USOO871 0133B2

(12) United States Patent (10) Patent No.: US 8,710,133 B2

Bohling et al. (45) Date of Patent: Apr. 29, 2014
(54) STABLE AOUEOUS COMPOSITE 7,285,590 B2 10/2007 Holub et al.
COMPOSITIONS 2003/0018103 A1 1/2003 Bardman et al.
2004/OO54063 A1 3/2004 Brown et al.
(75) Inventors: James Charles Bohling, Lansdale, PA 2005/0222299 A1 10, 2005 Garzon et al.
(US); John William Hook, III 2007/0021536 A1 1/2007 Pressley et al.
Warminster. PA (US); Melinda H 2008/0146724 A1 6/2008 Bohling et al.
s 2009/0326135 A1 12/2009 Nair et al.
Keefe, Willow Grove, PA (US); Arthur
Grigorievich Kravchenko, Philadelphia, 2010, 0120945 A1 5/2010 Sahlberg et al.
PA (US); Jeffrey J. Moretti, FOREIGN PATENT DOCUMENTS
Bordentown, NJ (US); Judith Niece
Varner, Lansdale, PA (US) EP 0625541 A2 11/1994
EP 2166044 A1 3, 2010
(73) Assignees: Rohm and Haas Company, JP 7O70505. A 3, 1995
Philadelphia, PA (US); Dow Global JP 2007023.279 A 2, 2007
Technologies LLC. Midland, MI (US)
OTHER PUBLICATIONS
(*) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 Conversion between Stormer Viscometer Krebs Units and Viscosity
U.S.C. 154(b) by 258 days. Cup Drain Time, by Gardco Paul N. Gardner Company, Inc. down
loaded from http://www.gardco.com/stormer krebs.conv PU
(21) Appl. No.: 13/218,977 G271.pdf on Jul. 30, 2013 (p. 3 of 4).*
1-1. Partial European Search Report issued in EP 11 177866, dated Jan.
(22) Filed: Aug. 26, 2011 9, 2012.
(65) Prior Publication Data * cited by examiner
US 2012/OO58278 A1 Mar. 8, 2012
Related U.S. Application Data Primary Examiner — Vu A Nguyen
(60) Provisional application No. 61/402.770, filed on Sep. (74) Attorney, Agent, or Firm — Ronald D. Bakule; Karl E.
3, 2010. Stauss
(51) Int. Cl.
BOIF 3/12 (2006.01) (57) ABSTRACT
CSK 3/22 (2006.01)
(52) U.S. Cl This invention provides a method for forming a stable aque
USPG 524/431,524/547 ous composition including composite particles by admixing
(58) Field of Classification search- - - - - - s TiO2 particles and adsorbing emulsion polymer particles at or
USPC 524/431, 547:523/205 below the critical composite ratio to an equilibrated viscosity
See application file for complete search history range of from 200 cps to 4000 cps. Also provided is a method
for forming a stable aqueous composition including compos
(56) References Cited ite particles by admixing TiO2 particles and adsorbing emul
sion polymer particles at a mixing intensity of greater than 2
U.S. PATENT DOCUMENTS hp/kgal. A method for providing a coating including compos
5,385,960 A 1/1995 Emmons et al. ite particles is also included.
6,080,802 A 6/2000 Emmons et al.
6,492.451 B1 12/2002 Dersch et al.
7,179,531 B2 2/2007 Brown et al. 6 Claims, No Drawings
 US 8,710,133 B2
1. 2
STABLE AOUEOUS COMPOSITE TiO2 may have a uniform composition or a heterogeneous
COMPOSITIONS composition with two or more phases. Typically, TiO2 can
have at least one coating of one or more of silica, alumina,
This invention relates to a method for preparing a stable Zinc oxide, and zirconia. We have found that specific types of
aqueous composition including composite particles by TiO2 require different levels of adsorbing monomer (P-acid
admixing TiO2 particles and adsorbing emulsion polymer monomer) in the emulsion polymer. For example, we have
particles at or below the critical composite ratio to an equili found that a TiO2 grade with a relatively high ratio of Al:Si
brated viscosity range of from 200 cps to 4000 cps. The requires adsorbing emulsion polymer incorporating much
invention also relates to a method for forming a stable aque less copolymerized adsorbing monomer than a TiO2 grade
ous composition including composite particles including: 10
with a lower Al:Siratio.
admixing TiO2 particles and adsorbing emulsion polymer The adsorbing emulsion polymer particles typically
particles at a mixing intensity of greater than 2 hp/kgal. A
method for providing a coating is also provided. include, as copolymerized units, at least one monomer
Titanium dioxide (TiO2) is an expensive component of including an adsorbing group selected from phosphorus acid
many paints. The efficacy of the TiO2 as a hiding pigment is 15 groups, phosphorous acid full ester groups, and polyacid
reduced when TiO2 particles are allowed to come too close sidechain groups; and salts thereof. The adsorbing emulsion
together on film formation and drying. It has been disclosed polymer particles typically include, as copolymerized units,
that the spacing of TiO2 and its resultant efficiency can be from 0.5 to 5%, preferably from 1 to 4%, more preferably
improved and enforced by employing an adsorbing emulsion from 1% to 2.5%, by weight based on emulsion polymer
polymer. A composite particle having a central TiO2 particle weight, monomer selected from the group consisting of Phos
bearing a plurality of adsorbed emulsion polymer particles phorous acid monomers, Phosphorus acid full-ester mono
engenders more efficient use of TiO2 as a hiding pigment. mers, acid macromonomers; and salts thereof, and at least one
U.S. Pat. No. 7,179,531 discloses polymer particles having second monoethylenically unsaturated monomer.
select functional or absorbing groups useful for preparing By Phosphorous acid monomer (“P-acid monomer'),
organic-inorganic composite particles that are Suitable for 25 herein is meant a phosphorus-containing acid monomer, the
providing dried coatings with improved hiding. The stability monomer containing at least one ethylenic unsaturation and a
of aqueous compositions comprising composite particles is phosphorus acid group. The phosphorus acid monomer may
subject to improvement. We have found that admixing TiO2 be in the acid form or as a salt of the phosphorus acid groups.
particles and adsorbing emulsion polymer particles at or Examples of phosphorus acid monomers include:
below the critical composite ratio to an equilibrated viscosity 30
range of from 200 cps to 4000 cps provides a desired level of O O
stability. We have also found that admixingTiO2 particles and
adsorbing emulsion polymer particles at a mixing intensity of RO-P-OH RO-P-OH
greater than 2 hp/kgal. provides a desired level of stability.
In a first aspect of the present invention, there is provided a 35 OR H
O O O O
method for preparing a stable aqueous composition compris
ing composite particles comprising: admixingTiO2 particles
and adsorbing emulsion polymer particles at or below the OR OR" OR H
critical composite ratio to an equilibrated viscosity range of O
from 200 cps to 4000 cps. 40
In a second aspect of the present invention there is provided
a method for forming a stable aqueous composition compris R
ing composite particles comprising: admixingTiO2 particles
and adsorbing emulsion polymer particles at a mixing inten
sity of greater than 2 hp/kgal. 45 wherein R is an organic group containing an acryloxy, meth
In a third aspect of the present invention, there is provided acryloxy, or a vinyl group; and R' and R" are independently
a method for forming a coating comprising (a) forming said selected from H and a second organic group. The second
aqueous composition of the first or second aspects of the organic group may be saturated or unsaturated. Suitable phos
present invention; (b) applying said aqueous composition to a phorus acid monomers include dihydrogen phosphate-func
Substrate; and (c) drying, or allowing to dry, said applied 50 tional monomers such as dihydrogen phosphate esters of an
aqueous composition. alcohol in which the alcohol also contains a polymerizable
The first and second aspects of the present invention are vinyl or olefinic group, such as allyl phosphate, mono- or
directed to a method for preparing a stable aqueous compo diphosphate of bis(hydroxy-methyl) fumarate or itaconate,
sition including composite particles. By “aqueous' herein is derivatives of (meth)acrylic acid esters, such as, for examples
meant water and from 0% to 30%, by wt.based on the weight 55 phosphates of hydroxyalkyl(meth)acrylates including 2-hy
of the medium, of water-miscible compound(s). By “stable droxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acry
aqueous composition herein is meant that the aqueous com lates, and the like. Other suitable phosphorous acid mono
position has less than 1000 ppm of grit, preferably less than mers include CH2=C(R) C(O) O-(R1O) P(O)
500 ppm of grit, and more preferably less than 250 ppm of (OH), where R—H or CH3 and R1=alkyl, such as the meth
grit. 60 acrylates SIPOMERTM PAM-100, SIPOMERTM PAM-200,
“Composite particles” as defined herein each include a and SIPOMERTM PAM-400 and the acrylate, SIPOMERTM
central TiO2 particle having a plurality of emulsion polymer PAM-300, available from Rhodia, Inc. Other suitable phos
particles adsorbed on the surface of the TiO2 particle. The phorus acid monomers are phosphonate functional mono
composite particles herein are formed by admixing TiO2 mers, disclosed in WO99/25780 A1, and include vinyl phos
particles and adsorbing emulsion polymer particles. By 65 phonic acid, allyl phosphonic acid, 2-acrylamido-2-
“TiO2 particle' herein is meant aparticle composed predomi methylpropanephosphonic acid, C-phosphonostyrene,
nantly of TiO2, including rutile TiO2 and anatase TiO2. The 2-methylacrylamido-2-methylpropanephosphonic acid. Fur
 US 8,710,133 B2
3 4
ther Suitable phosphorus functional monomers are 1.2-ethyl maleic acid, monomethyl itaconate, monomethyl fumarate,
enically unsaturated (hydroxy)phosphinylalkyl (meth)acry monobutyl fumarate, and maleic anhydride; and Sulfur-con
late monomers, disclosed in U.S. Pat. No. 4,733,005, and taining acid monomers. Preferred second acid-containing
include (hydroxy)phosphinylmethyl methacrylate. Preferred monomers are (meth)acrylic acid and styrene Sulfonic acid.
phosphorus acid monomers are dihydrogen phosphate mono 5 In certain embodiments of the invention the adsorbing
mers, which include 2-phosphoethyl (meth)acrylate, 2-phos emulsion polymer further includes, as copolymerized units,
phopropyl (meth)acrylate, 3-phosphopropyl (meth)acrylate, from 0.01% to 3%, preferably from 0.1% to 2%, by weight
and 3-phospho-2-hydroxypropyl (meth)acrylate. Preferred based on the weight of the adsorbing emulsion polymer,
are 2-phosphoethyl (meth)acrylate, 2-phosphopropyl (meth) aldehyde-reactive group-containing monomer. By 'alde
acrylate, 3-phosphopropyl (meth)acrylate, 3-phospho-2-hy 10
hyde-reactive group-containing monomer is meant herein a
droxypropyl (meth)acrylate, SIPOMERTM PAM-100, and monomer which, in a homogeneous Solution containing 20%
SIPOMERTM PAM-200.
The adsorbing emulsion polymer particle can include a by weight of the monomer and an equimolar amount of form
phosphorus acid full-ester group that is incorporated into the aldehyde at any pH from 1 to 14, will exhibit greater than 10%
adsorbing emulsion polymer by polymerization of the phos 15 extent of reaction between the monomer and formaldehyde
phorus acid full-ester monomer. on a molar basis in one day at 25°C. Included as ethylenically
The adsorbing emulsion polymer particle can include poly unsaturated aldehyde reactive group-containing monomers
acid sidechain groups that are incorporated into the polymer are, for example, vinyl acetoacetate, acetoacetoxyethyl
by polymerization of an acid macromonomer. As used herein, (meth)acrylate, acetoacetoxypropyl (meth)acrylate, allyl
acid macromonomer refers to an oligomer with a terminal acetoacetate, vinyl acetoacetamide, acetoacetoxyethyl
unsaturation and having monomers with acid groups as poly (meth) acrylamide, 3-(2-vinyloxyethylamino)-propiona
merized units. Suitable acid groups include carboxylic acids mide, N-(2-(meth) acryloxyethyl)-morpholinone-2.2-me
and phosphorus acids. The terminal unsaturation and the sec thyl-1-vinyl-2-imidazoline, 2-phenyl-1-vinyl-2-imidazoline,
tion of the acid macromonomer with the acid groups are 2-(3-oxazolidinyl)ethyl (meth)acrylate, N-(2-vinoxyethyl)-
attached directly or alternatively, attached through a linker 25
2-methyloxazolidine, 4.4-dimethyl-2-isopropenyloxazoline,
group. Various conventional polymerization methods are dimethylaminoethyl (meth)acrylate, 2-methyl-5-vinyl-pyri
Suitable for preparing the acid macromonomers including dine, 2-Vinoxyethylamine, 2-Vinoxyethylethylene-diamine,
anionic polymerization as disclosed in U.S. Pat. No. 4,158, 3-aminopropyl vinyl ether, 2-amino-2-methylpropyl vinyl
736; radical polymerization with chain transfer agents such as ether, 2-aminobutyl vinyl ether, tert-butylaminoethyl (meth)
cobalt complexes as described in U.S. Pat. No. 5,324.879; 30
acrylate, 2-(meth)acryloxyethyldimethyl-3-propiobetaine,
catalytic chain transfer polymerization with terminally unsat diethanolamine monovinyl ether, o-aniline vinyl thioether,
urated acid macromonomers used as chain transfer agents as (meth)acryloxyacetamido-ethylethyleneurea, ethyleneurei
described in U.S. Pat. No. 5.362,826; and high temperature doethyl (meth) acrylate, (meth)acrylamidoethyl-ethyl
radical polymerization as described in U.S. Pat. No. 5,710, eneurea, (meth)acrylamidoethyl-ethylenethiourea,
227. 35
N-((meth)acrylamidoethyl)-N-(1-hydroxymethyl)ethyl
The at least one copolymerized second ethylenically unsat eneurea, N-((meth)acrylamidoethyl)-N-(1-methoxy)methyl
urated monomer excludes acid group containing monomers ethyleneurea, N-formamidoethyl-N-(1-vinyl)ethyleneurea,
Such as, for example, P-acid monomer and acid macromono N-vinyl-N-(1-aminoethyl)-ethyleneurea, N-(ethyleneureido
mers and includes, for example, a (meth)acrylic ester mono ethyl)-4-pentenamide, N-(ethylenethioureido-ethyl)-10-un
mer including methyl (meth)acrylate, ethyl (meth)acrylate, 40 decenamide, butyl ethyleneureido-ethyl fumarate, methyl
butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl ethyleneureido-ethyl fumarate, benzyl N-(ethyleneureido
(meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl ethyl)fumarate, benzyl N-(ethyleneureido-ethyl)maleamate,
(meth)acrylate, ureido-functional (meth)acrylates and N-Vinoxyethylethylene-urea, N-(ethyleneureidoethyl)-cro
acetoacetates, acetamides or cyanoacetates of (meth)acrylic tonamide, ureidopentyl vinyl ether, 2-ureidoethyl (meth)
acid; styrene or Substituted Styrenes; vinyl toluene; butadi 45
acrylate, 2-(3-methylolimidazolidone-2-yl-1) ethyl acrylate,
ene; vinyl acetate or other vinyl esters; vinyl monomers such N-acryloxyalkyl oxazolidines, acylamidoalkyl vinyl alkyle
as vinyl chloride, vinylidene chloride, N-vinyl pyrollidone: neureas, dimethyaminoethyl methacrylate, and ethylenically
(meth)acrylonitrile; and N-alkylol (meth)acrylamide. unsaturated monomers containing aziridene functionality.
Optional multiethylenically unsaturated monomers include, Preferred is 0.25% to 2%, by weight based on adsorbing
for example, allyl (meth)acrylate, diallyl phthalate, butadi 50 emulsion polymer weight, of a copolymerizedureido meth
ene, 1,4-butylene glycol di(meth)acrylate, 1.2-ethylene gly acrylate.
col di(meth)acrylate, 1.6-hexanediol di(meth)acrylate, and The calculated glass transition temperature (“Tg) of the
divinyl benzene. The use of the term “(meth) followed by adsorbing emulsion polymer is typically from -20°C. to 50°
another term Such as (meth)acrylate or (meth)acrylamide, as C., or in the alternative, from -10° C. to 20° C. Tgs of the
used throughout the disclosure, refers to both acrylates or 55 polymers are calculated herein by using the Fox equation (T.
acrylamides and methacrylates and methacrylamides, respec G. Fox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, page
tively. 123 (1956)), that is, for calculating the Tg of a copolymer of
In certain embodiments of the invention the adsorbing monomers M1 and M2,
emulsion polymer further includes, as copolymerized units,
from 0.05% to 2%, preferably from 0.1% to 1%, and more 60
preferably from 0.1% to 0.6%, by weight, based on the weight wherein
of said emulsion polymer, second acid-containing monomer. Tg(calc.) is the glass transition temperature calculated for the
The secondacid-containing monomer excludes P-acid mono copolymer
mer, but includes S-acid monomers and carboxylic acid w(M1) is the weight fraction of monomer M1 in the copoly
monomers. Second acid-containing monomers include car 65 C
boxylic acid monomers such as, for example, acrylic acid, w(M2) is the weight fraction of monomer M2 in the copoly
methacrylic acid, crotonic acid, itaconic acid, fumaric acid, C
 US 8,710,133 B2
5 6
Tg(M1) is the glass transition temperature of the homopoly to 115 nm, as measured by a Brookhaven Model BI-90 Par
mer of M1 ticle Sizer supplied by Brookhaven Instrument Corp., Holts
Tg(M2) is the glass transition temperature of the homopoly ville, N.Y.
mer of M2, all temperatures being in K. The formation of the composite particle is carried out by
The glass transition temperature of homopolymers may be contacting dispersed TiO2 with the adsorbing emulsion poly
found, for example, in “Polymer Handbook’, edited by J. mer, typically with conventional low shear mixers. However,
Brandrup and E. H. Immergut, Interscience Publishers. higher mixing intensity mixing may be employed in certain
The adsorbing emulsion polymer is a polymer formed by embodiments of this invention. A balance of reactivity
emulsion polymerization in an aqueous medium. The emul between the TiO2 and latex is desired; if the reaction is too
sion polymerization techniques typically used in the method 10 rapid then paint make-ability will suffer and undesired grit
for forming the multistage emulsion polymer of the present will be formed. Alternately, if the reaction is too weak either
invention are well known in the art. Conventional surfactants no adsorption will take place or it will be slow, resulting in
may be used such as, for example, anionic and/or nonionic drifting viscosity and tint strength.
emulsifiers such as, for example, alkali metal or ammonium The formation of the composite particles in the method of
alkyl Sulfates, alkyl Sulfonic acids, fatty acids, phosphate 15 the first aspect of this invention is effected at or below the
Surfactants, and oxyethylated alkyl phenols. The amount of critical composite ratio. The critical composite ratio is
surfactant used is usually 0.1% to 6% by weight, based on the believed to be the effective saturation level of absorbing poly
weight of total monomer. Either thermal or redox initiation mer particles on the surface of the TiO2 particles. Below the
processes may be used. Conventional free radical initiators, critical composite ratio the surface of the TiO2 particles is
also referred to as catalysts, may be used such as, for example, effectively at the saturation leveland there is excess absorbing
hydrogen peroxide, t-butyl hydroperoxide, t-amyl hydroper latex in the continuous phase. Above the critical composite
oxide, ammonium and/or alkali persulfates, typically at a ratio portions of the TiO2 surface is exposed and the viscosity
level of 0.01% to 3.0% by weight, based on the weight of total of the mixture may rise exponentially with time, believed due
monomer. Redox systems using the same initiators coupled to bridge flocculation. Bridge flocculation is defined as bridg
with a suitable reductant, also referred to as an activator, Such 25 ing of two discrete TiO2 particles with one absorbing polymer
as, for example, sodium Sulfoxylate formaldehyde, sodium particle. The “critical composite ratio’ herein is that mea
hydrosulfite, isoascorbic acid, hydroxylamine Sulfate and sured by the method provided in the Experimental methods
sodium bisulfite may be used at similar levels, optionally in section.
combination with metal ions such as, for example iron and In the method of the first aspect of the present invention the
copper, optionally further including complexing agents for 30 stable aqueous composition is prepared at an equilibrated
the metal. Chain transfer agents such as mercaptains may be viscosity range of from 200 cps to 4000 cps, preferably from
used to lower the molecular weight of the polymers. Mixtures 200 cps to 2000 cps. By the “equilibrated viscosity” herein is
of Surfactants, initiators, reductants, chain transfer agents, meant the Brookfield viscosity measured at 30 minutes or
and the like may also be used. more, preferably after 24 hours, more preferably after 2 days,
The monomers may be added individually or in monomer 35 and most preferably after 14 days, at 25°C., after admixing
mixtures; they may be added neat or as an emulsion in water. was complete. Aqueous composite compositions having an
In certain embodiments the monomer herein is added in two equilibrated viscosity below 200 cps can have compromised
or more stages. stability due to settling. Aqueous composite compositions
In certain embodiments the second monoethylenically having an equilibrated viscosity above 4000 cps may be dif
unsaturated monomer is added throughout the reaction. Dur 40 ficult to pump depending on the handling requirements of the
ing a portion of certain embodiments the reaction, or stage, user. Aqueous composite compositions prepared above the
which corresponds to 5% to 50%, preferably from 10% to critical composite ratio can be subject to Substantial viscosity
45%, and more preferably from 15% to 40%, by weight of the build with time and would not be suitable for use in aqueous
total monomer addition, 75% to 100% of the adsorbing group coating compositions.
containing monomer is added concurrently with the second 45 In the second aspect of the present invention there is pro
monoethylenically unsaturated monomer. This stage rela vided a method for forming a stable aqueous composition
tively rich in adsorbing group containing monomer is some comprising composite particles comprising: admixing TiO2
times described as a “pulsed addition of monomer. In certain particles and adsorbing emulsion polymer particles at a mix
embodiments the pulse, or adsorbing group containing mono ing intensity of greater than 2 hp/kgal, preferably greater than
mer-rich stage, is begun at a point wherein from 0% to 65%, 50 6 hp/kgal. The intensity of the agitation was measured and
preferably from 0% to 50%, and more preferably from 0% to described by the power per unit volume of the mixing process,
30%, by weight of the total added monomer has been added. as known in the chemical engineering art and described, for
That is, it is preferable that the adsorbing group containing example, in Fluid Mixing Technology by James Y. Oldshue,
monomer pulse occurs relatively early in the reaction to form published by McGraw-Hill in 1983. The upper limit for mix
the adsorbing emulsion polymer. In such embodiments it is 55 ing intensity (power per unit volume) is the highest that the
preferred that optional second acid monomers and aldehyde chosen mixing method can reasonably provide without caus
reactive monomers are cofed with the adsorbing group con ing excessive gas dispersion or altering the particle size of the
taining monomer. adsorbing polymer particles or TiO2 particles through attri
Additional ingredients such as, for example, free radical tion or agglomeration. The upper limit depends on the equip
initiators, oxidants, reducing agents, chain transfer agents, 60 ment used and is not likely to exceed 10" hp/kgal.
neutralizers, Surfactants, and dispersants may be added prior In the method of the second aspect of the invention a
to, during, or Subsequent to any of the stages. Processes “stable aqueous composition” as defined by grit levels, the
yielding polymodal particle size distributions may be composite particles, the TiO2 particles, and the adsorbing
employed. polymer particles are defined and constituted as disclosed
The average particle diameter of the adsorbing emulsion 65 hereinabove. In one embodiment composite particles can be
polymer particles is typically from 40 nm to 150 nm, prefer formed with a rotor stator mixer. This can allow for continu
ably from 50 nm to 130 nm, and more preferably from 75 nm. ous flow of composite into a standard grind or letdown tank.
 US 8,710,133 B2
7 8
One mode of operation is combining a stream of TiO2 slurry The aqueous composition may optionally include organic
and adsorbing emulsion polymer in a tee fitting just upstream pigment particles. Suitable organic pigments also include
of the rotor stator. The discharge from the rotor stator would plastic pigments such as Solid bead pigments and micro
be a stable aqueous composition, i.e., low grit composite. A sphere pigments containing Voids or vesicles. Examples of
second mode of operation is preparing high grit composite in Solid bead pigments include polystyrene and polyvinyl chlo
a tank under low mixing intensity. The discharge of the tank ride beads. Examples of microsphere pigments, which
would then be passed through the rotor stator to break apart include polymer particles containing one or more Voids
the grit particles. include ROPAOUETM opaque polymer and vesiculated poly
Suitable mixing devices for the methods of the present mer particles.
invention include, for example, rotating devices, radial agita 10 The aqueous coating compositions including optional inor
tors, and axial agitators. Preferred is a shaft rotating on its ganic particles are prepared by techniques which are well
own axis with one or more structures such as blades or impel known in the coatings art. First, the inorganic particles are
lers attached to the shaft and oriented perpendicular to the typically well dispersed in an aqueous medium under high
axis. shear such as is afforded by a COWLESTM mixer. In one
The methods of the present invention, may be performed 15 embodiment the composite particles of the present invention
on an industrial scale and are typically performed in tanks and are added under low shear stirring along with other coatings
often performed in cylindrical tanks with dished or flat bot adjuvants as desired. Alternatively, the composite particles
toms or other geometries. In such vessels, mixing may be may be formed in situ during the formation of the aqueous
performed by any of a variety of means known in the art, coating composition. The aqueous composition may include,
including for example rotating impellers, homogenizers, in addition to composite particles, additional multistage
rotor-stator devices, static mixers, jet mixed systems, and emulsion polymer not associated with the composite par
combinations thereof. If rotating impellers are chosen, Suit ticles; also film-forming or non-film-forming solution or
able impellers include, for example, open impellers and close other emulsion polymers in an amount of 0% to 200% by
clearance impellers. If open impellers are chosen, Suitable weight of the adsorbing emulsion polymer of the present
impellers include, for example, radial flow impellers, axial 25 invention, and conventional coatings adjuvants such as, for
flow impellers, high shear impellers, high efficiency impel example, emulsifiers, coalescing agents(coalescents), plasti
lers and multiples and combinations thereof. Open impellers cizers, antifreezes, curing agents, buffers, neutralizers, thick
can be used with or without baffles or other internal devices eners, photosensitive moieties, rheology modifiers, humec
that redirect flow. If close clearance impellers are chosen, tants, wetting agents, biocides, plasticizers, antifoaming
Suitable impellers include, for example, gate impellers, heli 30 agents, UV absorbers, fluorescent brighteners, light or heat
cal impellers, anchor impellers, and multiples and combina stabilizers, biocides, chelating agents, dispersants, colorants,
tions thereof. In other cases, the methods of the present inven waxes, water-repellants, and anti-oxidants.
tion may be performed in pipelines. In pipelines that may be The aqueous coating composition optionally contains a
a part of a continuous process, for example, various Suitable volatile organic compound (“VOC). A VOC is defined
mixing means are known in the art and include for example 35 herein as a carbon containing compound that has a boiling
inline mixers and motionless mixers. Preferred mixers for point below 280° C. at atmospheric pressure. Water and
practicing the methods of the present invention are rotor ammonia are excluded from VOCs. Frequently a VOC is
stator devices. deliberately added to a paint or coating to improve the film
In one embodiment of the present invention, there are properties of a coating or to aid in the application properties of
provided certain aqueous compositions including composite 40 the composition employed to prepare the coating. Examples
particles formed by the methods of the present invention that are glycol ethers, organic esters, aromatic compounds, ethyl
may find utility as aqueous coating compositions. The ene and propylene glycol, and aliphatic hydrocarbons.
amount of inorganic particles in addition to composite par In one embodiment, the aqueous composition contains up
ticles included in the aqueous coating composition is from 0 to 20% VOC, preferably less than 5%, more preferably less
to 95 volume 96, based on the total dry volume of the aqueous 45 than 3%, and even more preferably less than 1.7%, by weight
composition and inorganic particles. Typically, the aqueous based on the total weight of the aqueous coating composition.
coating composition of this invention, when used to prepare Additional methods such as Steam stripping and choice of low
dried coatings, has a solids level in the range of from 20 to 50 VOC containing additives like biocides, defoamers, Soaps,
Volume 96, based on the Volume of the aqueous composition. dispersants, and thickeners are Suitable for further reducing
The pH of the aqueous composition is typically in the range of 50 the aqueous coating composition to less than 0.05% VOC by
from 3 to 11, and preferably, in the range of from 7 to 10. A weight based on the total weight of the aqueous coating
Suitable viscosity range for the aqueous composition is from composition.
50 to 130 Kreb units (KU), preferably from 70 to 120KU, and Additionally, the low VOC aqueous coating composition
more preferably from 90 to 110 KU. optionally contains coalescing agents that are not VOCs. A
Inorganic particles that may be used in addition to the 55 coalescing agent is a compound that is added to a water-borne
composite particles include: metal oxides such as Zinc oxide, emulsion polymer, paint, or coating, which reduces the mini
cerium oxide, tin oxide, antimony oxide, Zirconium oxide, mum film forming temperature (MFFT) of the emulsion poly
chromium oxide, iron oxide, lead oxide, aluminum oxide, mer, paint or coating by at least 1°C. The MFFT is measured
silicon oxide, titanium dioxide; Zinc sulfide, lithopone, cal using ASTM test method D2354. A non-VOC coalescing
cium carbonate, calcium sulfate, barium Sulfate, mica, clay, 60 agent is a coalescing agent which has a boiling point above
calcined clay, feldspar, nepheline syenite, wollastonite, diato 280° C. at atmospheric pressure. Examples of coalescing
maceous earth, alumina silicates, and talc. In one embodi agents that are not VOCs include plasticizers, low molecular
ment, the inorganic particles may have a particle size which is weight polymers, Surfactants, and autooxidizable plasticizers
from 1 to 100 nm, alternately from 1 to 50 nm. Examples of such as alkyl esters of unsaturated fatty acids. Preferred are
desired inorganic particles with a particle size of less than 100 65 alkyl esters prepared from oils such as linseed, tung, dehy
nm include Zinc oxide, silicon oxide, titanium dioxide, and drated castor, soybean, tall, Sunflower, and corn. Examples of
iron oxide. non-VOC coalescing agents include esters of unsaturated
 US 8,710,133 B2
10
fatty acids, such as mono-, di-, or tri-unsaturated fatty acids. BA, 205.1 g MMA, 2.52g ALMA, and 4.03 g MAA. A stage
Suitable unsaturated fatty acid esters include monounsat 2 monomer emulsion was prepared by mixing 275 g DI water,
urated fatty acid esters formed from palmitoleic acid, oleic 17.4 g (30% active) anionic surfactant A, 403.7 g BA, 220.9 g,
acid, or caproleic acid; diunsaturated fatty acid esters formed MMA, 5.6 g MAA, 59.9 g PEM, and 12.0 g UMA.
from linoleic acid; triunsaturated fatty acid esters formed A 5-liter reactor, four-necked round bottom flask equipped
from linolenic acid or eleosteric acid, or mixtures thereof. with a paddle stirrer, a thermocouple, nitrogen inlet, and
Conventional coatings application methods such as, for reflux condenser was assembled. To the flask was added 1000
example, brushing, rolling, and spraying methods such as, for
example, air-atomized spray, air-assisted spray, airless spray, g DI water and 50.0 g (30% active) anionic surfactant A, and
high Volume low pressure spray, and air-assisted airless spray stirring was started. The contents of the flask were heated to
may be used to apply the aqueous composition of this inven 10 84°C. under a nitrogen atmosphere. A solution of 2.4 g NaPS
tion. Additionally, for Some systems, other application tech in 35 g DI water was added. The stage 1 monomer emulsion
niques may be used to apply the aqueous polymer composi was fed into the reactor over 40 minutes at 16.7 g/min. A
tion, such as, caulk gun, roll coaters, and curtain coaters. The solution of 1.8g NaPS in 108 g DI water was fed separately to
aqueous polymer composition may be advantageously the flask for 40 minutes at 1.1 g/min. After the addition of
applied to Substrates such as, for example, plastic, wood, 15
stage 1 monomer emulsion the container was rinsed with a
metal, primed Surfaces, previously painted Surfaces, weath small portion of DI water and added into the flask. The NaPS
ered painted Surfaces, glass, composites, and cementitious co-feed was stopped and the reaction held at 83-86°C. for 30
Substrates. Drying to form the coating is typically allowed to minutes.
proceed under ambient conditions such as, for example, at 0° The stage 2 monomer emulsion was fed into the flask over
C. to 35°C. but may be accelerated with heat or low humidity. 60 minutes at 16.7 g/min. The NaPS co-feed was re-started
Abbreviations Used and fed for 60 minutes at 1.1 g/min. After the addition of stage
Butyl acrylate BA 2 monomer emulsion container was rinsed with a small por
Methyl methacrylate MMA tion of DI water and fed into the flask. The contents of the
Methacrylic acid MAA flask were maintained at 84-86°C. for 5 minutes. The batch
Ureido methacrylate (50% active) UMA 25 was then cooled to 65° C. As the batch was cooling, at 80°C.,
Phosphoethyl methacrylate (65% active) PEM a solution of 16.5 g (28% conc.) aqueous ammonia in 18.5g
Sodium 4-vinylbenzenesulfonate SSS
Sodium persulfate NaPS DI water was added and rinsed with 5 g DI water. A redox pair
Deionized water DI water was added. The batch was cooled to room temperature. While
cooling and <50° C., 21.8 g (28% conc.) aqueous ammonia
30
Experimental Methods was added. The particle size was 64 nm, solids of 39.1%, and
a pH of 8.1 The critical compositeratio for adsorbing polymer
Brookfield viscosities herein were measured using spindle a/TIPURETM 746 (TiO2) was determined to be 47 PVC.
#4 at 60 RPM unless stated otherwise.
The critical composite ratio herein is expressed as a pig Preparation of Composite
ment volume concentration (“PVC) and was determined as 35
follows: An aqueous TiO2 slurry was added to an adsorbing A 40 PVC, 35 volume solids composite particle composi
emulsion polymer at a PVC of 10-20 while mixing at ca. 450 tion was prepared by the following method: 33.89 g adsorb
rpm. Optionally, a pigment dispersant was added. The vis ing emulsion polymera, 0.86 g water, 0.5g TAMOLTM 2002
cosity of the mixture was measured on a Brookfield viscom (25% with KOH) and 0.05 gFOAMSTARTMA-34 were com
eter after ca. 3 minutes of mixing time. The PVC was then 40 bined. 41.55g TIPURETM 746 was added to the emulsion
incrementally increased in units of 4 by the addition of addi polymer mixture while stirred at 930 rpm using a bench
tional TiO2 slurry. The mixing rate was maintained at ca. 450 mixer. The Brookfield viscosity was 2020 cps after an aging
rpm. The time between TiO2 addition and viscosity measure period of 2 days.
ment was ca. 3 minutes. The time between TiO2 addition
steps was ca. 4 minutes. The critical composite ratio was 45 COMPARATIVE EXAMPLEA
determined from a plot of Brookfield viscosity and TiO2 PVC
and was taken as the intercept between the tangent line at Composite Particles Prepared Above the Critical
higher PVC and the steady state value at lower PVCs. Composite Ratio
Grit determination for composite samples. In this method
200 g of composite was passed through an apparatus which 50 A 50 PVC, 35 volume solids latex composite was prepared
holds a number of pre-weighed screens from 20 to 325 mesh by the following method. 28.24 g adsorbing emulsion poly
in Succession. Warm water was rinsed through the apparatus mera, 0.71 g water, 0.41 gTAMOLTM 2002 (25% with KOH)
to clean the screens, and then the apparatus was taken apart and 0.04 g FOAMSTARTTM A-34 were combined. 51.94 g
and the screens were dried in an oven. The final (dried weight) TIPURETM746 was added to the latex mixture while stirred at
of the screens minus the initial weight multiplied by a factor 55 950 rpm using a standard bench mixer. The Brookfield vis
of 5000 yielded a grit value in units of parts per million. cosity (BF) was 8200 cps after an aging period of 2 days.
The following Examples serve to illustrate the invention.
TABLE 1.1
EXAMPLE1
60 Impact of formulating the composite below and
above the critical composite ratio for adsorbing
Composite Particles Prepared Below the Critical polymer a? TIPURE M 746 (TiO2
Composite Ratio
Volume BF init 3 Hr BF 6 Hr BF 23 Hr BF
Preparation of Adsorbing Emulsion Polymera PVC Solids 3,60 3.60 3,60 3,60
65 10 O.35 6 6 6 30
A stage 1 monomer emulsion was prepared by mixing 150 2O O.35 10 10 8 30
g DI water, 12.6 g (30% active) anionic surfactant A, 292.3 g
 US 8,710,133 B2
11 12
TABLE 1.1-continued TAMOLTM165A (Dow Chemical Co.), 1 gram of BYK 348,
0.5 g FOAMSTARTM A-34 (Cognis GMBH) and 22.5 g.
Impact of formulating the composite below and MINEXTM 10 (Unimin Corp.). Finally the latex/grind mix
above the critical composite ratio for adsorbing
polymer a? TIPURE '746 (TiO2 ture was letdown with the following additives under bench
5 mixing. 108.15g RHOPLEXTMVSR-1050LOE (50% solids)
Volume BF init 3 Hr BF 6 Hr BF 23 Hr BF
PVC Solids 3,60 3,60 3,60 3.60 (Dow Chemical Co.), 17.50 g ROPAQUETM Ultra E. (Dow
Chemical Co.), 3.55g OPTIFILMTM Enhancer 400 (Eastman
30
40
O.35
O.35
16
50
2O
178
22
242
120
2020
Chemical CO.), 0.5 g FOAMSTARTM A-34, 14.33 g
50 O.35 358 810 4910 82OO 10
ACRYSOLTM RM-2020 NPR (Dow Chemical Co.), 2.60 g
ACRYSOLTM SCT-275 (Dow Chemical Co.) and 41.37 g
Water.

EXAMPLE 2
The coating properties are shown in Table 2.
COMPARATIVE EXAMPLEB
15
Preparation of Stable Aqueous Composite
Composition Attempted Composite Formation with Ineffective
Polymer c
Preparation of Adsorbing Emulsion Polymer b
Preparation of Ineffective Emulsion Polymer c
A primary monomer emulsion was prepared by mixing 555
g DI water, 68.7 g (30% active) anionic surfactant A, 939.6 g. A first monomer emulsion was prepared by mixing 200g of
BA, 748.2 g MMA, and 3.48 g MAA. A stage 1 monomer DI water, 28.25 g (30% active) anionic surfactant, 285.6 g.
emulsion was prepared by transferring 772 g of the primary BA, 197.22 g MMA, 20.40 g PEM, and 7.53 g (90% active)
monomer emulsion into a separate vessel, then adding 40.0 g 25 SSS. A second monomer emulsion was prepared by mixing
PEM diluted with 30 g DI water. A stage 2 monomer emulsion 420 g DI water, 28.75 g (30% active) anionic surfactant B,
was prepared by transferring 719 g of the primary monomer 651.1 g BA, 515.15g MMA, and 16.9 g UMA. The reactor
emulsion into a separate vessel. A stage 3 monomer emulsion was a 5-liter, four necked round bottom flask equipped with a
was prepared by adding 17.4 g UMA to the remaining pri paddle stirrer, a thermometer, nitrogen inlet, and a reflux
mary monomer emulsion. A 5-liter reactor, four-necked 30 condenser. To the flask was added 900 g DI water and 11.3g
round bottom flask equipped with a paddle stirrer, a thermo (30% active) anionic surfactant B. The contents of the flask
couple, nitrogen inlet, and reflux condenser was assembled. were heated to 84°C. under a nitrogen atmosphere and stir
To the flask was added 900 g DI water, 3.9 g (30% active) ring initiated. A portion of the first monomer emulsion (110g)
anionic surfactant. The contents of the flask were heated to was then added, quickly followed by a solution of 3.35 g
84°C. under a nitrogen atmosphere. The flask was charged 35 NaPS dissolved in 20 g DI water, and a rinse of 5 g DI water.
with 110.2 g of stage 1 monomer emulsion and stirred for 1 After stirring for 10 minutes, the remainder of the first mono
minute. A solution of 3.48g NaPS in 35 g DI water was added, mer emulsion with a 25 g DI water rinse and 0.40 g NaPS
and rinsed with 10 g DI water. After 3 minutes, stage 1 dissolved in 30 g DI water were added linearly and separately
monomer emulsion was fed into the reactor over 30 min, over 30 minutes. The contents of the flask were held at 84°C.
followed by a rinse of 25 g DI water. A separate solution of 40 for 20 minutes. A solution of 9 g (29% active) ammonium
1.74 g NaPS in 98 g DI water was fed separately to the flask hydroxide and 9 g DI water was then added to the flask over
for 100 minutes, followed by a rinse of a 5 g DI water. The a period of 10 minutes. The second monomer emulsion with
contents of the flask were maintained at 84-86°C. throughout a 25 g DI water rinse and 1.1 g NaPS dissolved in 80 g DI
the feeds. Stage 2 monomer emulsion was then fed over 30 water were added separately to the flask over a period of 80
minutes. Stage 3 monomer emulsion was added to the flask 45 minutes. The contents of the flask were maintained at a tem
over 30 minutes. The batch was then cooled to 65° C. During perature of 83-84°C. during the addition of the second mono
the cooling, at about 80°C., the batch was partially neutral mer emulsion. The contents of the flask were then cooled to
ized with a solution of 12 g (28% conc.) aqueous ammonia in 65° C. and a catalyst/activator pair was added to the flask. 37
12g DI water, then rinsed with 5 g DI water. A redox pair was g (42% solids) of TAMOLTM 2002 was added. The polymer
then added. The batch was cooled to room temperature. While 50 was then neutralized to pH 8.56 with dilute potassium
cooling and <50° C., the reaction was neutralized to pH 8.3 hydroxide. The particle size was 97 nm and the solids
with a dilute KOH solution over 20 minutes. After addition of 45.66%. There was no measurable critical composite ratio for
this feed, the container was rinsed with 4g DI water rinse and comparative adsorbing emulsion polymer c and TIPURETM
added to batch. The particle size was 114 nm, solids were R-746 (TiO2). This is believed to be due to lack of composite
45.5% TS, and pH of 8.3. The critical composite ratio for 55 formation, due at least in part to insufficient adsorbing mono
adsorbing polymer b/TIPURETM 746 (TiO2) was determined mer in the adsorbing emulsion polymer (for the TiO2 com
to be 36 PVC. position used)
Formation of Composite Particles. A 29.19 PVC, 34 volume solids coating was prepared by
A composite was formed by mixing 129.76 g emulsion the following method. A composite was first formed by mix
polymer b, 32.67g water, 1.92g TAMOLTM 2002 (25% with 60 ing 124.77 g adsorbing emulsion polymer c. 37.90 g water
KOH) and 0.58 grams FOAMSTARTM A-34.125 g and 0.58 gFOAMSTARTMA-34.125 g TIPURETM R-746 at
TIPURETM R-746 (E.I. DuPont de Nemours and Co.) at 19.5% solids was added to this mixture while stirred using a
19.5% solids was added to this mixture while stirred using a bench mixer. A sample of the composite was analyzed with an
bench mixer. A sample of the composite was analyzed with an optical microscope. Large grit particles were observed on the
optical microscope. No large grit particles were observed in 65 order of 50-500 microns. It is known that particles of this size
this sample. The composite mixture was then letdown with an are prone to settling with time which compromises storage
extender grind containing 13.95 g water, 0.54 g stability.
 US 8,710,133 B2
13 14
The composite mixture was then letdown with an extender aqueous Solution of potassium hydroxide was added. The
grind containing 13.95g water, 0.54 g TAMOLTM 165A, 1 g particle size was 85 nm and solids were 42.0% with a pH
BKY 348, 0.5g FOAMSTARTMA-34 and 22.50g MINEXTM adjusted to 8.2. The critical composite ratio of adsorbing
10. Finally the latex/grind mixture was letdown with the polymer d/TIPURETM 746 (TiO2) was determined to be 38
following additives under standard bench mixing. 108.15g PVC.
RHOPLEXTM VSR-1050LOE (50% solids), 17.50 g A36 PVC, 34.3 volume solids composite was prepared by
ROPAQUETM Ultra E, 3.5g OPTIFILMTM Enhancer 400, 0.5 the following method. 30.06 g adsorbing polymer d, 2.81 g
g FOAMSTARTM A-34, 14.33 g ACRYSOLTM RM-2020 water, 0.45 g TAMOLTM 2002 (25% with KOH) and 0.14g
NPR, 2.60 g ACRYSOLTM SCT-275 and 41.37 grams of FOAMSTARTMA-34 were combined. A mixture of 35.80 g
water. The coatings properties are shown in Table 2.1 10 TIPURETM 746 and 2.86 g water was added to the mixture
with bench mixing. The Brookfield viscosity was 2940 cps
TABLE 2.1
after an aging period of 14 days.
Performance of coatings containing composite COMPARATIVE EXAMPLE C
15
Coating Example 2 Comparative Example B Composite Prepared at a PVC and Volume Solids
Wt% copolymerized 2.3 1.2 that Gives Unacceptably High Viscosity
PEM in emulsion pol.
TiO2 TIPURETM R-746 TIPURETMR-746 A38 PVC, 36.3 volume solids composite was prepared by
Equilibrated Brookfield 288O 8O the following method. 29.32 g adsorbing polymer d, 2.74g
viscosity (#4 spindle, 60
rpm) water, 0.44 g TAMOLTM 2002 (25% with KOH) and 0.13 g
Observation trace grit settling FOAMSTARTMA-34 were combined. A mixture of 32.05g
60 gloss dry coating 41 28 TIPURETM 746 and 5.26 g water was added to the latex
S/mil dry coating 6.73 6.06 mixture with bench mixing. The Brookfield viscosity was
25 6200 cps after an aging period of 14 days.
The storage stable aqueous composition of the invention,
Example 2, provided higher gloss and Superior hiding perfor TABLE 3.1
mance of the coating compared to Comparative Example B. Viscosities of 14 day aged composites prepared
EXAMPLE 3 30
at varying PVC and volume Solids.
Volume Solids
Composite Prepared at a PVC and Volume Solids to PVC 36.3 35.3 34.3
Give Acceptable Viscosity
38 62OO 4300
Preparation of Adsorbing Emulsion Polymer d 35 37
36 438O
3985
2940

A stage 1 monomer emulsion was prepared by mixing

136.2 g DI water, 20.2 g (30% active) anionic surfactant A, The Viscosity of composite systems can be optimized by
235.4 g BA, 187.4 g MMA, 0.9 g MAA, and 36.8 g. PEM. A titration of the Pigment Volume Concentration (PVC) to a
stage 2 monomer emulsion was prepared by mixing 154.5g 40 level below the critical composite ratio that has the desired
DI water, 22.9 g (30% active) anionic surfactant A, 267.0 g end-use viscosity range for storage and handling.
BA, 212.6 g MMA, and 1.0 g MAA. A stage 3 monomer
emulsion was prepared by mixing 209.3 g DI water, 31.0 g EXAMPLE 4
(30% active)anionic surfactant A, 361.6 g. BA, 287.9 g MMA,
16.0 g of 50% aqueous solution of UMA, and 1.3 g MAA. A 45 Composite Prepared with 75 Nm Adsorbing
5-liter reactor, four-necked round bottom flask equipped with Emulsion Polymer
a paddle stirrer, a thermocouple, nitrogen inlet, and reflux
condenser was assembled. To the flask was added 1150 g DI Preparation of Adsorbing Emulsion Polymere
water and 6.0 g (30% active) of anionic surfactant A and
stirring was initiated. The contents of the flask were heated to 50 A stage 1 monomer emulsion was prepared by mixing 136
84°C. under a nitrogen atmosphere. A 110.0 g portion of the g DI water, 19.0 g (30% active) anionic surfactant A, 389.8 g.
stage 1 monomer emulsion was added to the kettle followed BA, 273.5g MMA, 5.38g MAA, and 3.36 g ALMA. A stage
by a 25 g DI water rinse. The contents were stirred for 1 2 monomer emulsion was prepared by mixing 312g DI water,
minute then a solution of 3.2 g NaPS in 40 g DI water was 29.0 g (30% active) anionic surfactant A, 501.1 g BA, 381.8g
added. After another 2 minutes monomer emulsion 1 was 55 MMA, 16.0 g UMA, 7.42 g MAA, and 29.7 g PEM. A 5-liter
added to the flask over 29 minutes. Concurrently, a solution of reactor, four-necked round bottom flask equipped with a
1.6 g NaPS in 98 g DI water was fed separately to the flaskat paddle stirrer, a thermocouple, nitrogen inlet, and reflux con
a rate of 1.0 g/min. After completion of monomer emulsion 1 denser was assembled. To the flask was added 1244 g DI
addition, monomer emulsion 2 was added over 28 minutes. water and 40 g (30% active) of an anionic surfactant A and
After completion of monomer emulsion 2 feed, monomer 60 stirring was initiated. The contents of the flask were heated to
emulsion 3 was added over 45 minutes. The contents of the 88°C. under a nitrogen atmosphere. A 137 g portion of the
flask were maintained at 84-86°C. during the additions. The stage 1 monomer emulsion was added to the kettle followed
monomer emulsion was rinsed with 20 g DI water after each by a 25 g DI water rinse. The contents were stirred for 1
stage of completion. The batch was then cooled to 65° C. and minute then a solution of 3.26 g NaPS in 40 g DI water was
12 g aqueous ammonia (28% active) in 12 g DI water was 65 added. After another 2 minutes monomer emulsion 1 was
added. A redox pair was then added. The batch was cooled to added to the flask over 40 minutes. Concurrently, a solution of
room temperature. While cooling and at <50° C., 160 g dilute 1.45 g NaPS in 118 g DI water was fed separately to the flask
 US 8,710,133 B2
15 16
at a rate of 1.07 g/min. After completion of monomer emul composite ratio of adsorbing emulsion polymer f (100 nm
sion 1 feed the initiator cofeed was stopped and batch was polymer particles)/KRONOSTM 4311 (TiO2) was 35 PVC.
held at temperature for 30 minutes. The initiator cofeed was The Brookfield viscosity was 6720 cps after an aging period
then restarted and monomer emulsion 2 was added over 70 of 30 minutes.
minutes. The contents of the flask were maintained at 84-86° The critical composite ratio can be adjusted by using dif
C. during the additions. The monomer emulsion flask was ferent size adsorbing emulsion polymer particles. The critical
rinsed with 140 g DI water. The batch was then cooled to 65° composite ratio is higher for Smaller latex particles. Two
C. and a solution of 11 g acqueous ammonia (28% conc.) in 22 composite mixtures were prepared at 41 PVC and 40 VS
g DI water was added. A redox pair was then added. The batch (Example 4 and Comparative Example D). The 41 PVC com
was cooled to room temperature. While cooling and at <50° 10 posite formed in Example 4 was below the critical composite
C., a dilute aqueous Solution of potassium hydroxide was ratio and had a Brookfield viscosity of 180 cps. The 41 PVC
added to pH of 7.8. The particle size was 75 nm and solids of composite formed in Example 4 Comparative was above the
40.8% with a pH of 7.8. critical composite ratio and had a Brookfield viscosity of
A 41.7 PVC, 40.1 volume solids composite was prepared 6720 cps.
by the following method. 49.02 g adsorbing polymere, 0.6 g. 15
water, 0.83 g TAMOLTM 2002 (18.1% with KOH) and 0.1 g COMPARATIVE EXAMPLEE
FOAMSTARTMA-34 were combined. 70.96 g KRONOSTM
4311 was added to the latex mixture while stirred at 466 rpm Composite Particles Prepared Using a Stirred Tank,
using a standard bench mixer. The critical composite ratio of Pitched Blade Turbine, Low Mixing Intensity
adsorbing emulsion polymer e (75 nm polymer particles)/
KRONOSTM 4311 (TiO2) was 55 PVC. The Brookfield vis Preparation of Adsorbing Emulsion Polymerg
cosity was 180 cps after an aging period of 30 minutes.
A stage 1 monomer emulsion was prepared by mixing 148
COMPARATIVE EXAMPLED g DI water, 27.5 g (30% active) anionic surfactant A, 419.8g.
25 BA, 303 g MMA, 3.65 g ALMA, and 3.65 g MAA. A stage 2
Composite Prepared with 100 Nm Adsorbing monomer emulsion was prepared by mixing 339.4 g DI water,
Emulsion Polymer 37.7 g (30% active) anionic surfactant A, 524.2 g BA, 432.9 g,
MMA, 17.3 g UMA, 10.1 g MAA, and 32.3 g PEM. A 5-liter
Preparation of Adsorbing Emulsion Polymer f reactor, four-necked round bottom flask equipped with a
30 paddle stirrer, a thermocouple, nitrogen inlet, and reflux con
A stage 1 monomer emulsion was prepared by mixing 148 denser was assembled. To the flask was added 985g DI water,
g DI water, 27.5 g (30% active) anionic surfactant A, 423.4g 4.35 g (30% active) anionic surfactant A with a 26 g DI water
BA, 297.1 g MMA, 5.84gMAA, 3.65 g ALMA. A stage 2 rinse. The contents of the flask were heated to 84°C. under a
monomer emulsion was prepared by mixing 339.4 g DI water, nitrogen atmosphere. The flask was charged with 110.1 g of
38.5 g (30% active) anionic surfactant A, 604.9 g BA, 354.1 g 35 stage 1 monomer emulsion, rinsed with 25 g DI water, and
MMA, 17.3 g UMA, 8.1 g MAA, and 32.3 g of PEM. A 5-liter stirred for 1 minute. A solution of 3.55g NaPS in 35 g DI
reactor, four-necked round bottom flask equipped with a water was added, and rinsed with 10 g DI water. After 3
paddle stirrer, a thermocouple, nitrogen inlet, and reflux con minutes, stage 1 monomer emulsion was fed into the reactor
denser was assembled. To the flask was added 929.0 g DI over 40 min, followed by a rinse of 35 g DI water. A separate
water and 3.50 g (30% active) of an anionic surfactant A and 40 solution of 1.58 g NaPS in 109 g DI water was fed separately
stirring was initiated. The contents of the flask were heated to to the flask at 1.0 g/min for 40 minutes. The contents of the
88°C. under a nitrogen atmosphere. A 110.1 g portion of the flask were maintained at 84-86° C. throughout the feeds.
stage 1 monomer emulsion was added to the kettle followed After completion of stage 1 monomer emulsion the separate
by a 25 g DI water rinse. The contents were stirred for 1 persulfate co-feed was stopped and the batch was held at
minute then a solution of 3.55g NaPS in 44 g DI water was 45 83-85°C. for 30 minutes. The monomer emulsion vessel was
added. After another 2 minutes monomer emulsion 1 was rinsed with 35 g DI into the flask. The stage 2 monomer
added to the flask over 40 minutes. Concurrently, a solution of emulsion was added to the flask and the remaining separate
1.58g NaPS in 118 g DI water was fed separately to the flask persulfate co-feed was re-started (at 1 g/min), and both feeds
at a rate of 1.07 g/min. After completion of monomer emul were added over 70 minutes. The batch was then cooled to 65°
sion 1 feed the initiator cofeed was stopped and the batch was 50 C. During the cooling, at about 80°C., a solution of 11.2g
held at temperature for 30 minutes. The initiator cofeed was (28% conc.) aqueous ammonia in 11.2 g DI water was added,
then restarted and monomer emulsion 2 was added over 70 then rinsed with 9 g DI water. A redox pair was then added.
minutes. The contents of the flask were maintained at 84-86° The batch was cooled to room temperature. While cooling
C. during the additions. The monomer emulsion was rinsed and <50° C., 35.6 g TAMOL 2002TM dispersant was added
with 50 g DI water. The batch was then cooled to 65° C. and 55 and rinsed with 15 g DI water. The batch was neutralized to
11 g of aqueous ammonia (28% conc.) in 22 g DI water was pH 8.0 with aqueous ammonia (28% conc.) and rinsed with 4
added. A redox pair was then added. The batch was cooled to g DI water. The particle size was 105 nm, solids were 45.5%,
room temperature. While cooling and at <50° C., a dilute and pH of 8.0.
aqueous Solution of potassium hydroxide was added to a pH
of 7.8. The particle size was 100 nm and solids of 46.9% with 60 Preparation of Composite
a pH of 7.8
A 40.8 PVC, 40.2% volume composite was prepared by the 1.543.1 g adsorbing polymerg was charged to a 1 gallon
following method. 42.74 g adsorbing emulsion polymer e. stainless steel cylindrical tank with a flat bottom. The tank
6.77 g water, 0.83 g TAMOLTM 2002 (18% with KOH) and diameter was 6.6 in and the height was 7.8 in. An agitator
0.10 grams of FOAMSTARTMA-34 were combined. 69.38g 65 shaft with a 3.5 in diameter, four bladed, 45° pitched blade
KRONOSTM 4311 (Kronos, Inc.) was added to the mixture turbine was placed in the tank. The off bottom clearance of the
while stirred at 460 rpm using a bench mixer. The critical impeller was 1.75 in. 161.8g DI water was added to the vessel
 US 8,710,133 B2
17 18
and the agitator speed was set to 260 rpm. 3.0 g FOAM 104.6 g perminute. The KRONOSTM4311 was pumped to the
STARTMA-34 were charged to the vessel followed by a 3.2g rotor stator chamber at 93.2 g per minute. The rotor stator
DI water rinse. 1,617.6 g KRONOSTM 4311 (TiO2) was speed was set at 3,200 rpm, which imparted a power per
pumped top surface to the vessel over 1 minute, followed by volume of 152.5 kW/m (773.9 hp/kgal). The PVC of the
a 147.7g rinse. The vessel contents were then mixed at 260 resulting mixture was 33.7%. The solids, total grit level in
rpm for an additional 5 minutes. This speed imparts a power ppm, and equilibrated viscosity of the composite are listed in
per volume of 0.32 kW/m (1.63 hp/kgal). A sample of the Table 7.1.
composite material was filtered through a 45 micron screen.
The concentration of grit particles greater than 45 micron was Example 7b
10
2.290 ppm on a dry mass basis.
The rotor stator speed was set at 2.540 rpm, which imparts
EXAMPLE 5 a powerper volume of 76.2 kW/m3 (387.0hp/kgal). The PVC
of the resulting mixture was 33.7%. The solids, total grit level
Preparation of Composite, Stirred Tank, Pitched in ppm, and equilibrated Viscosity of the composite are listed
Blade Turbine, High Power 15 in Table 7.1.

1,543.1 g adsorbing polymerg was charged to a 1 gallon Example7c

stainless steel cylindrical tank with a flat bottom. The tank
diameter was 6.6 in and the height was 7.8 in. An agitator The flow rates were changed to lower the ratio of adsorbing
shaft with a 3.5 in diameter, four bladed, 45° pitched blade polymerg to TiO2. The premix was pumped to the rotor stator
turbine was placed in the tank. The offbottom clearance of the chamber at 94.2g perminute. KRONOSTM4311 was pumped
impeller was 1.75 in. 161.8g DI water was added to the vessel to the rotor stator chamber at 93.2 g per minute. The rotor
and the agitator speed was set to 620 rpm. 3.0 g FOAM stator was set at 3,200 rpm, which imparted a power per
STARTMA-34 were charged to the vessel followed by a 3.2g volume of 152.5 kW/m (773.9 hp/kgal). The PVC of the
DI water rinse. 1,617.6 g KRONOSTM 4311 was pumped top 25 resulting mixture was 36.1%. The solids, total grit level in
surface to the vessel over 1 minute, followed by a 147.7 g ppm, and equilibrated viscosity of the composite are listed in
rinse. The vessel contents were then mixed at 620 rpm for an Table 7.1.
additional 5 minutes. This speed imparts a power per Volume
of 3.5 kW/m (17.8 hp/kgal). A sample of the composite Example 7D
30
material was filtered through a 45 micron screen. The con
centration of grit particles greater than 45 micron was 245 The rotor stator speedwas set at 2.540 rpm, which imparted
ppm on a dry mass basis. a powerper volume of 76.2 kW/m3 (387.0hp/kgal). The PVC
of the resulting mixture was 36.1%. The solids, total grit level
EXAMPLE 6 in ppm, and equilibrated Viscosity of the composite are listed
35 in Table 7.1.
Preparation of Composite
Example 7E
Use of Stirred Tank, Pitched Blade Turbine, Recycle Through
Rotor Stator to Break Up Grit The premix was pumped to the rotor stator chamber at
The material from Comparative Example E was recircu 40 104.6 g per minute. KRONOSTM4311 was pumped to the
lated through a rotor stator to break up the particles greater rotor stator chamber at 116.4 g per minute. The rotor stator
than 45 micron. Composite was pumped from the 1 gallon was set at 3,200 rpm, which imparted a power per volume of
tank with a Masterflex tubing pump at a rate of 210 g/minute 152.5 kW/m (773.9 hp/kgal). The PVC of the resulting mix
through a Silverson L4-R inline rotor stator and back into the ture was 38.9%. The solids, total grit level in ppm, and equili
1 gallon tank. The rotor speed was set to 3,200 rpm, which 45 brated viscosity of the composite are listed in Table 7.1.
imparts a power per volume of 152.5 kW/m (773.9hp/kgal). Example 7F
After 30 minutes of recycle flow, a sample was taken and the
grit concentration was 150 ppm. After 90 minutes of recycle
flow, a sample was taken and the grit concentration was 35 The rotor stator speedwas set at 2.540 rpm, which imparted
ppm. The recycled material was formulated into a coating and 50 a powerper volume of 76.2 kW/m3 (387.0hp/kgal). The PVC
had good hiding and gloss. of the resulting mixture was 38.9%. The solids, total grit level
in ppm, and equilibrated Viscosity of the composite are listed
EXAMPLE 7 in Table 7.1.

Preparation of Composite with Rotor Stator Mixing 55 TABLE 71

Composite parameters
Example 7a
Com- Rotor Total 24hr. Brookfield
Continuous Process, Feed Pre-Composite Polymer posite Stator Grit Viscosity (spindle
Run # PVC (rpm) (ppm) Solids #4, 60 rpm)
and Tio to a Rotor Stator 60
Example 7a 33.7 32OO 39 56.35% 480
7631.3 g adsorbing emulsion polymerg was premixed with Example 7b 33.7 2S4O 35 56.48% 330
1,530.4 DI water and 14.7 g FOAMSTARTMA-34 followed Example 7c 36.1 32OO 45 57.33% 1130
Example 7d 36.1 2S4O 33 57.33% 1040
by a 16 g DI water rinse. This premix was charged to a tank Example 7e 38.9 32OO 51 58.45% 6750
and blended for 5 minutes. KRONOSTM 4311 (TiO2) was 65 Example 7f 38.9 2S4O 43 58.60% 4200
charged to a separate tank and agitated mildly to avoid set
tling. The premix was pumped to the rotor Stator chamber at
 US 8,710,133 B2
19 20
Composite particles formed by the method of the present at least one second monoethylenically unsaturated mono
invention provide stable aqueous compositions as evidenced mer,
by low grit formation. said emulsion polymer having a calculated Tg of from -20°
Table 7.2 shows the impact of the conditions of composite C. to 50° C.;
formation on the final coating opacity and gloss. S/Mil was 5 wherein said emulsion polymer is formed by emulsion copo
evaluated following ASTM Test Method D-2805.70. lymerization of said at least one second monoethylenically
TABLE 7.2
Coating compositions and properties
Coating Coating Coating Coating Coating Coating
Example Example Example Example Example Example
7a. 7b 7c 7d 7e 7f
Ingredients
(in lbs)
Composite Pre-mix
Adsorbing polymerg 3.18.04 3.18.04 286.99 286.99 254.66 254.66
FOAMSTARA-34 O.62 O.62 O.S6 O.S6 OSO O.SO
Water 63.91 63.91 58.04 S8.04 51.02 51.02
KRONOSTM 4311 342.OO 342.00 342.01 342.01 342.03 342.03

Composite Pre-mix 724.57 724.57 687.60 687.60 648.21 648.21

Sub-Total
Letdown

RHOPLEXTMVSR- 2O2.63 2O2.63 230.81 230.81 260.14 260.14

1 OSO
Propylene Glycol 9.30 9.30 9.30 9.30 9.30 9.30
TEXANOLTM 4.66 4.66 4.66 4.66 4.66 4.66
FOAMSTARTMA-34 1.04 1.04 1.04 1.04 1.04 1.04
ACRYSOLTM RM- 26.OO 26.00 26.OO 26.00 26.OO 26.00
2020 NPR
Water 87.71 87.71 96.32 96.32 106.19 106.19
ACRYSOLTM RM- 2.8O 2.80 2.8O 2.80 2.80 2.80
8W
Grind Sub-Total 334.14 334.14 370.93 370.93 410.14 410.14

Total 1058.71 1058.71 1058.53 1058.53 1058.34 1058.34

Properties
KU Viscosity initial 112 115 113 113 11S 104
KU Viscosity 113 116 118 114 117 109
equilibrated
20° Gloss 38 36 36 37 36 33
60° Gloss 71 71 70 71 71 69
S.M. 7.43 7.39 7.34 7.47 7.49 7.51

45
Coatings formed by a continuous process system, Examples unsaturated monomer wherein 75% to 100%, by weight, of
7a-7 f, demonstrate desirable hiding and gloss Supporting the said P-acid monomer is added concurrently with said second
conclusion that composite can be prepared using a continuous monoethylenically unsaturated monomer during a stage com
process system. prising from 10% to 50% of the total monomer weight.
What is claimed is: 50 4. The method of claim 3 wherein said 75% to 100%, by
1. A method for forming a stable aqueous composition weight, of said P-acid monomer is added concurrently with
comprising composite particles comprising: admixing TiO2 said second monoethylenically unsaturated monomer during
particles and adsorbing emulsion polymer particles at or a stage beginning at from 0 to 50% of total added monomer
below the critical composite ratio at a mixing intensity of weight.
greater than 2 hp/kgal to an equilibrated viscosity range of 55
from 200 cps to 4000 cps. 5. The method of claim 3 or claim 4 wherein said stage
2. The method of claim 1 wherein said admixing occurs in wherein 75% to 100%, by weight, of said P-acid monomer is
a mixing Zone comprising at least one static stator element unsaturated monomerwith
added concurrently said second monoethylenically
further comprises the addition of from
and at least one rotating rotor element. 0.01% to 2%, by weight, based on the weight of said emulsion
3. The method of claim 1 wherein said adsorbing emulsion 60 polymer, second acid containing monomer.
polymer particles are multistage emulsion polymer particles 6. A method for forming a coating comprising
comprising, as copolymerized units: (a) forming said stable aqueous composition of claim 1:
from 0.5% to 5%, by weight P-acid monomer, based on the (b) applying said aqueous composition to a Substrate; and
weight of said emulsion polymer; (c) drying, or allowing to dry, said applied aqueous com
from 0% to 0.05% by weight multiethylenically unsatur- 65 position.
ated monomer, based on the weight of said emulsion
polymer; and