# Patent

## Title
Aqueous dispersion of polymeric particles

## Abstract

An aqueous dispersion of polymeric particles and process for forming thereof is provided. The particles comprise a first polymer comprising, as polymerized units, at least one monoethylenically unsaturated monomer and at least one multi-ethylenically unsaturated monomer and when dry, at least one void; and at least one second polymer, substantially encapsulating the first polymer, comprising, as polymerized units, at least one ethylenically unsaturated monomer.

## Background
This non-provisional patent application is claiming priority based on Provisional Patent Application No. 60/709,658, filed Aug. 19, 2005, the disclosure of which is incorporated herein by reference.


This invention relates to film-forming binders that can be used in aqueous coating compositions. More particularly, this invention relates to an aqueous dispersion of film-forming polymeric particles that also provide a high degree of white light scattering when the film dries.
Aqueous coating compositions that, when dried, have improved film integrity (e.g., scrub resistance) are desired, particularly in coating compositions having low or no volatile organic compounds (“VOC”) content. In some cases, particles having one or more voids provide such coating compositions, while concurrently reducing the mass of the particles, and thereby reducing the materials and energy which would have been expended in providing that mass. Particles, including one or more voids may also contribute to the opacity of dry coating films.
U.S. Pat. No. 6,139,961 discloses an aqueous dispersion of water-insoluble core/sheath polymer particles. The core contains a void encapsulated by a first shell polymer having a glass transition temperature greater than 50° C., and polymerized on the first shell is a second shell polymer having a glass transition temperature of −15° C. to −50° C. However, to the extent that such particles can form a film, we have discovered that they have poor opacity, probably because many of the voids collapse upon film formation.
The film-forming binder particles of this invention provide superior opacity characteristics i.e., improved and consistent hiding, in comparison to the prior art, when incorporated into coatings. A first aspect of the invention is an aqueous dispersion of polymeric particles where the particles comprise from 10% to 80% by weight, based on the weight of the polymeric particles, of a first polymer comprising, as polymerized units, at least one monoethylenically unsaturated monomer and from 0.05 to 90% by weight, based on the total weight of the first polymer, at least one multi-ethylenically unsaturated monomer and when dry, at least one void; and at least one second polymer comprising, as polymerized units, at least one ethylenically unsaturated monomer. The void has a diameter of from 100 to 1200 nanometers and the second polymer substantially encapsulates the first polymer, has a Tg of from −60° C. to 50° C. and is formed in a presence of the first polymer. In some embodiments the particles comprise from 25% to 33% by weight, based on the weight of the polymeric particles, of the first polymer and from 67% to 75% by weight, based on the weight of the polymeric particles, of the second polymer.
A second aspect of the invention is a process for forming an aqueous dispersion of polymeric particles. The process comprises providing an aqueous dispersion of multi-stage emulsion polymer, where the multi-stage polymer comprises a core stage polymer and a first shell stage polymer; forming a second shell stage polymer, substantially encapsulating the first shell stage polymer, by adding to the aqueous dispersion of multi-staged polymer at least one ethylenically unsaturated monomer and causing the monomer to polymerize in a presence of the multi-staged polymer; and adding a swelling agent to the aqueous dispersion prior to, during, or after the polymerization of the monomers comprising the second shell stage polymer. The core stage polymer comprises, as polymerized units, from 5 to 100% by weight, based on the weight of the core stage polymer, of hydrophilic monoethylenically unsaturated monomer, and from 0 to 95% by weight, based on the weight of the core stage polymer, of at least one nonionic monoethylenically unsaturated monomer. The first shell stage polymer has a Tg of at least 50° C. and comprises, as polymerized units, 0.05 to 90%, and preferably, 0.02 to 35%, by weight, based on the total weight of the first shell polymer, of at least one multi-ethylenically unsaturated monomer
Each of the first polymer and the second polymer includes at least one copolymerized ethylenically unsaturated monomer that can be the same or different. Suitable ethylenically unsaturated monomers include, for example, (meth)acrylic ester monomers, including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, ethyl methacrylate, isodecyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate; (meth)acrylonitrile, and (meth)acrylamide; acetoacetoxyethyl (meth)acrylate; acetoacetoxypropyl (meth)acrylate; 2-(3-oxazolidinyl)ethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate; ethyleneureido-functional monomers; allyl acetoacetate; ethylene; propylene; styrene and substituted styrenes; butadiene; vinyl acetate, vinyl butyrate and other vinyl esters; vinyl monomers, such as vinyl chloride, vinyl toluene, and vinyl benzophenone; and vinylidene chloride. Preferred first polymers and second polymers, independently, are all-(meth)acrylic, predominantly (meth)acrylic, styrene/(meth)acrylic, and vinyl acetate/acrylic, i.e., the polymer composition includes those monomers or classes of monomers. The term “(meth)” followed by another term such as acrylate or acrylamide, as used throughout the disclosure, refers to both acrylates or acrylamides and methacrylates and methacrylamides, respectively.
Each of the first polymer and the second polymer, independently, may contain from 0% to 7.5%, and preferably from 0% to 2.5%, by weight of a copolymerized monoethylenically unsaturated acid monomer, based on the weight of the polymer, such as, for example, acrylic acid; methacrylic acid; crotonic acid; itaconic acid; fumaric acid; maleic acid; monomethyl itaconate; monomethyl fumarate; monobutyl fumarate; maleic anhydride; 2-acrylamido-2-methylpropane sulfonic acid; vinyl sulfonic acid; styrene sulfonic acid; 1-allyloxy-2-hydroxypropane sulfonic acid; alkyl allyl sulfosuccinic acid; sulfoethyl (meth)acrylate; phosphoalkyl (meth)acrylates, such as phosphoethyl(meth)acrylate, phosphopropyl(meth)acrylate, and phosphobutyl(meth)acrylate; phosphoalkyl crotonate, phosphoalkyl maleate; phosphoalkyl fumarate; phosphodialkyl(meth)acrylate; phosphodialkyl crotonate; and allyl phosphate. In some embodiments, both an acid monomer and an amide monomer are incorporated into the second polymer, such as, for example, from 0.1 to 2.5 weight % itaconic acid and from 0.1 to 2.5% by weight acrylamide, each based on the weight of the second polymer.
Multi-ethylenically unsaturated monomers are herein defined as monomers bearing two or more ethylenically unsaturated bonds, such as, for example, allyl methacrylate, diallyl phthalate, 1,4-butyleneglycol dimethacrylate, 1,2-ethyleneglycol dimethacrylate, 1,6-hexanediol diacrylate, and divinyl benzene. Levels of such monomers must be selected, particularly for the second polymer, such that film formation is not materially compromised. In some embodiments, the first polymer comprises from 0.05 to 50%, preferably 0.2 to 35%, more preferably 0.5 to 30%, yet more preferably 1 to 25%, by weight, based on dry polymer weight, of copolymerized multi-ethylenically unsaturated monomers. In other embodiments, the first polymer contains from 0.05% to 5%, by weight based on dry polymer weight, copolymerized multi-ethylenically unsaturated monomers.
The glass transition temperature (“Tg”) of the first polymer is, preferably, greater than 50° C., more preferably, greater than 75° C., and most preferably, greater 90° C. The Tg of the second polymer is from −60° C. to 50° C., preferably −60° C. to 35° C., and more preferably from −20° C. to 20° C. In each instance, the Tg is calculated by using the Fox equation (T. G. Fox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, page 123(1956)). For copolymers comprising more than two different monomer types, the calculation may be expressed as:

1/Tg=Σ[w(Mi)/Tg,(Mi)],

where w(Mi) is the weight fraction of each monomer, and Tg,(Mi) the glass transition temperature of the homopolymer of Mi. For example, for calculating the Tg of a copolymer of monomers M1 and M2,

1/Tg(calc.)=w(M1)/Tg(M1)+w(M2)/Tg(M2), wherein

    Tg(calc.) is the glass transition temperature calculated for the copolymer;
    w(M1) is the weight fraction of monomer M1 in the copolymer;
    w(M2) is the weight fraction of monomer M2 in the copolymer;
    Tg(M1) is the glass transition temperature of the homopolymer of M1; and
    Tg(M2) is the glass transition temperature of the homopolymer of M2, where all temperatures are in Kelvin (K).


The glass transition temperatures of homopolymers may be found in “Polymer Handbook,” 4th edition edited by J. Brandrup, E. H. Immergut, and E. A. Grulke, Wiley-Interscience Publishers (1999).
The aqueous dispersion of polymeric particles of the present invention is typically formed by an emulsion polymerization process. The first polymer and the second polymer are preferably formed by a multistage polymerization process, wherein the second polymer is formed in the presence of the first polymer. In certain embodiments, the first polymer can itself include multiple polymers that may be formed in multiple stages. There may be two or more phases included in the second polymer, as long as each of the phases includes at least one copolymerized ethylenically unsaturated monomer and each has a Tg of from −60° C. to 50° C.
In some embodiments, the concentration of unpolymerized monomer in the reaction vessel is, at any time (T), is no greater than 6%, preferably, no greater than 5%, and more preferably, no greater than 4%, by weight, based on the total weight of reaction mixture present in the reaction vessel at time (T). The formation of the second polymer may be effected in the same reaction vessel or kettle as the formation of the first polymer. It may alternatively be carried out after a period of time in a different reaction vessel or kettle, such as a holding tank or a drain tank.
The polymerization techniques used to prepare aqueous emulsion polymers are well known in the art. In the polymerization of the aqueous dispersion of polymeric particles of this invention, each polymer is prepared independently in the sense that surfactants, initiators, and other additives are selected independently and may be the same or different in kind and amount for each polymer, recognizing, however, that the second polymer is prepared in the presence of previously prepared first polymer. In the emulsion polymerization process, conventional surfactants may be used, such as, for example, anionic and/or nonionic emulsifiers, such as, for example, alkali metal or ammonium salts of alkyl, aryl, or alkylaryl sulfates, sulfonates or phosphates; alkyl sulfonic acids; sulfosuccinate salts; fatty acids; ethylenically unsaturated surfactant monomers; and ethoxylated alcohols or phenols. The amount of surfactant used is usually 0.1% to 6% by weight, based on the weight of monomer.
Free radical polymerization processes, including, for example, thermal, redox, photochemical, and electrochemical initiation, may be used for the formation of the first polymer and the second polymer, independently. In some embodiments, the reaction temperature is maintained at from 5° C. to 65° C. during the formation of at least 10% by weight of the second polymer; a redox polymerization process is preferred during that interval. In certain embodiments, the polymerization of the second polymer is initiated at from 5° C. to 40° C., preferably, from 5° C. to 30° C., and more preferably, from 15° C. to 30° C., and allowed to rise such that during the formation of the at least 10% by weight of the second polymer, the reaction temperature is maintained at from 5° C. to 65° C. The monomer may be added neat, i.e., not an emulsion in water, or as an emulsion in water. The monomer may be added in one or more additions or continuously, linearly or not, over the reaction period, or combinations thereof.
Each of the first stage polymer and second stage polymer, independently, may be formed using suitable free radical initiators (oxidants), such as, for example, hydrogen peroxide; sodium or potassium peroxide; t-butyl hydroperoxide; t-alkyl hydroperoxide, t-alkyl peroxide, or t-alkyl perester wherein the t-alkylgroup includes at least 5 carbon atoms; cumene hydroperoxide; ammonium and/or alkali metal persulfates; sodium perborate; perphosphoric acid and salts thereof; potassium permanganate; and ammonium or alkali metal salts of peroxydisulfuric acid, typically, at a level of 0.01% to 3.0% by weight, based on the weight of monomer. Redox systems using one or more oxidants with a suitable reductant, such as, for example, sodium sulfoxylate formaldehyde; ascorbic acid; isoascorbic acid; alkali metal and ammonium salts of sulfur-containing acids, such as sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfide, hydrosulfide or dithionite; formadinesulfinic acid; hydroxymethanesulfonic acid; sodium 2-hydroxy-2-sulfinatoacetic acid; acetone bisulfite; amines, such as ethanolamine, glycolic acid; glyoxylic acid hydrate; lactic acid; glyceric acid, malic acid; tartaric acid; and salts of the preceding acids may be used. Redox reaction catalyzing metal salts of iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium, or cobalt may be used for the formation of the first polymer and the second polymer. Typical levels of catalytic metal salts used in accordance with the invention range from 0.01 ppm to 25 ppm. Mixtures of two or more catalytic metal salts may also be usefully employed. Chelating ligands, which can be used with catalytic metal salts, include multidentate aminocarboxylate ligands, such as, for example, nitrilotriacetic acid (NTA, a tetradentate ligand), ethylene diamine diacetic acid (EDDA, a tetradentate ligand), N-(hydroxyethyl) ethylene diamine triacetic acid (HEDTA, a pentadentate ligand), ammonia diacetic acid (ADA, a tridentate ligand) and ethylene diamine tetraacetic acid (EDTA, a hexadentate ligand).
Chain transfer agents, such as, for example, halogen compounds, including tetrabromomethane; allyl compounds; or mercaptans, such as alkyl thioglycolates, alkyl mercaptoalkanoates, and C4-C22 linear or branched alkyl mercaptans may be used to lower the molecular weight of the formed first polymer and second polymer, independently, and/or to provide a different molecular weight distribution than would otherwise have been obtained with any free-radical-generating initiator(s). Chain transfer agent(s) may be added in one or more additions or continuously, linearly or not, over most or all of the entire reaction period or during limited portion(s) of the reaction period.
The polymeric particles of the aqueous dispersion have an average particle diameter of from 200 to 1500 nanometers (nm), preferably of from 200-600 nm. Also contemplated are multimodal particle size emulsion polymers, where one or more of the particle size modes are polymeric particles of the present invention and wherein two or more distinct particle sizes or very broad distributions are provided, as is taught in U.S. Pat. Nos. 5,340,858; 5,350,787; 5,352,720; 4,539,361; and 4,456,726.
In some embodiments, the particles of the first polymer are uniform in composition. However, in certain embodiments, the particles of the first polymer include more than one phase and may be effected, for example, by a multistage emulsion polymerization. A multistage emulsion polymerization process in which at least two stages differing in composition are polymerized in sequential fashion usually results in the formation of at least two mutually incompatible polymer compositions, thereby resulting in the formation of at least two phases within the polymer particles. Such particles are composed of two or more phases of various geometries such as, for example, core/shell or core/sheath particles, core/shell particles with shell phases partially encapsulating the core, core/shell particles with a multiplicity of cores, and interpenetrating network particles. The multistage emulsion polymer can be formed in two or more stages, where the stages differ in molecular weight as well as, or in addition to, differ in composition.
The first polymer particles include, when dry, at least one void. First polymer particles, which include a single void formed by multistage emulsion polymerization, are known in the art and disclosed in U.S. Pat. Nos. 4,427,836; 4,469,825; 4,594,363; 4,880,842; 4,970,241; 4,677,003; 4,985,064; 5,225,279; 5,494,971; 5,545,695; 5,510,422; 5,527,613; 6,020,435; 6,252,004; 6,139,961; 6,673,451; and 6,784,262. The first polymer particles of the invention are also disclosed in published U.S. Publication Nos. 20010009929; 20010036990; and 20030129435. Suitable first polymer particles may also contain, when dry, multiple voids; by “multiple voids” herein is meant two or more voids, whether isolated or connected to other voids, whether substantially spherical in shape or not, including, for example, void channels, interpenetrating networks of void and polymer, and sponge-like structures, such as are disclosed, for example, in U.S. Pat. Nos. 5,036,109; 5,157,084; 5,216,044; and 5,989,630. Multiple voids may be formed within a first polymeric particle fully or partially enclosed by a shell polymer. In alternative embodiments, first polymer particles include one or more core polymer(s) that can be dissolved out of the first polymer particle to form, when dry, a void. In additional embodiments, first polymer particles, including or previously including pigment particles, such as, for example, titanium dioxide and silicon oxide, supercritical carbon dioxide, FREONTM, and oxidizable compounds are also contemplated. It is preferred that the predominant amount of the outermost polymeric surface of the first polymer particle has a Tg of greater than 50° C., preferably greater than 75° C., and more preferably greater 90° C.
In some embodiments, the first polymer with at least one void, when dry, may be formed according to the methods of U.S. Pat. No. 6,632,531. In such embodiments, a first polymer of the invention is preferably formed in the presence of at least one fugitive substance, i.e., any substance having a normal boiling point of less than 30° C., and the second polymer of the invention is polymerized in the presence of the first polymer. In such embodiments, the second polymer may be formed either before or after the removal of the fugitive substance.
In such embodiments, a fugitive substance is preferably selected from the group consisting of carbon dioxide, 2,2-dimethylypropane, dichlorofluoromethane, 1,2-dichlorotetrafluoroethane, butane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, dimethyl ether, 1,1-difluoroethane, octafluoropropane, chlorodifluoromethane, propane, pentafluoroethane, difluoromethane, sulfur hexafluoride, hexafluoroethane, carbon dioxide, chlorotrifluoromethane, trifluoromethane, ethane, tetrafluoromethane, methane, difluoromethane, hexafluoroethane, carbon dioxide, chlorotrifluoromethane, trifluoromethane, ethane, tetrafluoromethane, methane, and combinations thereof.
It is preferred that void size be in the range of from 100 to 1200 nm. In some embodiments where the inventive particles increase the opacity of films in which they are present, it is preferred that void size be in the range of from 200 to 600 nm, and more preferably 250 to 450 nm. In some embodiments, for instance, where the inventive particles are used in paper coatings, particularly in applications where the paper coatings undergo calendaring to improve gloss, it is preferred that void size be in the range of from 750 to 1200 nm, and more preferably 1000 to 1200 nm.
Aqueous dispersions comprising the inventive particles may further comprise from 5 to 95%, preferably, 5 to 50%, and more preferably, 5 to 35%, by weight, based on the total polymeric weight of the dispersion, unvoided, or solid particles. The unvoided particles may have Tg values ranging from −50° C. to 50° C. and typically have particle sizes of from less than 10 nm to more than 1000 nm, preferably from 30 to 500 nm, and more preferably from 40 to 200 nm. In such embodiments, there may be populations of voided particles having different mean particle sizes, i.e., bimodal or polymodal particle size distributions. In some embodiments, for example, when the inventive dispersions are used in the formulation of coatings that can be applied to aged or weathered substrates, it may be desirable to have from 20 to 35% by weight, based on the total polymeric content of the dispersion, of unvoided particles having a particle size of from 10 to 100 nm, and preferably 40 to 80 nm.
The polymeric particles of the invention include a first polymer and a second polymer substantially encapsulating the first polymer. “Substantially encapsulating the first polymer” means that greater than 50% of the surface area of the first polymer particle must be covered by the second polymer. Preferably, greater than 75%, and more preferably 100%, of the surface area of the first polymer particle is covered by the second polymer. The extent of coverage or encapsulation of the polymeric particles may be determined by scanning electron microscopy, with or without staining techniques, as is well-known in the art.
The aqueous dispersion of polymeric particles typically has a solids content of greater than 30%, and preferably, greater than 40%, by weight. The presence of polymer particles having a particle size smaller than the inventive particles may produce dispersions with solids content approaching 70% or more. Further, high solids content, or the presence of smaller particles, or combinations of both, may prevent settling or sedimentation of the inventive particles. High solids content herein refers to solids contents of greater than 50%, and preferably, greater than 60%, by weight.
The present invention in one embodiment serves to provide an aqueous coating composition suitable for use, when dry, as a coating, “coating” herein, including, for example, paint, clearcoat, topcoat, primer, paper coating, leather coating, textile and nonwoven fabric coating and saturant, elastomeric coating, caulk, sealant, and adhesive. Such a coating typically exhibits improvement in film formation, particularly at temperatures lower than 30° C. or at VOC levels below 5% by weight, based on the total weight of the aqueous coating composition, and/or film integrity, relative to a coating in which an aqueous dispersion of similar polymeric particles having a first polymer comprising less than 0.05% by weight, based on the weight of the first polymer, copolymerized multi-ethylenically unsaturated monomer.
The inventive polymers may be used advantageously as binders in the formulation of pigmented coatings. “Binder,” as used herein, refers to a component in a formulation that provides integrity to films formed by the drying of the formulation. In relatively low PVC coating formulations, the binder may achieve this effect by forming a fairly continuous film in which the other components, including pigments and extenders, are embedded. The binder may also act to form points of adhesion between particles of other components in the formulation, for instance, pigments and extenders. This binding mechanism is more common in relatively high PVC formulations where the binder may not be present in a quantity adequate to form a continuous film. Dispersions of polymeric particles are commonly used as binders in aqueous coatings formulations. Typically, binder particles are of such character as to be film-forming at the temperature at which the formulation is dried. Alternately, solvents or coalescents may be added to soften binder particles as to cause them to be film-forming.
Pigmented coating formulations using the inventive polymer particles as binders may provide greater opacity than analogous formulations using traditional non-voided polymer particles as binder. Alternately, a formulator may achieve a desired level of opacity in coating formulations using the particles of the invention as binder by using a lower level of pigment and/or extender than would be required to achieve the same level of opacity in a comparable formulation using traditional non-voided polymer particles as binder.
An aqueous coating composition having the aqueous dispersion of the invention is prepared by techniques that are well known in the coatings art. First, if the aqueous coating composition is to be pigmented, at least one pigment is typically well dispersed in an aqueous medium under high shear, such as is afforded by a COWLES® mixer. Then, the aqueous dispersion of polymeric particles is added under lower shear stirring, along with other coating adjuvants as desired. Alternatively, the aqueous dispersion of polymeric particles may be included in the pigment dispersion step. The aqueous coating composition may contain conventional coating adjuvants, such as, for example, tackifiers, pigments, extenders, emulsifiers, crosslinkers, coalescing agents, buffers, neutralizers, thickeners or rheology modifiers, humectants, wetting agents, biocides, plasticizers, antifoaming agents, colorants, waxes, and anti-oxidants. The aqueous coating composition may contain up to 75% by weight, based on the weight of the polymeric particles, of an emulsion polymer not meeting the description of the aqueous dispersion of polymeric particles of the invention, such as a film-forming and/or a non-film-forming emulsion polymer.
Examples of suitable pigments and extenders for use in the formulation of coatings include titanium dioxide, such as anatase and rutile titanium dioxides; zinc oxide; antimony oxide; iron oxide; magnesium silicate; calcium carbonate; organic and inorganic colored pigments; aluminosilcates; silica; various clays, such as kaolin and delaminated clay; and lead oxide. The amounts of pigment and extender in the aqueous coating composition vary from a pigment volume concentration (PVC) of 0 to 95 and thereby encompass coatings otherwise described in the art, for example, clear coatings, stains, flat coatings, satin coatings, semi-gloss coatings, gloss coatings, primers, and textured coatings. The pigment volume concentration is calculated by the following formula:




  
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In one embodiment, the aqueous coating composition includes a photosensitive moiety. The photosensitive moiety is capable of absorbing some portion of the solar light spectrum and, without being bound by a particular theory, potentially acting as a photoinitiator for crosslinking of the polymer during exterior exposure. The photosensitive moiety can be a photosensitive compound added to the aqueous coating composition before, during, or after the formation of the aqueous dispersion, or a photosensitive group that is chemically incorporated into one or more of the polymers, preferably the second polymer, of the aqueous dispersion of polymeric particles, for example, by copolymerization. Examples of photosensitive compounds are benzophenone derivatives, wherein one or both of the phenyl rings are substituted, such as, for example, benzophenone, 4-methyl benzophenone, 4-hydroxy benzophenone, 4-amino benzophenone, 4-chloro benzophenone, 4-hydroxycarboxyl benzophenone, 4,4′-dimethyl benzophenone, 4,4′-dichloro benzophenone, 4-carboxymethyl benzophenone, 3-nitro benzophenone, and substituted phenyl ketones, such as substituted phenyl acetophenones. The photosensitive groups may be present in one or more of the stages as copolymerized ethylenically unsaturated monomers that contain photosensitive groups. Examples of ethylenically unsaturated monomers that contain photosensitive groups include vinyl toluene, allyl benzoylbenzoates and monomers incorporating pendant benzophenonegroups, such as vinylbenzyl methylbenzoylbenzoate, hydroxymethacryloxypropyl methylbenzoylbenzoate, hydroxymethacryloxypropyl benzoylbenzoate, and hydroxymethacryloxypropoxy benzophenone. A preferred photosensitive compound is benzophenone. The aqueous coating composition may contain from 0.1 to 5%, preferably, from 0.1 to 3%, and more preferably, 0.1 to 1% by weight of one or more photosensitive compounds, based on dry polymer weight.
Preferably, the aqueous coating composition contains less than 5% VOC by weight, more preferably less than 3% VOC, and even more preferably less than 1.7% VOC by weight, based on the total weight of the aqueous coating composition. A volatile organic compound (VOC) is defined herein as a carbon-containing compound that has a boiling point below 280° C. at atmospheric pressure.
Additionally, the aqueous coating composition may contain coalescing agents, some of which are not VOCs, e.g., coalescing agents having a boiling point above 280° C. at atmospheric pressure. A coalescing agent is a compound that is added to an aqueous dispersion of polymeric particles, paint or coating and which reduces the minimum film forming temperature (MFFF) of the aqueous dispersion of polymeric particles or aqueous coating composition by at least 1° C. The MFFT is measured using ASTM test method D2354. Examples of coalescing agents that are not VOCs include plasticizers, low molecular weight polymers, surfactants, and autooxidizable plasticizers, such as alkyl esters of unsaturated fatty acids. Preferred are alkyl esters prepared from oils, such as linseed, tung, dehydrated castor, soybean, tall, sunflower, and corn. Examples of non-VOC coalescing agents include esters of unsaturated fatty acids, such as mono, di-, or tri-unsaturated fatty acids. Suitable unsaturated fatty acid esters include monounsaturated fatty acid esters formed from palmitoleic acid, oleic acid, or caproleic acid; diunsaturated fatty acid esters formed from linoleic acid; triunsaturated fatty acid esters formed from linolenic acid or eleosteric acid; or mixtures thereof. Suitable esters of unsaturated fatty acids includes alkyl esters, such as methyl and ethyl esters; substituted alkyl esters, such as esters formed from ethyleneglycol and propyleneglycol and alkyl ether esters of unsaturated fatty acids; diethyleneglycol, triethyleneglycol; dipropyleneglycol; tripropyleneglycol; and diethyleneglycol monobutyl ether. In one embodiment, the above autooxidizable plasticizers are used in conjunction with an aqueous dispersion of polymeric particles which contain 0.25% to 12.5% of acetoacetoxyethyl (meth)acrylate as copolymerized units, based on the total weight of the polymeric particles. Autooxidation can be enhanced by the use of metal ion catalysts, such as cobalt, zirconium, calcium, manganese, copper, zinc and iron. Simple salts, such as halides, nitrates, and sulfates may be used, but in many cases, an organic anion, such as acetate, naphthenate or acetoacetate, is used.
Typical methods of paint or coating preparation may introduce adventitious VOCs from the aqueous dispersion of polymeric particles, biocides, defoamers, soaps, dispersants, and thickeners. These typically account for 0.1% VOC by weight, based on the total weight of the aqueous coating composition. Additional methods such as, for example, steam stripping of the aqueous dispersion of polymeric particles and selection of low VOC containing additives, such as biocides, defoamers, soaps, dispersants, and thickeners, may be used to further reduce the paint or coating to less than 0.01% VOC by weight, based on the total weight of the aqueous coating composition.
The solids content of the aqueous coating composition may be from 10% to 85% by volume. The viscosity of the aqueous composition may be from 0.05 to 2000 Pa·s (50 cps to 2,000,000 cps), as measured using a Brookfield viscometer; the viscosities appropriate for different end uses and application methods vary considerably.
The aqueous coating composition may be applied by conventional application methods, such as, for example, brush or paint roller, air-atomized spray, air-assisted spray, airless spray, high volume low pressure spray, air-assisted airless spray, and electrostatic spray. The aqueous coating composition may be applied to a substrate, such as, for example, plastic, including sheets and films; glass; wood; metal, such as aluminum, steel, and phosphate or chromate-treated steel; previously painted surfaces; weathered surfaces; cementitious substrates; and asphaltic substrates, with or without a prior substrate treatment, such as a primer. The aqueous composition coated on the substrate is typically dried, or allowed to dry, at a temperature from 5° C. to 95° C.
A preferred process for forming dispersions of the invention wherein the first polymer comprises, when dry, at least one void is analogous to that disclosed in published U.S. Publication No. 20010009929. In the preferred process of the invention, there is provided an aqueous dispersion of multi-stage emulsion polymer, comprising a core stage polymer (the “core”) and a first shell stage polymer (the “first shell”). The core and first shell may themselves be comprised of more than one stage. There may also be one or more intermediate stages. Preferably, the multi-stage polymer comprises a core, an intermediate layer and a shell. The intermediate layer is as described in U.S. Publication No. 20010009929.
According to the preferred process, a second shell stage polymer (the “second shell”), which substantially encapsulates the first shell stage polymer, is subsequently formed by adding to the emulsion of multi-staged polymer at least one mono-ethylenically unsaturated monomer and causing at least 10% of the monomer to polymerize, at a temperature of from 5° C. to 65° C., in the presence of the multi-staged polymer. This temperature is at least 30° C. lower than the calculated Tg of the first shell stage polymer. The core of the multi-stage emulsion polymer is caused to swell by the addition of a swelling agent to the aqueous dispersion prior to, during, or after the polymerization of the monomers comprising the second shell stage polymer.
In this process, the first shell stage polymer has the characteristics herein attributed to the first polymer of the invention and the second shell stage polymer has the characteristics herein attributed to the second polymer of the invention. Preferably, the first stage shell polymer has a calculated Tg of at least 50° C. and comprises, as polymerized units, at least 50% by weight of nonionic monoethylenically unsaturated monomer.
The cores of the multi-stage polymers used in the preferred process are as described in U.S. Publication No. 20010009929. The cores, preferably, are emulsion polymers comprising, as polymerized units, from 5 to 100% by weight, based on the weight of the core, of at least one hydrophilic monoethylenically unsaturated monomer and from 0 to 95% by weight, based on the weight of the core stage polymer, of at least one nonionic monoethylenically unsaturated monomer.
The core, whether obtained by a single stage process or a process involving several stages, has an average particle size diameter of from 50 nm to 1.0 micron, and preferably, from 100 nm to 300 nm, in an unswollen condition. If the core is obtained from a seed polymer, such as one described in US Publication No. 20010009929, the seed polymer, preferably, has an average particle size of from 30 nm to 200 nm. The core may also optionally contain less than 20% by weight, and preferably from 0.1 to 3% by weight, based on the total weight of the core, of multi-ethylenically unsaturated monomer.
Within the context of the preferred process, suitable hydrophilic monoethylenically unsaturated monomers useful for making the core polymer include monoethylenically unsaturated monomers containing acid-functionality, such as monomers containing at least one carboxylic acid group, including acrylic acid, methacrylic acid, acryloxypropionic acid, (meth)acryloxypropionic acid, itaconic acid, aconitic acid, maleic acid or anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate. Acrylic acid and methacrylic acid are preferred.
One or more swelling agents may be used in the process. Suitable swelling agents include those which, in the presence of the multistage emulsion polymer and monomer, are capable of permeating shell polymers and swelling the core. Swelling agents may be aqueous or gaseous, volatile or fixed bases, or combinations thereof.
Suitable swelling agents include volatile bases, such as ammonia, ammonium hydroxide, and volatile lower aliphatic amines, such as morpholine, trimethylamine, and triethylamine; fixed or permanent bases, such as potassium hydroxide, lithium hydroxide, zinc ammonium complex, copper ammonium complex, silver ammonium complex, strontium hydroxide, and barium hydroxide. Solvents, such as, for example, ethanol, hexanol, octanol, Texanol® solvent and those described in U.S. Pat. No. 4,594,363, may be added to aid in fixed or permanent base penetration. Ammonia and ammonium hydroxide are preferred.
The core of the multi-stage emulsion polymer used in the preferred process may be caused to swell by the addition of a swelling agent to the aqueous dispersion prior to, during, or after the polymerization of the monomers comprising the second shell stage polymer, but after the formation of the first shell polymer. In a preferred embodiment, swelling agent is added to the aqueous dispersion at a time when the aqueous dispersion comprises at least 0.5% by weight, based on the total polymeric content of polymer in the dispersion, of unreacted monomer under conditions where there is no substantial polymerization of the monomer; and subsequently reducing the level of monomer by at least 50%. The phrase “under conditions wherein there is no substantial polymerization of the monomer” and the techniques for achieving such conditions are as described in U.S. Publication No. 20010009929.
Preferably, the amount of swelling agent is in the range of from 75 to 300%, and more preferably in the range of from 90 to 250%, based on the equivalents of the functionality in the core capable of being neutralized. It is also preferable to add the one or more swelling agents to the multistage emulsion polymer while the multistage emulsion polymer is at an elevated temperature, preferably at a temperature within 10° C. of the shell polymerization temperature. Swelling is generally very efficient, i.e., swelling in minimum amount of time under conditions of elevated temperature in the presence of monomer and no substantial polymerization occurring. Under these conditions, swelling is generally complete within 30 minutes, preferably within 20 minutes, and most preferably within 10 minutes, of adding the one or more swelling agents.
After swelling the multistage emulsion polymer in the presence of both monomer and swelling agent, it is desirable to reduce the level of monomer to less than 10,000 ppm, and preferably to less than 5,000 ppm, based on polymer solids. This can be accomplished by any suitable means. Preferably, the level of monomer is reduced by polymerizing the monomer. This can be accomplished by any suitable means, such as by adding one or more initiators recited above. It is preferred to begin to reduce the level of monomer within 20 minutes, and more preferably within 10 minutes, of adding the one or more swelling agents.
The following examples are presented to illustrate the invention. In the examples, the following abbreviations have been used:

    BA is Butyl Acrylate;
    MMA is Methyl Methacrylate;
    MAA is Methacrylic Acid;
    t-BHP is t-Butyl Hydroperoxide (70%);
    SDS is Sodium Dodecylbenzenesulfonate (23%);
    DI is Deionized;
    SPS is Sodium Persulphate;
    ALMA is Allyl Methacrylate;
    L is liter; wt is weight; vol is volume; g is gram; and min is minute.

Test Methods



Particle size: Measurements were made by CHDF using Matec CHDF-2000 (capillary hydrodynamic fractionation); Matec Applied Sciences, Northborough, Mass.
S/Mil Determination: An aqueous dispersion was drawn down over a black vinyl scrub chart. The wet film was dried at 30% relative humidity. A Kubelka-Munk scattering coefficient was determined on the dry film ( ̃2 mil thick) by the method of P. B. Mitton and A. E. Jacobson (Off. Digest, September 1963, p. 871-911). S/mil is measured using a Y-reflectometer with a 45/0 geometry. A Y-reflectometer is a light reflectance meter that measures the Y component of the XYZ color scale. A 45/0 geometry indicates that the light is incident to the coating at an angle of 45 degrees from normal, and that the scattered light is collected at an angle of 0 degrees from normal.
Scrub Resistance: The aqueous coating compositions were drawn down on black vinyl charts using a 7 mil opening film caster. The charts were air dried in a horizontal position for 7 days in an open room kept at 73.5° F. (23° C.)+/−3.5° and 50+/−5% relative humidity. Cut-through scrub resistance that measures the scrub resistance of a paint film by the number of scrub cycles required to erode the paint film to the substrate was determined. The procedure used a nylon bristle brush and a scrub medium prepared by blending an abrasive scrub medium type SC-2 from The Leneta Company, Inc. (Mahwah, N.J.), water and defoamer. The paint charts were secured in the abrasion tester on an aluminum plate containing shims. The brush was mounted in the holder and 10 g of scrub medium were spread evenly on the brush bristles. The cycle counter was set at zero and the test was started. After each 400 cycles before failure, 10 more grams of scrub medium was added. The number of cycles to remove the paint film fully in one continuous line across a 1⁄2 inch width of the shim was recorded. The reported values were an average of eight measurements.
BCOP hiding factor: A sample of the aqueous dispersion to be tested is blended with a BCOP (Binder Coated Opaque Polymer) Reference Dispersion (defined below). The relative quantities of the test dispersion and BCOP Reference Dispersion are selected such that the resultant blend comprises 30% by weight, based on the total polymer weight of the blend, of polymer solids from the test binder, and 70% by weight, based on the total polymer weight of the blend, of polymer solids from the BCOP Reference Dispersion. A 7 mil wet film of the blend is drawn down over a black vinyl scrub chart (Leneta # P121010N). The black vinyl scrub chart has been measured for thickness (in mils) in four defined areas using, for example, an Ames gauge (#2-212C) available from the Ames Corporation of Waltham, Mass. The film is dried for two hours in a low relative humidity (<40% Relative Humidity, where if Relative Humidity is any %<40% during drying, BCOP hiding factor will not change substantially) chamber or room. The reflectance of the dry film is measured by a reflectometer, for instance, a Gardner Instrument Reflectometer (BYK-Gardner of Columbia, Md.), over the four defined areas. The thickness of the film is also determined over each of the defined areas using the Ames gauge. The BCOP hiding factor is calculated for each of the four defined areas as:




  
    BCOP
    ⁢
    
      
    
    ⁢
    hiding
    ⁢
    
      
    
    ⁢
    factor
  
  =
  
    R
    
      
        (
        
          1
          -
          R
        
        )
      
      ⨯
      t
    
  




    where R=reflectance; and
    t=film thickness in mils.


The average of the four measurements is taken as the BCOP hiding factor for the dried film. Preferably, in the invention, the BCOP hiding factor is at least 0.1.
BCOP 80% hiding factor: The procedure and calculation as described for the determination of the BCOP hiding factor are reproduced with the exception that the film is dried overnight at 25° C./80% Relative Humidity in a temperature/humidity chamber (Hotpack, Model #417532 available from SP Industries, Inc. of Warminster, Pa.) and then dried at <40% Relative Humidity for one hour in a low humidity chamber/room.
BCOP Stability Factor:
BCOP stability factor=1−(BCOP 80% hiding factor/BCOP hiding factor)
In the invention, preferably, the BCOP stability factor is less than 0.5
BCOP Reference Dispersion
The BCOP Reference Dispersion is formed by the following process: 936 g BA, 840.6 g MMA, 23.4 g AA, and 82.7 g of a 30% aqueous solution of polyethyleneglycol lauryl ether sodium sulfate were combined with 674 g of deionized water and the mixture was agitated with a hand-held homogenizer for 30 seconds to form an emulsion. 938 g of deionized water and 3.6 g of a 30% aqueous solution of polyethyleneglycol lauryl ether sodium sulfate were added to a 4 neck 5 L round bottom glass kettle equipped with temperature control, condenser, and mechanical agitation. The kettle was heated to 85° C. under nitrogen while stirring. With the kettle temperature at 85° C., a 76 g aliquot of the homogenized monomer emulsion was added to the kettle, immediately followed by 7.2 g of APS dissolved in 20 g of water. The resulting mixture was held with agitation for 5 min. The remaining monomer emulsion was then fed to the kettle over approximately 80 min while maintaining the reaction temperature at 85° C.
Upon completion of the monomer emulsion feed, the contents of the kettle were held at 85° C. for an additional 10 min before being allowed to cool to 60° C. 20 g of 0.10 wt % iron sulfate solution were added to the kettle followed by the addition of 3.6 g of 70% t-butyl hydroperoxide dissolved in 58 g of water and 1.8 g of iso-ascorbic acid dissolved in 58 g of water over approximately 30 min. The kettle was allowed to cool to ambient temperature. At 30° C., the pH of the emulsion was adjusted to pH 9 by addition of ammonium hydroxide. The emulsion was removed from the kettle and filtered. The final latex was 49.0 wt % solids. Particle size was 106 nm.


EXAMPLES
Example 1
Preparation of polymer cores for preparation of first polymer: A 66 MMA/34 MAA wt % polymer core was prepared according to the teachings of Examples 1-16 of U.S. Pat. No. 6,020,435.
Core #1 The filtered dispersion had a solids content of 31.9 wt % and an average particle size of 108 nm.
Core #2 The filtered dispersion had a solids content of 31.8 wt % and an average particle size of 127 nm.
Core #3 The filtered dispersion had a solids content of 30.8 wt % and an average particle size of 139 nm.
Example 2
Preparation of first polymer(neutralized): A 5 L, four necked round bottom flask was equipped with paddle stirrer, thermometer, nitrogen inlet, and reflux condenser. DI water, 1000 g, was added to the kettle and heated to 89° C. under a nitrogen atmosphere. To the heated kettle water was added 3.7 g SPS in 30 g DI water. This was immediately followed by 219.4 g of Core #1 (Example 1). A monomer emulsion I (ME I), which was prepared by mixing 70 g DI water, 4.7 g SDS, 70.0 g styrene, 61.6 g MMA, and 8.4 g MAA, was added to the kettle over a period of 60 min at 78° C. Upon completion of ME I, a second monomer emulsion (ME II) was prepared by mixing 218.0 g DI water, 9.3 g SDS, 657.3 g styrene, 12.6 g MAA, 4.2 g linseed oil fatty acid, and 2.1 g ALMA. Monomer Emulsion II (ME II) was added to the kettle along with a separate mixture of 0.93 g SPS dissolved in 60 g DI water over 60 min. The temperature of the reaction mixture was allowed to increase to 92° C. Upon completion of the ME HII and co-feed, 22 g of a solution of 0.1% iron sulfate and 1% versene in water was added to the kettle. Next, a third monomer emulsion (ME III) which was prepared by mixing 54.0 g DI water, 2.0 g SDS, 168 g styrene, and 2.0 g 4-hydroxy TEMPO was added to the kettle. This was followed by the addition of 500 g hot DI water (90° C.). With the kettle temperature of  ̃85° C., a solution of 31.0 g 50% sodium hydroxide dissolved in 600 g hot DI water added to the kettle over 10 min. 10 min after the completion of the sodium hydroxide addition, a solution of 1.0 g SPS mixed with 20 g DI water was added to the kettle and the batch was held for 30 min at 85° C. The reaction mixture was then cooled to room temperature and filtered. The final neutralized latex had a solids content of 26.4 wt %, a particle diameter of 398 nm, and a pH of 8.3.
Example 3
Preparation of first polymer (unneutralized): A 5 L, four necked round bottom flask was equipped with paddle stirrer, thermometer, nitrogen inlet, and reflux condenser. DI water, 1200 g, was added to the kettle and heated to 89° C. under a nitrogen atmosphere. To the heated kettle water was added 5.25 g SPS dissolved in 30 g DI water. This was immediately followed by 314.5 g of Core #2 (Example 1). A ME I, which was prepared by mixing 100 g DI water, 6.7 g SDS, 100 g styrene, 88.0 g MMA, and 12 g MAA, was added to the kettle over a period of 60 min at 78° C. Upon completion of ME I, a ME II was prepared by mixing 400 g DI water, 18 g SDS, 1179 g styrene, 18.0 g MAA, 6 g linseed oil fatty acid, and 3.0 g ALMA. ME II was added to the kettle along with a separate mixture of 1.3 g SPS dissolved in 90 g DI water over 60 min. The temperature of the reaction mixture was allowed to increase to 92° C. Upon completion of the ME II and co-feed, the reaction mixture was held for 30 min at 85° C. and then cooled to room temperature and filtered to remove any coagulum formed. The final unneutralized latex had a solids content of 39.9 wt %, an average particle diameter of 375 nm, and a pH of 2.2.
Example 4
Preparation of first polymer (unneutralized): A first polymer was prepared using 315 g of Core #1 (Example 1) following the procedure used in Example 3. The final unneutralized latex had a solids content of 39.8 wt %, an average particle diameter of 315 nm, and a pH of 2.1.
Example 5
Preparation of first polymer (unneutralized): A first polymer was prepared using 315 g of Core #3 (Example 1) following the procedure used in Example 3. The final unneutralized latex had a solids content of 40.1 wt %, an average particle size of 350 nm, and a pH of 2.2.
Example 6
Preparation of first polymer (unneutralized): A 5 L, four necked round bottom flask was equipped with paddle stirrer, thermometer, nitrogen inlet, and reflux condenser. DI water, 1200 g, was added to the kettle and heated to 89° C. under a nitrogen atmosphere. To the heated kettle water was added 5.25 g SPS dissolved in 30 g DI water. This was immediately followed by 314.5 g of Core #3 (Example 1). A ME I, which was prepared according to Example 3, was added to the kettle over a period of 60 min at 78° C. Upon completion of ME I, a ME II was prepared according to Example 3. MEII was added to the kettle along with a separate mixture of 1.3 g SPS dissolved in 90 g DI water over 60 min. The temperature of the reaction mixture was allowed to increase to 92° C. Upon completion of the ME II and co-feed, the reaction mixture was held for 30 min at 85° C. and then cooled to room temperature and filtered. The final unneutralized latex had a solids content of 40.0 wt %, an average particle diameter of 380 nm, and a pH of 2.2.
Example 7
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, DI water, 700 g, was added to the kettle and heated to 85° under a nitrogen atmosphere. 1704 g of the first polymer of Example 2 was added to the kettle and the temperature was adjusted to 60° C. A monomer emulsion (ME) was prepared by mixing 270 g DI water, 15.0 g SDS, 378 g MMA, and 522 g BA. With the kettle temperature at 60° C., a solution of 20 g 0.1% ferrous sulfate mixed with 2 g 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.3 g t-BHP mixed with 80 g DI water, along with a separate solution of 1.8 g iso-ascorbic acid mixed with 80 g DI water, were both added to the kettle at a rate of 0.5 g/min. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle over 120 min. There was no external heat applied to the reaction. The temperature of the kettle was kept at 60° C. for the duration of the ME feed. Upon completion of the ME feed, the co-feed solutions were continued for another 30 min. The dispersion was then cooled to 25° C. and filtered. The filtered dispersion had a solids content of 34.8 wt %, and an average particle diameter of 526 nm.
Example 8
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, DI water, 700 g, was added to the kettle and heated to 85° C. under a nitrogen atmosphere. 1704 g of the first polymer of Example 2 was added to the kettle and the temperature was adjusted to 50° C. An ME was prepared by mixing 270 g DI water, 15.0 g SDS, 378 g MMA, and 522 g BA. With the kettle temperature at 50° C., a solution of 20 g 0.1% ferrous sulfate mixed with 2 g 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.3 g t-BHP mixed with 80 g DI water, along with a separate solution of 1.8 g iso-ascorbic acid mixed with 80 g DI water, were both added to the kettle at a rate of 0.5 g/min. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle over 120 min. There was no external heat applied to the reaction. The temperature of the kettle was kept at 500 for the duration of the ME feed. Upon completion of the ME feed, the co-feed solutions were continued for another 30 min. The dispersion was then cooled to 25° C. and filtered. The filtered dispersion had a solids content of 35.5 wt %, and an average particle size of 493 nm.
Example 9
Formation of aqueous dispersion of polymeric particles: Example 8 was repeated except that DI water, 700 g, was added to the kettle and heated to 76° C. under a nitrogen atmosphere. After 1704 g of the first polymer of Example 2 was added to the kettle, the temperature was adjusted to 40° C. The temperature of the kettle was kept at 40-44° C. for the duration of the ME feed. The filtered dispersion had a solids content of 34.6 wt %, and an average particle size of 508 nm. The Kubelka-Munk scattering coefficient (S/Mil) was measured on the dried polymer film and found to be 0.89.
Example 10
Formation of aqueous dispersion of polymeric particles: Example 8 was repeated except that DI water, 700 g, was added to the kettle and heated to 66° C. under a nitrogen atmosphere. After 1704 g of the first polymer of Example 2 was added to the kettle, the temperature was adjusted to 30° C. The temperature of the kettle was allowed to increase to 58° C. over the duration of the ME feed. The filtered dispersion had a solids content of 34.5 wt %, and an average particle size of 490 nm. The Kubelka-Munk scattering coefficient (S/Mil) was measured on the dried polymer film and found to be 1.07.
Example 11
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 5 was added to the kettle and the temperature was adjusted to 25° C. A monomer emulsion (ME) was prepared by mixing 270 g DI water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the kettle temperature at 25° C., a solution of 20 g 0.1% ferrous sulfate mixed with 2 g 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g t-BHP mixed with 80 g DI water, along with a separate solution of 2.0 g iso-ascorbic acid mixed with 80 g DI water, were both added to the kettle at a rate of 0.5 g/min. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 40 min, the ME feed rate was increased to 10 g/min. Upon completion of 90% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 68 C. Next, 900 g hot DI water (90° C.) was added to the kettle. The ME feed was then resumed at a rate of 30 g/min until completion. Immediately after completion of the ME feed, 32 g ammonium hydroxide (28%) was added to the kettle. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered. The filtered dispersion had a solids content of 38.3 wt %, and an average particle diameter of 446 nm. The Kubelka-Munk scattering coefficient (S/Mil) was measured on the dried polymer film and found to be 0.92.
Example 12
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 5 was added to the kettle and the temperature was adjusted to 30° C. A ME was prepared by mixing 270 g DI water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the kettle temperature at 30° C., a solution of 20 g 0.1% ferrous sulfate mixed with 2 g 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g t-BHP mixed with 80 g DI water, along with a separate solution of 2.0 g iso-ascorbic acid mixed with 80 g DI water, were both added to the kettle at a rate of 0.5 g/min. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 40 min, the ME feed rate was increased to 10 g/min. Upon completion of 90% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 72° C. Next, 900 g hot DI water (90° C.) was added to the kettle. The ME feed was then resumed at a rate of 30 g/min until completion. Immediately after completion of the ME feed, 32 g ammonium hydroxide (28%) was added to the kettle. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered. The filtered dispersion had a solids content of 38.5 wt %, and an average particle diameter of 461 nm. The Kubelka-Munk scattering coefficient (S/Mil) was measured on the dried polymer film and found to be 0.85.
Example 13
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 5 was added to the kettle and the temperature was adjusted to 40° C. A ME was prepared by mixing 270 g DI water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the kettle temperature at 40° C., a solution of 20 g 0.1% ferrous sulfate mixed with 2 g 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g t-BHP mixed with 80 g DI water, along with a separate solution of 2.0 g iso-ascorbic acid mixed with 80 g DI water, were both added to the kettle at a rate of 0.5 g/min. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 40 min, the ME feed rate was increased to 10 g/min. Upon completion of 90% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 73° C. Next, 900 g hot DI water (90° C.) was added to the kettle. The ME feed was then resumed at a rate of 30 g/min until completion. Immediately after completion of the ME feed, 32 g ammonium hydroxide (28%) was added to the kettle. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered. The filtered dispersion had a solids content of 38.5 wt %, and an average particle diameter of 466 nm. The Kubelka-Munk scattering coefficient (S/Mil) was measured on the dried polymer film and found to be 0.83.
Example 14
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 5 was added to the kettle and the temperature was adjusted to 50° C. A ME was prepared by mixing 270 g DI water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the kettle temperature at 50° C., a solution of 20 g 0.1% ferrous sulfate mixed with 2 g 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g t-BHP mixed with 80 g DI water, along with a separate solution of 2.0 g iso-ascorbic acid mixed with 80 g DI water, were both added to the kettle at a rate of 0.5 g/min. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 40 min, the ME feed rate was increased to 10 g/min. Upon completion of 90% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 77° C. Next, 900 g hot DI water (90° C.) was added to the kettle. The ME feed was then resumed at a rate of 30 g/min until completion. Immediately after completion of the ME feed, 32 g ammonium hydroxide (28%) was added to the kettle. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered. The filtered dispersion had a solids content of 38.4 wt %, and an average particle diameter of 466 nm. The Kubelka-Munk scattering coefficient (S/Mil) was measured on the dried polymer film and found to be 0.63.
Example 15
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 5 was added to the kettle and the temperature was adjusted to 60° C. A ME was prepared by mixing 270 g DI water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the kettle temperature at 60° C., a solution of 20 g 0.1% ferrous sulfate mixed with 2 g 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g t-BHP mixed with 80 g DI water, along with a separate solution of 2.0 g iso-ascorbic acid mixed with 80 g DI water, were both added to the kettle at a rate of 0.5 g/min. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 40 min, the ME feed rate was increased to 10 g/min. Upon completion of 90% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 79° C. Next, 900 g hot DI water (90° C.) was added to the kettle. The ME feed was then resumed at a rate of 30 g/min until completion. Immediately after completion of the ME feed, 32 g ammonium hydroxide (28%) was added to the kettle. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered to remove any coagulum. The filtered dispersion had a solids content of 38.5 wt %, and an average particle diameter of 461 nm. The Kubelka-Munk scattering coefficient (S/Mil) was measured on the dried polymer film and found to be 1.44. However, this polymer film showed evidence of porosity or dry hiding. Porosity was confirmed by wetting the polymer film with Isopar® L available from Exxon Mobil Chemical Co. Hiding decreased on the polymer film under the area wetted by the Isopar L.
Comparative Example A
Example #8 from U.S. Pat. No. 4,427,836 was reproduced. The BCOP hiding factor was found to be 0.038.
Comparative Example B
Example #1 from U.S. Pat. No. 6,139,961 was reproduced. The BCOP hiding factor was found to be 0.060.
Comparative Example C
Formation of aqueous dispersion of polymeric particles: A 5 L, four necked round bottom flask was equipped with paddle stirrer, thermometer, nitrogen inlet, and reflux condenser. 1125 g of the first polymer of Example 5 was added to the kettle and the temperature was adjusted to 85° C. A ME was prepared by mixing 270 g DI water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the kettle temperature at 85° C., a solution of 2.7 g SPS mixed in 90 g DI water was added to the kettle over a two hour period, along with the ME prepared previously. The temperature of the kettle was kept at 85° C. for the duration of the ME feed. Upon completion of 85% of the ME, without stopping the ME or co-feed, 900 g hot water was added to the kettle along with 32 g ammonium hydroxide. After the remaining 15% of ME and co-feed were fed to the kettle, the reaction was held for 15 min at 85° C. The dispersion was then cooled to 25° C. and filtered to remove any coagulum. The filtered dispersion had a solids content of 39.1 wt %, and an average particle diameter of 519 nm.
Example 16
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 3 was added to the kettle and the temperature was adjusted to 25° C. A ME was prepared by mixing 270 g DI water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the kettle temperature at 25° C., a solution of 20 g 0.1% ferrous sulfate mixed with 2 g 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g t-BHP mixed with 80 g DI water, along with a separate solution of 2.0 g iso-ascorbic acid mixed with 80 g DI water, were both added to the kettle at a rate of 0.5 g/min. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 40 min, the ME feed rate was increased to 10 g/min. Upon completion of 85% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 68° C. Next, 900 g hot DI water (90° C.) was added to the kettle. The ME feed was then resumed at a rate of 30 g/min until completion. Immediately after completion of the ME feed, 32 g ammonium hydroxide (28%) was added to the kettle. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered. The filtered dispersion had a solids content of 37.2 wt %, and an average particle diameter of 530 nm. The Kubelka-Munk scattering coefficient (S/Mil) was measured on the dried polymer film and found to be 1.39.
Example 17
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, DI water, 350 g, was added to the kettle and heated to 30° C. under a nitrogen atmosphere. 1125 g of the first polymer of Example 4 was added to the kettle and the temperature was adjusted to 19° C. A ME was prepared by mixing 270 g DI water, 15.0 g SDS, 378 g MMA, and 522 g BA. Of this ME, 227.5 g was removed and placed in a separate container. Then, 7.2 g MAA was added to the removed 227.5 g of ME. This additional ME was designated ME2. With the kettle temperature at 19° C., a solution of 20 g 0.1% ferrous sulfate mixed with 2 g 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.3 g t-BHP mixed with 75 g DI water, along with a separate solution of 1.80 g iso-ascorbic acid mixed with 75 g DI water, were both added to the kettle at a rate of 0.5 g/min. Two min after the start of the co-feed solutions, ME2 prepared previously was added to the kettle at a rate of 5 g/min. The temperature of the kettle was allowed to increase over the duration of the ME2 feed. When the ME2 feed reached completion, 32 g ammonium hydroxide was added to the kettle. The original ME was then fed to the kettle at a rate of 10 g/min. Upon completion of 85% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 2 min. Next, 600 g hot DI water (90° C.) was added to the kettle. The remaining 15% of ME feed was then added to the kettle as a shot. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered to remove any coagulum. The filtered dispersion had a solids content of 37.6 wt %, and an average particle diameter of 471 nm. The Kubelka-Munk scattering coefficient (S/Mil) was measured on the dried polymer film and found to be 1.24.
Example 18
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 6 was added to the kettle and the temperature was adjusted to 25° C. A ME was prepared by mixing 270 g DI water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the kettle temperature at 25° C., a solution of 20 g 0.1% ferrous sulfate mixed with 2 g 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g t-BHP mixed with 80 g DI water, along with a separate solution of 2.0 g iso-ascorbic acid mixed with 80 g DI water, were both added to the kettle at a rate of 0.5 g/min. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 40 min, the ME feed rate was increased to 10 g/min. Upon completion of 85% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 68° C. Next, 800 g hot DI water (90° C.) was added to the kettle. The ME feed was then resumed at a rate of 30 g/min until completion. Immediately after completion of the ME feed, 32 g ammonium hydroxide (28%) was added to the kettle. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered to remove any coagulum. The filtered dispersion had a solids content of 39.4 wt %, and an average particle diameter of 505 nm. The Kubelka-Munk scattering coefficient (S/Mil) was measured on the dried polymer film and found to be 1.52.
Example 19
Formulation and evaluation of aqueous coating compositions: Aqueous coating compositions, including the following ingredients listed in Table 19.1 were prepared.







TABLE 19.1







Aqueous coating compositions










Material
Weight (g)














TI-PURE TM R-746
43.0



Aqueous Dispersion of Polymer Particles
98.61



TERGITOL TM 15-S-40
0.40



COLLOID TM 643
0.40



TEXANOL TM
2.66



NATROSOL TM 250 MHR (3%)
47.0



Water
3.15

















TABLE 19.2







Evaluation of examples and dry aqueous coating compositions












Aqueous Dispersion

Dry density
Scrubs



Example #
S/Mil
g/cc
w/Texa
















 7
no film
0.986
 598



 8
no film
0.8679
 705



 9
0.89
0.8806
 655



10
1.07
0.8876
 700



11
0.92
1.0135



12
0.85
1.0194
1067



13
0.83
1.0042
 962



14
0.63
1.0075
 923



15
1.44*
1.0092
 832{circumflex over ( )}



Comp. C
no film
1.0756
 813{circumflex over ( )}



16
1.39
0.9337
 908



17
1.24
0.94
 506



  18@
1.52
0.8994
 821







*porosity



{circumflex over ( )}poor films; scrubs misleading



@formulated with 2% TEXANOL TM



ascrub data for aqueous coating compositions using the examples in formulations according to Ex. 19






The dry aqueous coating compositions, including the aqueous dispersion of polymer particles of Examples 7-18 of the invention exhibit lower dry density, and thereby savings in polymer mass and energy to prepare the polymer with a useful level of film integrity as measured by scrub resistance relative to the corresponding coatings, including the aqueous dispersion, Comparative Example C.
Example 20
Formation and evaluation of aqueous traffic paint coating composition An aqueous dispersion of polymeric particles of this invention (33.3% by weight first polymer and 66.7% second encapsulating polymer having Tg=10° C.) (Example 20) and a commercial traffic paint binder (Comp. Example D) were formulated in a fast dry traffic paint as per Table 20.1







TABLE 20.1







Traffic Paint Compositions











Example


Ingredient
Comp. Ex. D
20












FASTRACK TM 3427 quick-setting binder
455.8
0


from Rohm and Haas Company,


Philadelphia, PA


Aqueous Dispersion of Polymer Particles
0
482.4


Ammonium Hydroxide, 28%
0
3.9


Polyamine, 26.5% aqueous
0
8.8


(as disclosed in U.S. Pat. No. 5,804,627)


TAMOL TM 901 (30%) dispersant
7.1
5.6


(ammonium salt of a polyelectrolyte) from


Rohm and Haas Company


SURFYNOL TM CT-136 acetylenic surfactant
2.8
2.8


from Air Products and Chemicals, Inc.,


Allentown, PA


DREWPLUS TM L-493 defoamer from Drew
5.5
5.5


Chemical Company, Kearny, NJ


TI-PURE TM R-900 titanium dioxide from
100.0
49.8


E.I. duPont de Nemours & Company,


Wilmington, DE


OMYACARB TM-5 calcium carbonate from
760.2
789.4


Omya Inc., Proctor, VT


After 15 min, added


Methanol
30.0
0


TEXANOL ® solvent ester alcohol from
29.9
13.1


Eastman Chemicals, Kingsport, TN


NATROSOL ® 250HR(2%) thickener from
6.7
22.0


Aqualon, Inc, Wilmington, DE


Water
8.6
2.8









The traffic paint of Example 20 was formulated with about half the level of titanium dioxide of the comparative traffic paint (Com. Example D) and yet exhibited improved hiding and total reflectance as shown in Table 20.2.







TABLE 20.2







Evaluation of dry traffic paint











Test
Comp. Ex. D
Ex. 20















Hiding by Contrast Ratio
0.90
0.95



Total Reflectance
86.0
88.5










Example 21
Preparation of first polymer: Using the same equipment as in Example 6, 1200 g DI water is added to the kettle and heated to 89° C. under a nitrogen atmosphere. 5.25 g of sodium persulfate is dissolved in 30 g of DI water was added to the heated kettle. This is immediately followed by the addition of 314.5 g of Core #3 (Example 1). The ME I is prepared by mixing 10 g of DI water, 6.7 g of SDS(23%), 100.0 g of styrene, 88.0 g of methyl methacrylate, and 12.0 g of methacrylic acid and added to the kettle over a period of 60 min at 78° C. Upon completion of ME I, a ME II is prepared by mixing 400 g of DI water, 18.0 g of SDS(23%), 1181.4 g of styrene, 18.0 g of methacrylic acid, 6.0 g of linseed oil fatty acid (LOFA) and 0.6 g of ALMA. ME II is added to the kettle, along with a separate mixture of 1.3 g of sodium persulfate dissolved in 90 g of DI water over 60 min. The temperature of the reaction mixture is allowed to increase to 92° C. Upon completion of the ME II and co-feed, the reaction mixture is held for 30 min at 85° C. The batch is cooled to room temperature and filtered to remove any coagulum formed. It is expected that the final unneutralized latex will have a solids content of  ̃40.0%, an average particle size of  ̃380 nm, and a pH of  ̃2.2.
Example 22
Preparation of first polymer: A 5 L, four necked round bottom flask is equipped with paddle stirrer, thermometer, nitrogen inlet, and reflux condenser. 1200 g of DI water is added to the kettle and heated to 89° C. under a nitrogen atmosphere. 5.25 g of sodium persulfate dissolved in 30 g of DI water is added to the heated kettle. This is immediately followed by the addition of 314.5 g of Core #3 (Example 1). Prepare ME I by mixing 100 g of DI water, 6.7 g of SDS(23%), 100.0 g of styrene, 88.0 g of methyl methacrylate, and 12.0 g of methacrylic acid and add to the kettle over a period of 60 min at 78° C. Upon completion of ME I, prepare ME II by mixing 400 g of DI water, 18.0 g of SDS(23%), 582.0 g of styrene, 18.0 g of methacrylic acid, 6.0 g of linseed oil fatty acid (LOFA) and 600.0 g of BGDMA. Add ME II to the kettle along with a separate mixture of 1.3 g of sodium persulfate dissolved in 90 g of DI water over 60 min. Allow the temperature of the reaction mixture to increase to 92° C. Upon completion of the ME II and co-feed, hold the reaction mixture for 30 min at 85° C. Cool the batch to room temperature and filter to remove any coagulum formed. It is expected that the final unneutralized latex will have a solids content of  ̃40.0%, an average particle size of  ̃380 nm, and a pH of  ̃2.2.
Example 23
Formation of aqueous dispersion of polymeric particles: A 5 L, four necked round bottom flask is equipped with paddle stirrer, thermometer, nitrogen inlet, and reflux condenser. 1125 g of the first polymer of Example #21 is added to the kettle and the temperature is adjusted to 25° C. Prepare ME by mixing 270 g of DI water, 15.0 g of sodium dodecylbenzenesulfonate (SDS, 23%), 369 g of methyl methacrylate, 9.0 g of methacrylic acid, and 522 g of butyl acrylate. With the kettle temperature at 25° C., a solution of 20 g of 0.1% ferrous sulfate mixed with 2 g of 1% versene is added to the kettle. Next, co-feeds, including a solution of 2.8 g of t-butyl hydroperoxide(70%) mixed with 80 g of DI water, along with a separate solution of 2.0 g of iso-ascorbic acid mixed with 80 g of DI water are both added to the kettle at a rate of 0.5 gram/minute. Two min after the start of the co-feed solutions, the ME prepared previously is added to the kettle at a rate of 5 g/min. Apply no external heat to the reaction. The temperature of the kettle is allowed to increase over the duration of the ME feed. After 45 min, the ME feed rate is increased to 10 g/min. Upon completion of 90% of the ME feed, stop the ME and co-feeds and hold the reaction for 5 min. The temperature of the reaction at this point will be  ̃72° C. Next, add 900 g of hot DI water (90° C.) to the kettle. Resume the ME feed at a rate of 30 g/minute until completion. Immediately after completion of the ME feed, add 32 g of ammonium hydroxide (28%) to the kettle. Hold the reaction for 5 min. Resume the co-feed solutions at a rate of 1.0 gram/minute until their completion. Cool the dispersion to 25° C. and filter to remove any coagulum. It is expected that the filtered dispersion will have a solids content of  ̃38.0%, and an average particle size of  ̃450 nm. The BCOP hiding factor is expected to be >0.1 and the BCOP stability factor is expected to be <0.5.
Example 24
Formation of aqueous dispersion of polymeric particles: An aqueous dispersion is prepared by following the procedure of Example 23, but substituting 1125 g of a first polymer made by Example 22. The filtered dispersion will have a solids content of  ̃38.0 wt %, and an average particle size of  ̃450 nm. The BCOP hiding factor is expected to be >0.1 and the BCOP stability factor is expected to be <0.5.
Example 25
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 5 was added to the kettle and the temperature was adjusted to 25° C. A ME was prepared by mixing 270 g of DI water, 15.0 g of SDS, 369 g of methyl methacrylate, 9.0 g of methacrylic acid, and 522 g of butyl acrylate. With the kettle temperature at 25° C., a solution of 20 g of 0.1% ferrous sulfate mixed with 2 g of 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g of t-butyl hydroperoxide (70%) mixed with 80 g of DI water, along with a separate solution of 2.0 g of iso-ascorbic acid mixed with 80 g of DI water, were both added to the kettle at a rate of 0.5 gram/minute. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 40 min, the ME feed rate was increased to 10 g/min. Upon completion of 85% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 72° C. Next, 600 g of hot DI water (90° C.) was added to the kettle. 2 g of an inhibitor, 4-hydroxy TEMPO, were added to the remaining ME and this mixture was fed to the kettle at a rate of 30 g/minute until completion. Immediately after completion of the ME feed, 32 g of ammonium hydroxide (28%) mixed with 30 g of DI water was added to the kettle. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered to remove any coagulum. The filtered dispersion had a solids content of 41.2%, and an average particle size of 485 nm. The BCOP hiding factor was 0.43 with a BCOP stability factor of 0.39. In this example, when 20% of the ME had been added to the kettle, an aliquot of the reaction mixture was withdrawn, and gas chromatographic analysis of this aliquot determined that the reaction mixture contained 1.6% unpolymerized monomer by weight, based on the weight of total reaction mixture when the aliquot was withdrawn.
Example 26
Formation of aqueous dispersion of polymeric particles: An aqueous dispersion was prepared following the recipe and procedure of Example 25, except that the first polymer was added to the kettle and adjusted to 40° C. The filtered dispersion had a solids content of 41.2 wt %, and an average particle size of 495 nm. The BCOP hiding factor was 0.40 with a BCOP stability factor of 0.43.
Example 27
Formation of aqueous dispersion of polymeric particles: An aqueous dispersion was prepared following the recipe and procedure of Example 25, except that the first polymer was added to the kettle and adjusted to 50° C. The filtered dispersion had a solids content of 41.3 wt %, and an average particle size of 498 nm. The BCOP hiding factor was 0.37 with a BCOP stability factor of 0.39.
Example 28
Formation of aqueous dispersion of polymeric particles: An aqueous dispersion was prepared following the recipe and procedure of Example 25, except that the first polymer was added to the kettle and adjusted to 60° C. The filtered dispersion had a solids content of 41.2 wt %, and an average particle size of 505 nm. The BCOP hiding factor was 0.18 with a BCOP stability factor of 0.65.
Example 29
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 5 was added to the kettle and the temperature was adjusted to 78° C. A monomer emulsion (ME) was prepared by mixing 270 g of DI water, 15.0 g of SDS, 369 g of methyl methacrylate, 9.0 g of methacrylic acid, and 522 g of butyl acrylate. With the kettle temperature at 78° C., a solution of 3.0 g of sodium persulfate mixed with 30 g of DI water was added to the kettle. Next, the ME prepared previously was added to the kettle at a rate of 5 g/min and a solution of 1.0 gram of sodium persulfate mixed with 60 g of DI water was added to the kettle at a rate of 0.5 g/min. The temperature of the kettle was allowed to increase to 83° C. over the duration of the ME feed. After 45 min, the ME feed rate was increased to 10 g/min. Upon completion of 85% of the ME feed and completion of the co-feed catalyst, the ME feed was stopped and the reaction was held for 5 min. A solution of 20 g of 0.1% ferrous sulfate mixed with 2 g of 1% versene was added to the kettle. The temperature of the reaction at this point was 83° C. Next, 600 g of hot DI water (90° C.) was added to the kettle. 2 g of an inhibitor, 4-hydroxy TEMPO, was added to the remaining ME and this mixture was fed to the kettle at a rate of 30 g/min until completion. Immediately after completion of the ME feed, 32 g of ammonium hydroxide (28%) mixed with 30 g of DI water was added to the kettle. The reaction was held for 5 min. Next, co-feeds, including a solution of 2.0 g of t-butyl hydroperoxide(70%) mixed with 50 g of DI water, along with a separate solution of 1.0 gram of iso-ascorbic acid mixed with 50 g of DI water, were both added to the kettle at a rate of 1.0 g/min until completion. The dispersion was then cooled to 25° C. and filtered to remove any coagulum. The filtered dispersion had a solids content of 41.4 wt %, and an average particle size of 501 nm. The BCOP hiding factor was 0.05 with a BCOP stability factor of 0.60.
Example 30
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 5 was added to the kettle and the temperature was adjusted to 25° C. A ME was prepared by mixing 270 g of DI water, 15.0 g of SDS, 189 g of methyl methacrylate, 180.0 g of styrene, 9.0 g of methacrylic acid, and 522 g of butyl acrylate. With the kettle temperature at 25° C., a solution of 20 g of 0.1% ferrous sulfate mixed with 2 g of 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g of t-butyl hydroperoxide(70%) mixed with 80 g of DI water, along with a separate solution of 2.0 g of iso-ascorbic acid mixed with 80 g of DI water, were both added to the kettle at a rate of 0.5 gram/minute. 2 min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 40 min, the feed rate of the ME was increased to 10 g/min. Upon completion of 85% of the ME feed, the co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 62° C. Next, 900 g of hot DI water (90° C.) was added to the kettle. The remaining portion of the ME was then added to the kettle a rate of 30 g/min followed by the addition of 32 g of ammonium hydroxide (28%). The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered to remove any coagulum. The filtered dispersion had a solids content of 38.1 wt %, and an average particle size of 546 nm. The BCOP hiding factor was <0.1. In this example, when 20% of the ME had been added to the kettle, an aliquot of the reaction mixture was withdrawn and gas chromatographic analysis of this aliquot determined that the reaction mixture contained 6.5% unpolymerized monomer by weight, based on the weight of total reaction mixture when the aliquot was withdrawn.
Example 31
Preparation of first polymer: Using the same equipment as in Example 6, DI water, 1200 g, was added to the kettle and heated to 89° C. under a nitrogen atmosphere. To the heated kettle, water was added 5.25 g of sodium persulfate dissolved in 30 g of DI water. This was immediately followed by 314.5 g of Core #3 (Example 1). A ME I, which was prepared by mixing 100 g of DI water, 6.7 g of SDS(23%), 100.0 g of styrene, 88.0 g of methyl methacrylate, and 12.0 g of methacrylic acid, was added to the kettle over a period of 60 min at 78° C. Upon completion of ME I, a ME II was prepared by mixing 400 g of DI water, 18.0 g of SDS, 1170 g of styrene, 18.0 g of methacrylic acid, 6.0 g of linseed oil fatty acid (LOFA), and 21.8 g of divinyl benzene (55% active). ME II was added to the kettle along with a separate mixture of 1.3 g of sodium persulfate dissolved in 90 g of DI water over 60 min. The temperature of the reaction mixture was allowed to increase to 92° C. Upon completion of the ME II and co-feed, the reaction mixture was held for 30 min at 85° C. and then cooled to room temperature and filtered to remove any coagulum formed. The final unneutralized latex had a solids content of 40.0 wt %, an average particle size of 375 nm, and a pH of 2.2.
Example 32
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 31 was added to the kettle and the temperature was adjusted to 25° C. A ME was prepared by mixing 270 g of DI water, 15.0 g of SDS, 369 g of methyl methacrylate, 9.0 g of methacrylic acid, and 522 g of butyl acrylate. With the kettle temperature at 25° C., a solution of 20 g of 0.1% ferrous sulfate mixed with 2 g of 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g of t-butyl hydroperoxide(70%) mixed with 80 g of DI water, along with a separate solution of 2.0 g of iso-ascorbic acid mixed with 80 g of DI water, were both added to the kettle at a rate of 0.5 gram/minute. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 45 min, the ME feed rate was increased to 10 g/min. Upon completion of 85% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 72° C. Next, 600 g of hot DI water (90° C.) was added to the kettle. Two grams of an inhibitor, 4-hydroxy TEMPO, was added to the remaining ME and this mixture was fed to the kettle at a rate of 30 g/minute until completion. Immediately after completion of the ME feed, 32 g of ammonium hydroxide (28%) mixed with 30 g of DI water was added to the kettle. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered to remove any coagulum. The filtered dispersion had a solids content of 41.2 wt %, and an average particle size of 489 nm. The BCOP hiding factor was 0.54 with a BCOP stability factor of 0.06. In this example, when 20% of the ME had been added to the kettle, an aliquot of the reaction mixture was withdrawn and gas chromatographic analysis of this aliquot determined that the reaction mixture contained 1.0% unpolymerized monomer by weight, based on the weight of total reaction mixture when the aliquot was withdrawn.
Example 33
Formation of aqueous dispersion of polymeric particles: An aqueous dispersion was prepared following the recipe and procedure of Example 32, except that the first polymer was added to the kettle and adjusted to 50° C. The filtered dispersion had a solids content of 41.3 wt % and an average particle size of 490 nm. The BCOP hiding factor was 0.53 with a BCOP stability factor of 0.11.
Example 34
Formation of aqueous dispersion of polymeric particles: An aqueous dispersion was prepared following the recipe and procedure of Example 32, except that the first polymer was added to the kettle and adjusted to 60° C. The filtered dispersion had a solids content of 41.4 wt % and an average particle size of 487 nm. The BCOP hiding factor was 0.55 with a BCOP stability factor of 0.13.
Example 35
Formation of aqueous dispersion of polymeric particles: An aqueous dispersion was prepared following the recipe and procedure of Example 29, except that 1125 g of the first polymer prepared in Example 31 was used. The filtered dispersion had a solids content of 41.5 wt % and an average particle size of 503 nm. The BCOP hiding factor was 0.51 with a BCOP stability factor of 0.34.
Example 36
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 31 was added to the kettle and the temperature was adjusted to 25° C. A ME was prepared by mixing 270 g of DI water, 15.0 g of SDS, 189 g of methyl methacrylate, 180.0 g of styrene, 9.0 g of methacrylic acid, and 522 g of butyl acrylate. With the kettle temperature at 25° C., a solution of 20 g of 0.1% ferrous sulfate mixed with 2 g of 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g of t-butyl hydroperoxide(70%) mixed with 80 g of DI water, along with a separate solution of 2.0 g of iso-ascorbic acid mixed with 80 g of DI water, were both added to the kettle at a rate of 0.5 g/min. 2 min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5 g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the three hour ME feed. Upon completion of the ME feed, the co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 61° C. Next, 600 g of hot DI water (90° C.) was added to the kettle. Then, 32 g of ammonium hydroxide (28%) was added to the kettle and the reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered to remove any coagulum. The filtered dispersion had a solids content of 46.1 wt %, and an average particle size of 495 nm. The BCOP hiding factor was 0.40 with a BCOP stability factor of 0.90. In this example, when 20% of the ME had been added to the kettle, an aliquot of the reaction mixture was withdrawn and gas chromatographic analysis of this aliquot determined that the reaction mixture contained 6.3% unpolymerized monomer by weight, based on the weight of total reaction mixture when the aliquot was withdrawn.
Example 37
Formation of bimodal aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 0.31 was added to the kettle along with 125 g of a 40% solids aqueous dispersion of 99% styrene/1% acrylic acid polymer particles with an average particle size of 60 nm and the temperature was adjusted to 25° C. A ME was prepared by mixing 270 g of DI water, 15.0 g of SDS, 369 g of methyl methacrylate, 9.0 g of methacrylic acid, and 522 g of butyl acrylate. With the kettle temperature at 25° C., a solution of 20 g of 0.1% ferrous sulfate mixed with 2 g of 1% versene was added to the kettle. Next, co-feeds, including a solution of 2.8 g of t-butyl hydroperoxide (70%) mixed with 80 g of DI water, along with a separate solution of 2.0 g of iso-ascorbic acid mixed with 80 g of DI water, were both added to the kettle at a rate of 0.5 gram/minute. Two min after the start of the co-feed solutions, the ME prepared previously was added to the kettle at a rate of 5g/min. There was no external heat applied to the reaction. The temperature of the kettle was allowed to increase over the duration of the ME feed. After 45 min, the ME feed rate was increased to 10 g/min. Upon completion of 85% of the ME feed, the ME and co-feeds were stopped and the reaction was held for 5 min. The temperature of the reaction at this point was 67° C. Next, 600 g of hot DI water (90° C.) was added to the kettle. Two grams of an inhibitor, 4-hydroxy TEMPO, was added to the remaining ME and this mixture was fed to the kettle at a rate of 30 g/min until completion. Immediately after completion of the ME feed, 32 g of ammonium hydroxide (28%) mixed with 30 g of DI water was added to the kettle. The reaction was held for 5 min. The co-feed solutions were then resumed at a rate of 1.0 g/min until their completion. The dispersion was then cooled to 25° C. and filtered to remove any coagulum. The filtered dispersion had a solids content of 41.0 wt %. The dispersion was found to have two particle size modes. The large mode had a size of 471 nm while the small mode was found to be 99 nm with a weight ratio of 81% large/19% small. The BCOP hiding factor was 0.50 with a BCOP stability factor of 0.14.
Example 38
Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 6, 1125 g of the first polymer of Example 31 is added to the kettle and the temperature adjusted to 25° C. A ME is prepared by mixing 270 g of DI water, 15.0 g of SDS, 171 g of 2-ethyl hexyl acrylate, 9.0 g of methacrylic acid, and 720 g of butyl acrylate. With the kettle temperature at 25° C., a solution of 20 g of 0.1% ferrous sulfate mixed with 2 g of 1% versene is added to the kettle. Next, co-feeds, including a solution of 2.8 g of t-butyl hydroperoxide(70%) mixed with 80 g of DI water, along with a separate solution of 2.0 g of iso-ascorbic acid mixed with 80 g of DI water, are both added to the kettle at a rate of 0.5 gram/minute. Two min after the start of the co-feed solutions, the ME prepared previously is added to the kettle at a rate of 5 g/min. There is no external heat applied to the reaction. The temperature of the kettle is allowed to increase over the duration of the ME feed. After 45 min, the ME feed rate is increased to 10 g/min. Upon completion of 85% of the ME feed, the ME and co-feeds are stopped and the reaction is held for 5 min. The temperature of the reaction at this point is expected to be  ̃72° C. Next, 600 g of hot DI water (90° C.) is added to the kettle. 2 g of an inhibitor, 4-hydroxy TEMPO, is added to the remaining ME and this mixture is fed to the kettle at a rate of 30 g/min until completion. Immediately after completion of the ME feed, 32 g of ammonium hydroxide (28%) mixed with 30 g of DI water is added to the kettle. The reaction is held for 5 min. The co-feed solutions are then resumed at a rate of 1.0 gram/minute until their completion. The dispersion is then cooled to 25° C. and filtered to remove any coagulum. It is expected that the filtered dispersion will have a solids content of  ̃41.0 wt %, and an average particle size of  ̃485 nm. The BCOP hiding factor is expected to be >0.1 with a BCOP stability factor of <0.50.
Example 39
Formation of aqueous dispersion of polymeric particles: An aqueous dispersion is prepared following the recipe and procedure of Example 38, except that the ME used is prepared by mixing 270 g of DI water, 15.0 g of SDS, 612 g of methyl methacrylate, 9.0 g of methacrylic acid, and 279 g of butyl acrylate is used. It is expected that the filtered dispersion will have a solids content of  ̃41.0 wt %, and an average particle size of  ̃485 nm. The BCOP hiding factor is expected to be >0.1 with a BCOP stability factor of <0.50.
Example 40
Formation of aqueous dispersion of polymeric particles: An aqueous dispersion is prepared following the recipe and procedure of Example 38, except that the ME used is prepared by mixing 270 g of DI water, 15.0 g of sodium dodecylbenzenesulfonate (SDS, 23%), 675 g of methyl methacrylate, 9.0 g of methacrylic acid, and 216 g of butyl acrylate is used. It is expected that the filtered dispersion will have a solids content of  ̃41.0 wt %, and an average particle size of  ̃485 nm. The BCOP hiding factor is expected to be >0.1 with a BCOP stability factor of <0.50.
Example 41
Comparison of binders: Dry films resulting from two pigmented coating formulations, Formulation 1 and Formulation 2, are described. Formulation 1 uses particles of Example 32 as binder. Formulation 2 uses particles of Dispersion X as binder. The percentages expressed in this comparison and in Table 41.1 are % volume based on the combined volume of binder, pigment, and extender. TiO2 and RopaqueTM Ultra are used as examples of pigments. CaCO3, silica, and clay are used as examples of extenders. The dry film of Formulation 1 comprises 45% polymer particles of Example 47, 5% coatings grade rutile TiO2, and 50% CaCO3 having an average particle size of 5 microns. The dry film of Formulation 2 comprises, by volume, based on the total volume of binder, pigment and extender, 32% polymer particles of Dispersion X, 8% of the same TiO2 used in Formulation 1, and 60% of the same CaCO3 used in Formulation 1. Dispersion X is an aqueous dispersion of non-voided polymer particles having an average particle diameter of 489 nm formed by emulsion polymerization of a mixture of monomers consisting of, by weight, 41% methyl methacrylate, 58% butyl acrylate, and 1% methacrylic acid. The dried film of Formulation 1 displays opacity equal to, or greater than, the dried film of Formulation 2.
Table 41.1 similarly compares the opacity of dry films resulting from formulations using Example 32 and Dispersion X as binders at various levels of pigments and extenders.







TABLE 41.1







Opacity of Films From Formulations Using Inventive and Non-Inventive Polymers


as Binders








Binder Using Inventive Polymers
Binder 


(Formulation 1)
Using Non-inventive Polymers (Formulation 2)





68% Particles of Example 47, 5% TiO2,
57% Particles of Dispersion X, 8% TiO2,


27% 5μ Clay
35% 5μ Clay


79% Particles of Example 47, 8% TiO2,
61% Particles of Dispersion X, 12% TiO2,


13% 5μ Clay
27% 5μ Clay


69% Particles of Example 47, 6% TiO2,
38% Particles of Dispersion X, 12% TiO2,


25% 2μ Silica
50% 2μ Silica


51% Particles of Example 47, 9% TiO2,
40% Particles of Dispersion X, 15% TiO2,


40% 5μ CaCO3
45% 5μ CaCO3


78% Particles of Example 47, 7% TiO2,
40% Particles of Dispersion X, 15% TiO2,


15% 5μ CaCO3
45% 5μ CaCO3


79% Particles of Example 47, 8% TiO2,
42% Particles of Dispersion X, 18% TiO2,


13% 5μ CaCO3
40% 5μ CaCO3


84% Particles of Example 47, 10% TiO2,
62% Particles of Dispersion X, 18% TiO2,


6% 2μ Silica
20% 2μ Silica


87% Particles of Example 47, 11% TiO2,
58% Particles of Dispersion X, 22% TiO2,


2% 5μ CaCO3
20% 5μ CaCO3


79% Particles of Example 47, 13% TiO2,
68% Particles of Dispersion X, 22% TiO2,


8% 5μ CaCO3
10% 5μ CaCO3


73% Particles of Example 47, 12% TiO2,
72% Particles of Dispersion X, 18% TiO2,


15% 5μ Clay
10% 5μ Clay


89% Particles of Example 47, 11% TiO2
82% Particles of Dispersion X, 18% TiO2


70.5% Particles of Example 47, 14.5%
61% Particles of Dispersion X, 25% TiO2,


TiO2, 15% 5μ Clay
15% 5μ Clay


87.5% Particles of Example 47, 12.5%
76% Particles of Dispersion X, 18% TiO2,


TiO2
6% Ropaque TM Ultra


76% Particles of Example 47, 9% TiO2,
35% Particles of Dispersion X, 15% TiO2,


15% 8μ CaCO3
40% 8μ CaCO3, 10% Ropaque TM Ultra


72% Particles of Example 47, 8% TiO2,
35% Particles of Dispersion X, 15% TiO2,


15% 5μ CaCO3, 5% Ropaque TM Ultra
40% 5μ CaCO3, 10% Ropaque TM Ultra









Dry films resulting from coating formulations, such as those described for Formulation 1, Formulation 2, and in Table 41.1 will typically also comprise from 0.5 to 20% by volume, based on the total volume of the dry film, dispersants, coalescents, solvents, defoamers, thickeners, wetting agents, surfactants, waxes, biocides, colored pigments, and other adjuvants commonly found in coatings. The inventive dispersions may also be used in formulations with non-voided binder polymers to achieve varying balances of opacity and binding characteristics.

## Claims

1. An aqueous dispersion of polymeric particles, the particles comprising:
a core stage polymer comprising, as polymerized units, from 5 to 100% by weight, based on the weight of the core, of at least one hydrophilic monoethylenically unsaturated monomer and from 0 to 95% by weight of at least one nonionic monoethylenically unsaturated monomer;
from 25% to 33% by weight, based on the weight of the polymeric particles, of a first shell stage polymer comprising, as polymerized units, at least one monoethylenically unsaturated monomer and at least one multi-ethylenically unsaturated monomer present in an amount of from 0.05% to 90% by weight, based on the total weight of the first shell stage polymer, and when dry, at least one void, the void having a diameter of from 100 to 1200 nanometers; and
from 67% to 75% by weight, based on the weight of the polymeric particles, of at least one second shell stage polymer comprising, as polymerized units, at least one ethylenically unsaturated monomer, the second shell stage polymer substantially encapsulating the first shell stage polymer and having a Tg of from −60° C. to 50° C., the second shell stage polymer formed in a presence of the first shell stage polymer.

2. The aqueous dispersion of claim 1 wherein the at least one multi-ethylenically unsaturated monomer is present in an amount of from 0.2% to 35% by weight, based on the total weight of the first shell stage polymer.

3. The aqueous dispersion of claim 1 wherein the first shell stage polymer has a Tg of at least 50° C.

4. The aqueous dispersion of claim 1 having a BCOP hiding factor of at least 0.1.

5. The aqueous dispersion of claim 1 having a BCOP stability factor of less than 0.5.

6. An aqueous coating composition comprising the polymeric particles according to claim 1 having a Pigment Volume Concentration of from 0 to 95.

7. A process for forming an aqueous dispersion of polymeric particles comprising:
providing an aqueous dispersion of multi-stage emulsion polymer, the multi-stage emulsion polymer comprising a core stage polymer and a first shell stage polymer, the core stage polymer comprising, as polymerized units, from 5 to 100 percent by weight, based on the weight of the core stage polymer, of hydrophilic monoethylenically unsaturated monomer, and from 0 to 95 percent by weight, based on the weight of the core stage polymer, of at least one nonionic monoethylenically unsaturated monomer; and the first shell stage polymer having a calculated Tg of at least 50° C. and comprising, as polymerized units, 0.05 to 90% by weight, based on the total weight of the first shell stage polymer, of at least one multi-ethylenically unsaturated monomer, and when dry, at least one void, the void having a diameter of from 100 to 1200 nanometers;
forming a second shell stage polymer, substantially encapsulating the first shell stage polymer and having a Tg of from −60° C. to 50° C., by adding to an aqueous dispersion of the product which is a combination of the core stage polymer and the first shell stage polymer at least one ethylenically unsaturated monomer and causing the monomer to polymerize to provide polymer particles comprising from 25% to 33% by weight, based on the weight of the polymeric particles, of the first shell stage polymer and from 67% to 75% by weight, based on the weight of the polymeric particles, of the second shell stage polymer; and
adding a swelling agent to the aqueous dispersion prior to, during, or after the polymerization of the monomers comprising the second shell stage polymer.

8. The process of claim 7 wherein the first shell stage polymer comprises, as polymerized units, from 0.2 to 35% by weight, based on the total weight of the first shell stage polymer, of at least one multi-ethylenically unsaturated monomer.

9. The process of claim 7 wherein the adding comprises charging the swelling agent at a time when the aqueous dispersion comprises at least 0.5% by weight, based on the total polymeric content of polymer in the dispersion, unreacted monomer and under conditions wherein there is no substantial polymerization of the monomer; and
subsequently reducing the level of monomer by at least 50%.

10. The aqueous dispersion of claim 1 wherein the at least one multi-ethylenically unsaturated monomer is present in an amount of from 0.05% to 50% by weight, based on the total weight of the first shell stage polymer.

11. The aqueous dispersion of claim 1 wherein the at least one multi-ethylenically unsaturated monomer is at least one of the monomers selected from the group consisting of allyl methacrylate, diallyl phthalate, 1,4-butyleneglycol dimethacrylate, 1,2-ethyleneglycol dimethacrylate, 1,6-hexanediol diacrylate, and divinyl benzene.

12. The aqueous dispersion of claim 1 wherein
the at least one hydrophilic monoethylenically unsaturated monomer of the core stage polymer comprises methacrylic acid and the at least one nonionic monoethylenically unsaturated monomer comprises methyl methacrylate;
the at least one mono-ethylenically unsaturated monomer the first shell polymer is selected from the group consisting of methyl methacrylate, methacrylic acid, butyl acrylate, styrene, and mixtures thereof;
the at least one multi-ethylenically unsaturated monomer is selected from the group consisting of allyl methacrylate, butylene glycol dimethacrylate and divinyl benzene; and
the at least one mono-ethylenically unsaturated monomer the second shell polymer is selected from the group consisting of methyl methacrylate, methacrylic acid, 2-ethylhexyl acrylate, butyl acrylate, styrene, and mixtures thereof.

13. An aqueous dispersion of polymeric particles, the particles comprising:
a core stage polymer comprising, as polymerized units, from 5 to 100% by weight, based on the weight of the core, of at least one hydrophilic monoethylenically unsaturated monomer and from 0 to 95% by weight of at least one nonionic monoethylenically unsaturated monomer;
from 25% to 33% by weight, based on the weight of the polymeric particles, of a first shell stage polymer comprising, as polymerized units, at least one monoethylenically unsaturated monomer and at least one multi-ethylenically unsaturated monomer present in an amount of from 0.05% to 90% by weight, based on the total weight of the first shell stage polymer, and when dry, at least one void, the void having a diameter of from 100 to 1200 nanometers; and
from 67% to 75% by weight, based on the weight of the polymeric particles, of at least one second shell stage polymer formed by a polymerization of at least one monoethylenically unsaturated monomer in the presence of the first shell stage polymer, the second shell stage polymer substantially encapsulating the first shell stage polymer and having a Tg of from −60° C. to 50° C.