles have a 0011 A preferred concentration of structural units of the
particle size by dynamic light scattering of from 80 nm to phosphorus acid monomer, preferably PEM, is from 0.2 to
500 nm, and wherein the coating composition has an above 4, more preferably to 2 weight percent, based on the weight
critical pigment Volume concentration. of the polymer particles.
US 2017/0210931 A1 Jul. 27, 2017

0012. The polymer particles preferably comprise 0.1 to 2 5.5; to 8.0, more preferably to 7.5, and most preferably to
weight percent, based on the weight of the polymer particles, 7.2. The pH of the polymerization medium is maintained at
structural units of a Sulfur acid monomer or a salt thereof. such a level to minimize the hydrolysis of the vinyl acetate
Examples of suitable sulfur acid monomers include sulfo monomer or of the polymer, and is preferably buffered
ethyl methacrylate, Sulfopropyl methacrylate, vinyl Sulfonic throughout the polymerization process to maintain a pH in
acid, 2-acrylamido-2-methyl propanesulfonic acid, and the range of from 4.5, more preferably from 5.5; to 8, more
2-methacrylamido-2-methyl propanesulfonic acid, and salts preferably to 7. Because the polymerization reaction is
thereof. Preferred sulfur acid monomers are 2-acrylamido carried out at a pH that does not promote the hydrolysis of
2-methyl propanesulfonic acid and vinyl Sulfonic acid, and vinyl acetate, very low levels of acetic acid or a salt thereof
salts thereof. The polymer particles more preferably com (i.e., the hydrolysis products of vinyl acetate) are formed
prise 0.5 to 1.5 weight percent, based on the weight of the during the polymerization process. Consequently, yields of
polymer particles, structural units of 2-acrylamido-2-methyl useful polymer are improved, VOCs are reduced, and pro
propanesulfonic acid or a salt thereof. duction of a less desirable hydrophilic polymer (due to
generation of pendant OH groups as a consequence of
0013 The polymer particles may also include up to 19.9 hydrolysis) is reduced.
weight percent structural units of one or more acrylate or 0017. In a first step of preparing the composition of the
methacrylate monomers, such as ethyl acrylate, butyl acry present invention the stable aqueous dispersion of the poly
late, 2-ethylhexyl acrylate, methyl methacrylate, or butyl mer particles is contacted with pigment particles, preferably
methacrylate, or combinations thereof. Preferably, the poly an aqueous dispersion of pigment particles (also known as a
mer particles contain less than 10 weight percent structural slurry), more preferably a TiO, slurry, to form the aqueous
units of one or more acrylate monomers, more preferably not dispersion of polymer particles that preferably adsorb to the
more than 5 weight percent, and most preferably no struc Surface of the pigment particles. The aqueous dispersion of
tural units of acrylate monomers. polymer particles is advantageously adjusted to a pH in the
0014. In another embodiment, the polymer particles can range of 8 to 10 before, during, or after contacting the
also include from 0.1, preferably from 0.5 weight percent, to pigment particles, preferably an aqueous dispersion of TiO2
19.9, more preferably to 10, more preferably to 5, and most particles, to form the composite of polymer particles and the
preferably to 3 weight percent structural units of a vinyl ester pigment particles. This combination can then be admixed
of a branched alkyl carboxylic acid (also known as a vinyl with extender particles to form the above critical PVC
versatate), based on the weight of the polymer particles. An composition.
example of a commercially available vinyl versatate is 0018. Furthermore, the stable aqueous dispersion of poly
VA-VeoVa 10 monomer.
0015 The polymer particles preferably adsorb to the mer particles can be combined with extender first and this
surface of the pigment particles. For example, when TiO is mixture can be combined with the pigment particles, pref
erably as an aqueous dispersion. Also, the extender particles
blended with a VA-PEM latex, adsorption can be seen by can be combined with pigment particles, preferably as an
way of Scanning electron microscopy or centrifugation. As aqueous dispersion, which can then be admixed with the
used herein, "adsorb’ refers to polymer particles contacting aqueous dispersion of polymer particles (i.e., the latex).
or attaching to the surface of the TiO, particles in a manner (0019. In above critical PVC paints there is a relatively
other than covalent bonding. Preferably the T of the poly low concentration of opacifying pigment and it is well
mer particles by the Fox equation is at least 25° C. and known that a large proportion of the opacity (or hiding)
preferably not more than 50° C., more preferably not more comes from air voids that are present due to the absence of
than 40°C. Preferably, the polymer particles have a particle adequate film forming binder to encapsulate the entirety of
size by dynamic light scattering of not less than 100 nm, the pigments and extenders present in the formulation.
more preferably not less than 150 nm, more preferably not Optimizing opacity in low pigment content coatings is
less than 250 nm, and most preferably not less than 350 nm especially important to maintaining the low cost advantage
to not greater than 450 nm. of these types of formulations.
0016. The aqueous dispersion of polymer particles is 0020. The term “critical pigment volume concentration'
preferably prepared by forming an at least partially neutral (CPVC) refers to the lowest concentration of polymer
ized solution of the phosphorus acid monomer, then con required to wet the surface of the pigment particles. Below
tacting the solution with vinyl acetate and optionally the CPVC there is an excess amount of polymer relative to the
sulfur acid monomer, or salt thereof and optionally the vinyl amount of pigments and extenders. As such, at PVCs at or
ester of the alkyl carboxylic acid under emulsion polymer below CPVC, an adequate relative amount of binder volume
ization conditions. As used herein, the term “at least partially to pigment/extender Volume is present, leading to a Substan
neutralized phosphorus acid monomer refers to an aqueous tially nonporous dry coating.
Solution of a phosphorus acid monomer containing not less
than /2 the molar amount of neutralizing agent required to 0021. Above CPVC, the volume of binder is insufficient
neutralize the monomer, up to the amount required to to coat all pigment and extender to form a porous dry
completely neutralized the monomer, preferably up to the coating, resulting in a deterioration of the properties and
amount required to reach a pH equal to the highest pK, performance of the consequent coating. For example, abra
(preferably the second pK) of the monomer. For example, sion resistance and stain resistance and removal are Superior
if the neutralizing agent is ammonia, and the phosphorus for coatings at or below CPVC as compared to coatings
acid monomer is PEM, the suitable molar ratio of ammonia above CPVC. Nevertheless, the cost advantages of above
to PEM would be at least 1:1 and preferably up to 2:1. CPVC paints sometimes outweigh the disadvantages of
Suitable neutralizing agents include, for example, ammonia, diminished properties.
KOH, NaOH, ethanolamine, and aminomethyl propanol. It 0022. The CPVC of a coating can be conveniently deter
is preferred that pH of the aqueous solution of the phospho mined using reflectance (integrated sphere, spectral reflec
rus acid monomer, prior to contact with the vinyl acetate and tance included, 10 degree observer/D65), as follows: The
optionally one or more additional monomers, be in the range difference in reflectance of a coated film in the dry state is
of from 4.5, more preferably from 5.0, most preferably from compared to the same film that has been rewetted with a
US 2017/0210931 A1 Jul. 27, 2017

penetrating solvent that has refractive index similar to that of Solution and IAA Solution additions were complete a redox
the polymer (such as Isopar L. solvent) that fills the air voids pair was added to reduce residual monomers. The reaction
of the dry coating. When a coating is above CPVC, the was maintained at 72.5° C. for the duration of the entire
Y-reflectance of the re-wetted coating will decrease by at reaction (4 h total), after which time the latex was cooled to
least 2% from the initial Y-reflectance value of the dry and a biocide added. The pH of the final latex was adjusted
coating. Preferably, the above-critical PVC is at least 60, to 6.3 with aq. NH. Water was added to adjust to the listed
more preferably at least 65, and preferably not greater than Solids.
90.
0023. It has surprisingly been discovered that hiding is EXAMPLE 1.
improved in above-critical paint formulations with an Preparation of VA/PEM/AMPS Latex
increase in binder particle size; in contrast, for below-critical
paint formulations, the relationship between particle size 0025. Example 1 was prepared substantially as described
and hiding is inverse: higher particle sizes result in reduced for Comparative Example 1 except that 104 g of polymer
hiding. seed (32.85% in water, 41 nm PS) was used and the
monomer emulsion was prepared by first mixing DI water
(370 g) and PEM (8.5 g) in a vessel and adjusting the pH to
Abbreviations 6.8 with NaOH (5.3 g). FES-77 (27.4 g), 15-S-40 (49.9 g),
Abbreviation Chemical name or description (%’s in water are indicated) 15-S-9 (17.1) and DS-4 (32.6 g) were then added followed
by Na-AMPS (19.1 g) and VA (1687 g).
FES-32 Disponil FES-32 fatty ether sulfate (30% aq)
PEM Phosphoethyl methacrylate, 60% active EXAMPLE 2
NaPS Sodium persulfate
FES-77 Disponil FES-77 fatty ether sulfate (33% aq)
5-S-40: TERGITOLTM Secondary Alcohol Ethoxylate (70% aq) Preparation of VA/VeoVa/AMPS/PEM
TMN-10 TERGITOLTM TMN-10
DS-4 Rhodacal DS-4 sodium dodecylbenzene sulfonate (22% aq) 0026. Example 2 was prepared substantially as described
Na-AMPS Sodium 2-acrylamido-2-methyl-1-propanesulfonate for Comparative Example 1 except that 104 g of polymer
(50% aq) seed (32.85% in water, 41 nm PS) was used and the mono
BA Butyl acrylate
VA Vinyl acetate mer emulsion was prepared by first mixing DI water (369 g)
AA Soascorbic acid and PEM (34.1 g) in a vessel and adjusting the pH to 6.8
-BHP -Butyl hydroperoxide with NaOH (16.7 g). FES-77 (27.4 g), 15-S-40 (49.9 g),
PS
TiO, slurry
Particle Size
Ti-Pure R-746 TiO, slurry
15-S-9 (17.1) and DS-4 (32.6 g) were then added followed
Natrosol Natrosol 250 MHR by Na-AMPS (19.1 g), VeoVa 10 monomer (43.6 g) and VA
Natrosol soln Natrosol 250 MHR (3% in water) (1687 g).
CF-10* TRITONTM CF-10 Surfactant
Foamaster Foamaster VL Defoamer EXAMPLE 3
Texanol Texanol Coalescent
TiO, PVC TiO2 Pigment Volume Concentration in the Paint Preparation of VA/PEM/AMPS Latex
731A TAMOLTM 731A Dispersant
*TAMOL, CELLOSIZE, and TERTIGOL are Trademarks of The Dow Chemical Company 0027. Example 3 was prepared substantially as described
or its Affiliates. for Comparative Example 1 except that 104 g of polymer
seed (32.85% in water, 41 nm PS) was used and the
COMPARATIVE EXAMPLE 1. monomer emulsion was prepared by first mixing DI water
(370 g) and PEM (34.1 g) in a vessel and adjusting the pH
to 6.8 with NaOH (50% aq, 16.9 g). FES-77 (27.4 g),
Preparation of BA/VA/PEM/AMPS Latex 15-S-40 (49.9 g), 15-S-9 (17.1) and DS-4 (32.6 g) were then
0024 Deionized (DI) water (654 g) was added to a 5-L added followed by Na-AMPS (19.1 g) and VA (1661 g).
4-necked round bottom flask equipped with a mechanical 0028. The particle sizes (determined using a Brookhaven
stirrer, nitrogen gas blanket, thermometer, condenser, heat BI90 particle size analyzer) and T (calculated using the Fox
ing mantel and temperature controller and heated to 71° C. equation) of the latex binder compositions are shown in
Table 1.
under nitrogen atmosphere. Next, Cu(NO) (1% aq, 0.85g)
and 51.9 g of seed polymer (32.85% in water, 41 nm) were TABLE 1.
added to the reactor. The monomer emulsion was prepared
by first mixing DI water (335.9 g) and PEM (8.5 g) in a VA/BA/PEM Latex Compositions
vessel and adjusting the pH to 6.8 with NaOH (50% aq, 5.3
g). FES-77 (27.4 g), 15-S-40 (49.9 g), 15-S-9 (17.1 g) and Binder EX. Binder Monomer Composition PS (nm) T (C.)
DS-4 (32.6 g) were then added followed by BA (570 g), VA Comp 1 VA/BA/AMPS/PEM 2O7 -4.9
(1117 g) and Na-AMPS (19.2 g). An initiator solution was 65.33.9.0.6.O.S
prepared separately by mixing DI water (58 g), t-BHP (1.5 1 WABAAMPSPEM 174 29.7
g) and NaPS (2.3 g). A separate solution of DI water (50 g), 98.9, O.O.6.O.S
2 VAWeova-10, AMPSPEM 291 29.6
NaOH (50% aq, 1.0 g) and IAA (2.3 g) was prepared. Flow 9.S.S. 2.5,0.6.2.O
of the monomer emulsion as well as the NaPS/tBHP and 3 WABAAMPSPEM 434 3O.S
IAA solutions to the reactor flask were started at the same
time. The monomer emulsion was added over 120 min while
a - % PEM is uncorrected for active amount, which is ~60% of the reported percentage
the tEBHP/NaPS solution and the IAA Solution were added
over 155 minutes. After the monomer emulsion, initiator
US 2017/0210931 A1 Jul. 27, 2017

Above-Critical PVC Paint Formulations TABLE 3

0029. An above critical PVC paint (60.6 PVC (total) was Above-Critical Paint Formulation 2 (70.0 PVC)
prepared using the following procedure: Part A

0030 Binder emulsion was added to a paint container and Binder Emulsion Sufficient to obtain 30% vol based on total
mixed using a 3-blade pitched metal stirrer, aqueous ammo dry vol of binder, pigment, and extender
nia (28% aq) was added to neutralize the binder to a pH of NH (28% aq) Quantity to achieve pH of 8-9
TiO2 slurry 72.8 g.
8-9. After the addition of the base was complete, TiO, and CF-10 0.5 g.
Defoamer were added sequentially to the emulsion. In a Foamaster 0.5 g.
separate container the mill based (part B) was prepared on Mill base part B 9.
a Cowles disperser. After preparation, the mill based was Natrosol 3.35 g
added to part A while mixing. Finally, Part C was added in Water 186.0 g
order to the mixture of Part A and Part B while mixing. CF-10 0.91 g
Foamaster 0.91 g
Adequate level of thickener was added until a Krebs Unit NH (28% aq) 0.09 g
viscosity of 90-100 was obtained. 731A 11.02 g
Omyacarb 5 extender 101.92 g
Minex 10 extender 54.36 g
Method for Reflectance Measurement Optiwhite extender 54.36 g
Grind Sub-total 412.45 g
0031. Both dry coating samples and Iso-Par L re-wetted Part C
coating samples were measured for Y-reflectance using a
Xrite USA model Xrite&400, XriteColor Master CM-2 using Texanol () 10% based on binder T,
the spectral component included mode and under D65/10 Natrosol Soln sufficient to achieve 90-100 KU viscosity
Water sufficient to achieve 33.3% volume solids
observer conditions. The Iso-par L oil was applied to the dry
coating using a 1-inch nylon paint brush and allowed to
penetrate for 5 min prior to making reflectance measure Kubelka-Munk S/Mil Test Method
ments. Table 2 shows the ingredients and amounts used to 0033. The paints were evaluated for hiding using the in
make Paint Formulation 1.
accordance with the Kubelka-Munk S/mil test method, as
TABLE 2
described in the following procedure.
0034) Four draw-downs were prepared on Black Release
Above-Critical Paint Formulation 1 (60.6 PVC) Charts (Leneta Form RC-BC) for each paint using a 1.5-mil
Bird draw down bar and the charts allowed to dry overnight.
Part A Using a template, 3.25"x4" rectangles were cut out on each
chart. The Y-reflectance was measured using a X-Rite Color
Binder Emulsion Sufficient to obtain 39.4% by vol based on i7 Spectrophotometer in each of the scribed areas five times
total dry Vol of binder, pigment, and extender and the average Y-reflectance recorded. A thick film draw
NH (28% aq) Sufficient achieve pH of 8-9 down was prepared for each paint on the Black Release
TiO2 slurry 76.0 g Charts using a 3" 25 mill block draw down bar and the charts
CF-10 0.52g
Foamaster 0.52g were allowed to dry overnight. The Y-reflectance was mea
Mill base part B 9. sured in five different areas of the draw down and the
average Y-reflectance recorded. Kubelka-Munkhiding value
Natrosol 2.95 g S is given by Equation 1:
Water 164.2 g
CF-10 0.80 g
Foamaster 0.80 g R 1 - (RRX R). Equation 1
S = -- XIn-
NH (28% aq) 0.08 g XX (1 - R2) 1 RB
731A 9.73 g R
Omyacarb 5 extender 90.00 g
Minex 10 extender 48.00 g
Optiwhite extender 48.00 g where X is the average film thickness, R is the average
reflectance of the thick film and R is the average reflectance
Grind Sub-total 364.60 g over black of the thin film. X can be calculated from the
Part C
weight of the paint film (W), the density (D) of the dry
Texanol 10% based on binder T,
film; and the film area (A). Film area for a 3.25"x4" template
was 13 in.
Natrosol Soln sufficient to achieve 90-100 KU viscosity
Water sufficient to achieve 34.8% volume solids

X (mils) = -
W(g)x 1000(millin) --
D(Ibs/gal) x 1.964(g/in/Ibs/gal)x A(in)
0032. A second above critical PVC paint (Paint Formu
lation 2, 70.0 PVC (total) was prepared using the procedure
substantially described to make Paint Formulation 1. Table I0035) Table 4 shows the effect of particle size and T on
3 shows the ingredients and amounts used to make Paint hiding for the 60.6 PVC and 70 PVC paint formulations
Formulation 2. (Paint Formulation 1 and Paint Formulation 2 respectively).
US 2017/0210931 A1 Jul. 27, 2017

TABLE 4 from 25°C. to 40°C., wherein the polymer particles have a

particle size by dynamic light scattering of from 350 nm to
Hiding Data for Above-Critical PVC Paint Formulations 1 and 2 450 nm.
Binder Example No. Comp. 1 1 2 3 7. The coating composition of claim 1 wherein the PVC
PS (nm) 2O7 174 291 434
of the composition is from 60 to 90.
T (C.) -4.9 29.7 29.6 3O.S 1. A coating composition comprising an aqueous disper
Dry S/mil Formulation 1 5.59 5.93 6.04 6.62 sion of polymer particles, pigment particles, and extender
stol deviation O.O2 O.OS O.O1 O.04 particles wherein the polymer particles comprise, in a single
Dry S/mil Formulation 2 6.95 7.44 7.61 7.99 phase and based on the weight of the polymer particles, from
stol deviation O.O1 O.OS O.13 O.OS
80 to 99.8 weight percent structural units of vinyl acetate
and from 0.1 to 6 weight percent structural units of a
10036) As the data show, the effect of T on hiding is phosphorus acid monomer or a salt thereof, wherein the
dramatic for the above-critical paint formulations. Hiding polymer particles have a particle size by dynamic light
increases as particle size increases from 174 nm to 434 nm. scattering of from 80 nm to 500 nm, and wherein the coating
1. A coating composition comprising an aqueous disper composition has an above-critical pigment volume concen
sion of polymer particles, pigment particles, and extender tration.
particles wherein the polymer particles comprise, in a single 2. The coating composition of claim 1 wherein the particle
phase and based on the weight of the polymer particles, from polymers comprise, based on the weight of the polymer
80 to 99.8 weight percent structural units of vinyl acetate particles, from 85 to 98 weight percent structural units of
and from 0.1 to 6 weight percent structural units of a vinyl acetate and from 0.2 to 2 weight percent of a phos
phosphorus acid monomer or a salt thereof, wherein the phorus acid monomer or a salt thereof.
polymer particles have a particle size by dynamic light
scattering of from 80 nm to 500 nm, and wherein the coating 3. The coating composition of either of claims 1 or 2
composition has an above-critical pigment volume concen wherein the polymer particles have a particle size by
tration. dynamic light scattering of from 150 nm to 450 nm, wherein
2. The coating composition of claim 1 wherein the particle the phosphorus acid monomer is phosphoethyl methacrylate
polymers comprise, based on the weight of the polymer or a salt thereof.
particles, from 85 to 98 weight percent structural units of 4. The coating composition of claim 3 wherein the
vinyl acetate and from 0.2 to 2 weight percent of a phos wherein the particle polymers comprise, from 90 to 98
phorus acid monomer or a salt thereof. weight percent structural units of vinyl acetate and from 0.2
3. The coating composition of claim 2 wherein the poly to 2 weight percent structural units of phosphoethyl meth
mer particles have a particle size by dynamic light scattering acrylate or a salt thereof, based on the weight of the polymer
of from 150 nm to 450 nm, wherein the phosphorus acid particles, and wherein the polymer particles further com
monomer is phosphoethyl methacrylate or a salt thereof. prise from 0.2 to 1.5 weight percent structural units of a
4. The coating composition of claim 3 wherein the sulfur acid monomer or a salt thereof, wherein the polymer
wherein the particle polymers comprise, from 90 to 98 particles have a particle size by dynamic light scattering of
weight percent structural units of vinyl acetate and from 0.2 from 250 nm to 450 nm.
to 2 weight percent structural units of phosphoethyl meth 5. The coating composition of claim 4 which further
acrylate or a salt thereof, based on the weight of the polymer comprises from 0.5 to 5 weight percent of structural units of
particles, and wherein the polymer particles further com a vinyl versatate.
prise from 0.2 to 1.5 weight percent structural units of a 6. The coating composition of any of claims 1 to 5
sulfur acid monomer or a salt thereof, wherein the polymer wherein the polymer particles have a T as calculated by the
particles have a particle size by dynamic light scattering of Fox equation of from 25°C. to 40°C., wherein the polymer
from 250 nm to 450 nm. particles have a particle size by dynamic light scattering of
5. The coating composition of claim 4 which further from 350 nm to 450 nm.
comprises from 0.5 to 5 weight percent of structural units of 7. The coating composition of any of claims 1 to 6
a vinyl versatate. wherein the PVC of the composition is from 60 to 90.
6. The coating composition of claim 1 wherein the poly
mer particles have a T as calculated by the Fox equation of k k k k k