BRPI0603204B1 - AQUOSA DISPERSION, AQUOUS COATING COMPOSITION, AND, PROCESS FOR FORMING AQUOSA DISPERSION OF POLYMERIC PARTICLES - Google Patents

Description

“WATER DISPERSION, WATER COATING COMPOSITION, AND PROCESS TO FORM A WATER DISPOSAL OF POLYMER Particles” This non-provisional patent application is claiming priority based on US Provisional Patent Application No. 60 / 709,664, filed August 19 2005, the disclosure of which is incorporated herein by reference.

This invention relates to film-forming binders which may be used in aqueous coating compositions. More particularly, this invention relates to an aqueous dispersion of film-forming polymer particles that also provide a high degree of white light scattering when the film dries.

Aqueous coating compositions which, when dried, have improved film integrity (e.g., frictional resistance) are desired, particularly in coating compositions having low or zero volatile organic compound ("VOC") content. In some cases, particles having one or more voids provide such coating compositions, while reducing the particulate mass, and thereby reducing the materials and energy that would have to be consumed in providing that mass. Particles including one or more voids may also contribute to the opacity of dry coating films.

U.S. Patent No. 6,139,961 describes an aqueous dispersion of water-insoluble core / shell polymer particles. The core contains a void encapsulated by a first shell polymer having a glass transition temperature greater than 50 ° C, and polymerized over 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 found that they have unsatisfactory opacity, probably because many voids collapse under film formation.

The film-forming binder particles of this invention provide superior opacity characteristics i.e. consistent and improved masking compared to the prior art when incorporated into coatings. A first aspect of the invention is an aqueous dispersion comprising polymeric particles. The particles comprise from 10% to 80% by weight, based on the total polymeric weight of the particles when dried, of a first polymer and at least one second polymer comprising as polymerized units at least one ethylenically unsaturated monomer. The first polymer comprises, when dry, at least one void having a diameter of 100 nm to 1,200 nm and the second polymer substantially encapsulates the first polymer and has a Tg of -60 ° C to 50 ° C. The aqueous dispersion has a BCOP masking factor of at least 0.1.

A second aspect of the invention is a process for forming an aqueous dispersion of polymeric particles comprising providing an aqueous multistage emulsion polymer dispersion comprising a core stage polymer and a first shell stage polymer; form a second shell stage polymer substantially encapsulating the first shell stage polymer by adding in the aqueous dispersion to at least one monoethylenically unsaturated monomer and causing at least 10% of the monoethylenically unsaturated monomer to polymerize at a temperature of 5 ° C at 65 ° C in a presence of the multistage polymer; and adding a swelling agent to the aqueous dispersion prior to, during, or after polymerization of the monoethylenically unsaturated monomers of the second shell stage polymer.

In this process, the core stage polymer comprises, as polymerized units, from 5 to 100 weight percent, based on a weight of core stage polymer, hydrophilic monoethylenically unsaturated monomer, and from 0 to 95 weight percent , based on the weight of core stage polymer, of at least one nonionic monoethylenically unsaturated monomer. The first shell stage polymer has a calculated Tg of at least 50 ° C and comprises, as polymerized units, at least 50 weight percent nonionic monoethylenically unsaturated monomer. The polymerization temperature is at least 30 ° C lower than the calculated Tg of the first shell stage polymer. The first polymer may be a condensation polymer, for example a polyester. The first polymer may include at least one copolymerized monoethylenically unsaturated monomer and may be formed by a free radical addition polymerization process.

Suitable monoethylenically unsaturated monomers include, for example, (meth) acrylic ester monomers including, for example, (meth) acrylic ester monomers including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylate decyl, 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-butyl aminoethyl (meth) acrylate; ethylene-ureido-functionalized 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) acrylics, predominantly (meth) acrylics, styrene / (meth) acrylic, and vinyl / acrylic acetate, i.e., the polymer composition includes those monomers or classes of monomers. The use of the term "(met)" followed by another term such as acrylate or acrylamide, as used throughout the description, refers to both acrylates or acrylamides and methacrylates or 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-methyl-propane sulfonic acid; vinyl sulfonic acid; styrene sulfonic acid; 1-allyloxy-2-hydroxypropane sulfonic acid; alkyl allyl sulfosuccinic acid; sulfoethyl (meth) acrylate; phospho-alkyl (meth) acrylates such as phospho-ethyl (meth) acrylate, phospho-propyl (meth) acrylate, and phospho-butyl (meth) acrylate; phosphoalkyl crotonate, phosphoalkyl maleate; phosphoalkyl fumarate; phospho-dialkyl (meth) acrylate; phospho-dialkyl crotonate; and allyl phosphate. In some embodiments, both an acid monomer and an amide monomer are incorporated in the second polymer, such as, for example, from 0.1% to 2.5% by weight of itaconic acid and from 0.1% to 2.5%. by weight of acrylamide, each based on polymer weight.

Multiethylenically unsaturated monomers are defined herein as monomers having two or more ethylenically unsaturated bonds, such as, for example, allyl methacrylate, allyl phthalate, 1,4-butylene glycol dimethacrylate, 1,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, and divinyl benzene. Levels of such monomers have to 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 from 0.2% to 35%, more preferably from 0.5% to 30%, more preferably from 1% to 25%, by weight, based on polymer dry weight, of copolymerized multiethylenically unsaturated monomers. In other embodiments, the first polymer contains from 0.05% to 5% by weight based on polymer dry weight of copolymerized multiethylenically unsaturated monomers. The glass transition temperature ("Tg") of the first polymer is preferably greater than 50 ° C, more preferably greater than 75 ° C, and more preferably greater than 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 case, 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 types of monomer, the calculation may be expressed as: where w (Mi) is the weight fraction of each monomer, and Tg, (Mi) the homopolymer glass transition temperature Mi. For example, for the calculation of Tg of a copolymer of monomers M1 and M2, where 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 M1 homopolymer; and Tg (M2) is the glass transition temperature of the homopolymer of M2, where all temperatures are in Kelvin (K).

Homopolymer glass transition temperatures can 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 multi-stage polymerization process in which the second polymer is formed in the presence of the first polymer. In certain embodiments, the first polymer may itself include multiple polymers that may be formed in multiple stages. There may be two or more phases included in the second polymer, provided that each phase includes at least one copolymerized monoethylenically unsaturated monomer and each has a Tg of from -60 ° C to 50 ° C.

In some embodiments, at least 10, preferably 20, more preferably 50, and more preferably 100,% by weight of the total second polymer is formed by polymerization at a temperature of 5 ° C to 65 ° C, preferably 10 ° C. at 50 ° C, more preferably from 20 ° C to 40 ° C, the polymerization temperature being at least 30 ° C lower than the Tg of the first polymer. Preferably at least the first 10%, more preferably at least 20%, or more preferably at least 50% of the second polymer is formed by polymerization at a temperature of 5 ° C to 65 ° C, preferably 10 ° C. at 50 ° C, and more preferably from 20 ° C to 40 ° C, the polymerization temperature being at least 30 ° C lower than the Tg of the first polymer. The temperature at which the second polymer is formed may be allowed to rise above 65 ° C during the formation of the second polymer provided that at least 10% of the second polymer is formed at a temperature of 5 to 65 ° C, the temperature of polymerization is at least 30 ° C lower than the Tg of the first polymer.

In some embodiments, the concentration of unpolymerized monomer in the reaction vessel is at any time (T) no greater than 6%, preferably no greater than 5%, and more preferably no greater than 4%, by weight, based on the total weight of the reaction mixture present in the reaction vessel over time (T). Second polymer formation may be effected in the same reaction vessel or vessel as that of first polymer formation. It may alternatively be performed after a period of time in a different reaction vessel or vessel, such as a storage tank or a drainage tank.

Polymerization techniques used to prepare aqueous emulsion polymers are well known in the art. In polymerizing the aqueous dispersion of polymeric particles of this invention, each polymer is independently prepared in that surfactants, initiators, and other additives are independently selected and may be the same or different in type and amount for each polymer, however recognizing that The second polymer is prepared in the presence of a 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, alkyl-, aryl-, or alkyl-alkali metal or ammonium salts. aryl 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 from 0.1% to 6% by weight based on the weight of monomer.

Free radical polymerization processes, including, for example, thermal initiation, redox, photochemistry, and electrochemistry, may be used for the formation of the first polymer and the second polymer independently. In some embodiments, the reaction temperature is maintained at 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, 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 in such a manner. that during the formation of at least 10% by weight of second polymer, the reaction temperature is maintained at from 5 ° C to 65 ° C. The monomer may be added neat, i.e. not as an emulsion in water, or as an emulsion in water. The monomer may be added in one or more additions or continuously, linearly or otherwise, over the reaction period or combinations thereof.

Each of the first stage polymer and the 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-alkyl group includes at least 5 carbon atoms; cumene hydroperoxide; ammonium and / or alkali metal persulphates; sodium perborate; perfosphoric acid and its salts; Potassium permanganate; and ammonium or alkali metal salts of peroxy disulfuric 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 formaldehyde sulfoxylate; Ascorbic acid; isoascorbic acid; alkali metal or ammonium salts of sulfur-containing acids such as sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfide, hydrosulfide or dithionite; formalin sulfinic acid; hydroxy methanesulfonic acid; sodium-2-hydroxy-2-sulfinate-acetic acid; acetone bisulfite; amines, such as ethanol amine; glycolic acid; glycolic acid hydrate; lactic acid; glyceric acid, malic acid; Tartaric acid; and salts of the foregoing acids may be used. Redox reaction metal salts of iron, copper, manganese, silver, platinum, vanadium, nickel, chrome, palladium, or cobalt may be employed for the formation of the first polymer and the second polymer. Typical levels of catalytic metal salts used according to the invention range from 0.01 ppm to 25 ppm. Mixtures of two or more catalytic metal salts may also usefully be employed. Chelating binders, which may be employed with the catalytic metal salts, include multidentate amino carboxylate binders, such as, for example, nitrile triacetic acid (NTA, a tetradentate binder), ethylene diamino diacetic acid (EDDA, a tetradentate binder), N- (hydroxyethyl) ethylene diamine triacetic acid (HEDTA, a pentadentate binder), ammonia diacetic acid (ADA, a tridentate binder) and ethylene diamine tetraacetic acid (EDTA, a hexadent binder) ).

Chain transfer agents, such as, for example, halogen compounds, including tetrabromomethane; allyl compounds; or mercaptans, such as alkyl thio glycolates, alkyl mercapto alkanoates, and linear or branched C 4 -C 22 alkyl mercaptans may be used to decrease the molecular weight of the independently formed first and second polymer and / or to provide a different molecular weight distribution than would otherwise have been obtained with any free radical generator primer (s). Chain transfer agent (s) may be added in one or more additions or continuously, linearly or otherwise, during 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 200 nanometers to 1,500 nanometers (nm), preferably 200-600 nm. Multimodal particle size emulsion polymers are also contemplated, in which one or more of the particle size modes are polymeric particles of the present invention and in which two or more distinct particle sizes or very wide distributions are provided as taught in the above. US Pat. 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 multistage emulsion polymerization. A multistage emulsion polymerization process in which at least two stages differing in composition are sequentially polymerized 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 polymeric particles. . Such particles are composed of two or more phases of various geometries such as, for example, core / shell or core / shell particles, shell phase core / shell particles particularly encapsulating the core, multiple core / shell particles. of nuclei, and particles of interpenetrating network. The multistage emulsion polymer may be formed in two or more stages, where the stages differ in molecular weight as well as, or in addition, differ in composition.

In some embodiments, the first polymer particles include, when dried, at least one void. First polymer particles, which include a single void formed by multistage emulsion polymerization, are known in the art and are described in U.S. Patent 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 described in U.S. Published Nos. 20010009929; 20010036990; and 20030129435. Suitable first polymer particles may also contain, when dried, multiple voids; "multiple voids" means here two or more voids, whether isolated or connected to other voids; are substantially spherical in shape or not, including, for example, void channels, interpenetrating void and polymer networks, and sponge-like structures such as those described, for example, in U.S. Patent Nos. 5,036,109; 5,157,084; 5,216,044; and 5,989,630. Multiple voids may be formed within a first polymer particle wholly or partially enclosed by a shell polymer. In alternative embodiments, the first polymer particles include one or more core polymer (s) that can be dissolved from the first polymer particle to form, when dried, a void. In further embodiments, first polymer particles including or previously including pigment particles such as, for example, titanium dioxide and silicon dioxide, supercritical carbon dioxide, FREON ™, 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 greater than 50 ° C, preferably greater than 75 ° C, and more preferably greater than 90 ° C.

In some embodiments, the first polymer with at least one void, when dry, may be formed according to U.S. Patent Methods 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, ie, any substance having a normal boiling point below 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 removal of the fugitive substance.

In such embodiments, a fugitive substance is preferably selected from the group consisting of carbon dioxide, 2,2-dimethyl propane, dichlorofluoromethane, 1,2-dichloro-tetrafluoroethane, butane, 1,1,2, 2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, dimethyl ether, 1,1-difluoroethane, octafluoropropane, chloro-difluoromethane, propane, pentafluoroethane, difluoromethane, sulfur hexafluoride, hexafluoroethane, carbon dioxide, chloro-trifluoromethane, trifluoromethane, ethane, tetrafluoromethane, methane, difluoro-methane, hexafluoroethane, carbon dioxide, chloro-trifluoromethane, trifluoromethane methane, ethane, tetrafluoromethane, methane, and combinations thereof.

In embodiments in which the first polymer particles include, when dried, at least one void, it is preferred that the void size be within the range of 100 nm to 1,200 nm. In some embodiments in which the particles of the invention increase the opacity of films in which they are present, it is preferred that the void size is within the range of 200 nm to 600 nm, and more preferably from 250 nm to 450 nm. In some embodiments, for example, where the particles of the invention are used in paper coatings, particularly in applications where paper coatings are calendered to improve gloss, it is preferred that the void size is within the 750 nm range. at 1,200 nm, and more preferably from 1,000 nm to 1,200 nm.

Aqueous dispersions comprising the particles of the invention may additionally comprise 5% to 95%, preferably 5% to 50%, and more preferably 5% to 30% by weight, based on the total dispersion weight of non-empty silica particles. Non-empty particles may have Tg values ranging from -50 ° C to 50 ° C and typically have particle sizes smaller than 10 nm to greater than 1,000 nm, preferably 30 nm to 500 nm, and more preferably 40 µm. nm at 200 nm. In such embodiments, there may be empty particle populations having different mean particle sizes, i.e. bimodal or polymodal particle size distributions. In some embodiments, for example, when the dispersions of the invention are used in formulating coatings that can be applied to aged or worn substrates, it may be desirable to have from 20% to 35% by weight based on the total polymer content of the dispersion. non-empty particles having a particle size of 10 nm to 100 nm, and preferably 40 nm 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 more than 50% of the surface area of the first polymer particle must be covered by the second polymer. Preferably, more 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 polymer 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 greater than 30%, and preferably greater than 40% by weight. The presence of polymer particles having a particle size smaller than that of the particles of the invention may produce dispersions with solids content approaching 70% or more. In addition, high solids content, or the presence of smaller particles, or a combination of both, may prevent sedimentation or precipitation of the particles of the invention. High solids content herein refers to solids contents 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, clear coat, topcoat, primer, paper coating , leather lining, nonwoven or textile lining, and elastomeric lining, saturating, caulking, sealing, and adhesive. Such a coating typically exhibits improvement in film formation, particularly at temperatures below 30 ° C or 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, of copolymerized multiethylenically unsaturated monomer.

The polymers of the invention may advantageously be used as binding agents in the formulation of pigmented coatings. "Binder" as used herein refers to a component in a formulation that provides integrity to the films formed by drying the formulation. In relatively low PVC coating formulations, the binder can achieve this effect by the very continuous film formation in which the other components, including pigments and diluents, are embedded. The binder may also act to form particle adhesion points of the other components in the formulation, for example pigments and diluents. This bonding mechanism is most common in relatively high PVC formulations in which the binder may not be present in an amount suitable to form a continuous film. Polymeric particle dispersions are commonly used as binding agents in aqueous coating formulations. Typically, binder particles are of such character as film-forming at the temperature at which the formulation is dried. Alternatively, solvents or coalescing agents may be added to soft binder particles to make them film-forming.

Pigmented coating formulations using the polymeric particles of the invention as binding agents may provide greater opacity than analogous formulations using traditional non-empty polymeric particles as the binding agent. Alternatively, a formulator can achieve a desired level of opacity in coating formulations using the particles of the invention as a binder by employing a lower level of pigment and / or diluent than would be required to achieve the same level of opacity in a coating. comparable formulation using traditional non-empty polymeric particles as binder.

An aqueous coating composition having the aqueous dispersion of the invention is prepared by techniques which are well known in the coating art. First, if the aqueous coating composition is to be pigmented, at least one pigment will typically be well dispersed in an aqueous medium under high shear, as provided by a COWLES® mixer. Then, the aqueous dispersion of polymeric particles is added under minor shear agitation, along with other coating adjuvants as desired. Alternatively, the aqueous dispersion of polymer particles may be included in the pigment dispersion step. The aqueous coating composition may contain conventional coating adjuvants such as, for example, tackifiers, pigments, diluents, emulsifiers, crosslinking agents, coalescing agents, buffers, neutralizers, rheology modifying or thickening agents, humectants, wetting agents, biocides, plasticizers, defoaming agents, colorants, waxes, and antioxidants. The aqueous coating composition may contain up to 75% by weight, based on the weight of polymeric particles, of an emulsion polymer not meeting the description of the aqueous dispersion of polymeric particles of the invention, such as a non-film forming emulsion polymer and / or film maker.

Examples of suitable pigments and diluents for use in the formulation of coatings include titanium dioxide, such as anatase and rutile titanium dioxide; zinc oxide; antimony oxide; iron oxide; magnesium silicate; calcium carbonate; organic and inorganic colored pigments; aluminosilicates; silica; various clays, such as kaolin and delaminated clay; and lead oxide. The amounts of pigment and diluent in the aqueous coating composition range from a bulk pigment (PVC) concentration of 0 to 95 and thus include coatings other than those described in the art, for example transparent coatings, stains, flat coatings, coating coatings. satin, semi-gloss coatings, glossy coatings, primer coatings, and textured coatings. The pigment volume concentration is calculated by the following formula: PVC (%) - (pigment volume (s) + diluent volume (i)) total dry ink volume In one embodiment, the aqueous coating composition includes a photosensitive group. The photosensitive group that is capable of absorbing some portion of the sunlight spectrum and, without being bound by a specific theory, potentially acting as a photoinitiator to crosslink the polymer during exposure to the outside. The photosensitive group may be a photosensitive compound added to the aqueous coating composition before, during, or after formation of the aqueous dispersion, or a photosensitive group which 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, in which one or both phenyl rings are substituted, such as, for example, benzophenone, 4-methyl-benzophenone, 4-hydroxy-benzophenone, 4-amino-benzophenone, 4-chloro- benzophenone, 4-hydroxycarbonylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4-carboxymethylbenzophenone, 3-nitrobenzophenone, and substituted phenyl ketones such as phenylaceto-phenones. Photosensitive groups may be present at one or more stages as copolymerized ethylenically unsaturated monomers containing photosensitive groups. Examples of ethylenically unsaturated monomers containing photosensitive groups include vinyl toluene, allyl benzoyl benzoates and monomers incorporating pendant benzophenone groups, such as vinyl benzyl methyl benzoyl benzoate, hydroxy methacryloxy propyl methyl benzoyl benzoate, hydroxy methacryloxy propyl benzoyl benzoate, and hydroxy methacryloxy propoxy 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 from 0.1% to 1% by weight of one or more photosensitive compounds, based on the weight of dry polymer.

Preferably, the aqueous coating composition contains less than 5 wt% VOC, more preferably less than 3 wt% VOC, and even more preferably less than 1.7 wt% VOC, based on the total weight of the product. aqueous coating composition. A volatile organic compound (VOC) is defined herein as a carbon-containing compound having a boiling point below 280 ° C at atmospheric pressure.

Additionally, the aqueous coating composition may contain coalescing agents, some of which are not VOCs, for example, coalescing agents having a boiling point above 280 ° C at atmospheric pressure. A coalescing agent is a compound which is added in an aqueous polymer particle dispersion, paint or coating and which reduces the minimum film-forming temperature (MFFT) of the aqueous polymer particle dispersion or aqueous coating composition by at least 1Â °. Ç. MFFT is measured using the ASTM D2354 test method. Examples of non-VOC coalescing agents include plasticizers, low molecular weight polymers, surfactants, and self-oxidizing plasticizers such as unsaturated fatty acid alkyl esters. Preferred are alkyl esters prepared from oils such as flaxseed, tung, dehydrated castor, soybean, talol, sunflower, and corn. Examples of non-VOC coalescing agents include unsaturated fatty acid esters such as mono-, di-, or tri-unsaturated fatty acids. Suitable unsaturated fatty acid esters include monounsaturated fatty acid esters formed of palmitoleic acid, oleic acid, or caproleic acid; diunsaturated fatty acid esters formed of linoleic acid; triunsaturated fatty acid esters formed of linolenic acid or eleosteric acid; or mixtures thereof. Suitable esters of unsaturated fatty acids include alkyl esters, such as methyl and ethyl esters; substituted alkyl esters such as esters formed of ethylene glycol and propylene glycol and unsaturated fatty acid alkyl esters; diethylene glycol, triethylene glycol; dipropylene glycol; tripropylene glycol; and diethylene glycol monobutyl ether. In one embodiment, the above self-oxidizing plasticizers are used in conjunction with an aqueous dispersion of polymeric particles containing 0.25% to 12.5% acetoacetoxyethyl (meth) acrylate as copolymerized units based on total particle weight. polymeric. Self-oxidation 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 employed. Typical methods of preparing paint or coating may introduce adventitious VOCs from aqueous dispersion of polymeric particles, biocides, defoamers, soaps, dispersants, and thickeners. These typically correspond to 0.1% by weight of VOC based on the total weight of the aqueous coating composition. Additional methods such as, for example, vapor extraction of aqueous dispersion of polymeric particles and selection of low VOC additives such as biocides, defoamers, soaps, dispersants, and thickeners may be used to further reduce paint or coating. to less than 0.01% by weight of VOC 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 Pa.s to 2000 Pa.s as measured using a Brookfield viscometer; Appropriate viscosities for different application methods and end uses vary considerably. The aqueous coating composition may be applied by conventional application methods such as, for example, brush, paint roller, air atomized spraying, air assisted spraying, airless spraying, high volume low pressure spraying, sprayless spraying. air assisted air, and electrostatic spraying. 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; worn surfaces; cement substrates; and asphalt substrates, with or without prior substrate treatment, such as primer. The coated aqueous composition on the substrate is typically dried, or allowed to dry, at a temperature of 5 ° C to 95 ° C.

A preferred process for forming dispersions of the invention in which the first polymer comprises, when dried, at least one void is analogous to that described in US Published Publication No. 20010009929. In the preferred process of the invention, an aqueous emulsion polymer dispersion is provided. multistage, comprising a core stage polymer (the "core") and a first shell stage polymer (the "first shell"). The core and first shell may be comprised of more than one stage. There may also be one or more intermediate stages. Preferably, the multistage 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 substantially formed by the addition of at least one monoethylenically monomer to the multistage polymer emulsion. unsaturated and causing at least 10% of the monomer to polymerize at a temperature of 5 ° C to 65 ° C in the presence of multistage polymer. This temperature is at least 30% lower than the calculated Tg of the first shell stage polymer. The multistage emulsion polymer core is forced to swell by the addition of a swelling agent to the aqueous dispersion before, during, or after polymerization of the monomers comprising the second shell stage polymer.

In this process, the first shell stage polymer has the characteristics assigned herein to the first polymer of the invention and the second shell stage polymer has the characteristics assigned herein to the second polymer of the invention. Preferably, the first shell stage 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.

Preferred cores of the multistage polymers used in the process are as described in US 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 obeyed by a one-stage process or a multi-stage process, has an average particle diameter of 50 nm to 1.0 pm, and preferably 100 nm to 300 nm, in an untouched condition. If the nucleus is obtained from a seed polymer such as that described in U.S. Publication No. 20010009929, the seed polymer preferably will have an average particle size of 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 core weight of multiethylenically unsaturated monomer.

Within the context of the preferred process, suitable hydrophilic monoethylenically unsaturated monomers useful for preparing 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, acrylopropionic acid, (meth) acryloxypropionic acid, itaconic acid, aconitic acid, maleic acid or anhydride, fimaric acid, crotonic acid, monomethyl maleate, monoethyl 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 monomer and polymer in multistage emulsion, are capable of permeating the 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, trimethyl amine, and triethyl amine; fixed or permanent bases such as potassium hydroxide, lithium hydroxide, ammonium and zinc complex, ammonium and copper complex, ammonium and silver complex, strontium hydroxide, and barium hydroxide. Solvents, such as, for example, ethanol, hexanol, octanol, Texanol® solvent and those described in U.S. Patent 4,594,363, may be added to aid in fixed or permanent base pentration. Ammonia or ammonium hydroxide are preferred. The multistage emulsion polymer core used in the preferred process may be forced to swell by the addition of a swelling agent to the aqueous dispersion before, during, or after polymerization of the monomers comprising the second shell stage polymer but after formation. of the first shell polymer. In a preferred embodiment, the 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 polymer polymer content in the dispersion, of unreacted monomer under conditions in which there is more substantial polymerization of the monomer; and substantially reducing the monomer level by at least 50%. The phrase "under conditions in which there is no substantial monomer polymerization" and the techniques for achieving such conditions are as described in U.S. Publication No. 20010009929.

Preferably, the amount of swelling agent is within the range of 75% to 300%, and most preferably within the range of 90% to 250%, based on the functionality equivalents in the neutralizable core. 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 minimal amount of time under high temperature conditions in the presence of monomer and without substantial polymerization occurring. Under these conditions, swelling is generally complete within 30 minutes, preferably within 20 minutes, and more preferably within 10 minutes, of the addition of one or more swelling agents.

Following swelling of the polymer in multistage emulsion in the presence of both monomer and swelling agent, it is desirable to reduce the monomer level to less than 10,000 ppm, and preferably to less than 5,000 ppm, based on polymer solids. This can be accomplished by any appropriate means. Preferably, the monomer level is reduced by monomer polymerization. This may be accomplished by any appropriate means, such as by adding one or more primers cited above. It is preferred to begin reducing the monomer level within 20 minutes, and more preferably within 10 minutes, by adding 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 dodecyl benzene sulfonate (23%);

D1 is deionized; SPS is sodium persulfate; ALMA is allyl methacrylate;

L is liter, p is weight; vol is volume; g is grass; and min is minute. TEST METHODS

Particle Size: Measurements were made by CHDF using Matec CHDF-2000 (capillary hydrodynamic fractionation); Matec Applied Sciences, Northborough, MA.

S / Mil Determination: An aqueous dispersion was spread on a black vinyl friction card. The wet film was dried at 30% relative humidity. Kubelka-Munk scattering coefficient was determined on the dry film (~ 50.8 micrometer thickness) by the P.B. Mitton and A.E. Jacobson (Off. Digest, Sept. 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 light is incident on the coating at a 45 degree angle from normal, and that scattered light is collected at a 0 degree angle from normal.

Friction Resistance: Aqueous coating compositions were spread on black vinyl cards using a 177.8 micrometer film pourer. The cards were air dried in a horizontal position for 7 days in an open room kept at 23 ° C ± 1.9 ° C and at a relative humidity of 50% ± 5%. Cut-off frictional resistance that measures the frictional resistance of an ink film over the numerous friction cycles required to erode the ink film onto the substrate has been determined. The procedure used a nylon bristle brush and a friction medium prepared by mixing the SC-2 abrasive friction medium from The Leneta Company, Inc. (Mahwah, NJ), water and defoamer. The ink cards were held in the abrasion tester on an aluminum plate containing shims. The brush was mounted on the holder and 10 g of friction medium was evenly spread over the brush bristles. The cycle counter was set to zero and the test started. After every 400 cycles before rupture, an additional 10 grams of friction medium was added. The number of cycles to completely remove the ink film in one continuous line across a 1.27 cm width of shim film was recorded. Reported values were an average of eight measurements.

BCOP Screening Factor: A sample of aqueous dispersion to be tested is mixed with a BCOP (Bead Coated Opaque Polymer) Reference Dispersion (as defined below). The relative amounts of the BCOP Test Dispersion and Reference Dispersion are selected such that the resulting mixture comprises 30 wt%, based on the total weight of the blend polymer, test binder polymer solids, and 70% by weight based on the total polymer weight of the BCOP Reference Dispersion polymer solids blend. A 177.8 micrometer wet film of the mixture is spread over a black spinning vinyl card (Leneta # P121010N). Black friction vinyl card has been measured for thickness (in micrometer) in four defined areas using, for example, an Ames gauge (# 2-212C) available from Ames Corporation of Waltham, MA. The film is dried for two hours in a low relative humidity chamber or room (relative humidity <40%, where if the relative humidity is any <40% during drying, the BCOP masking factor will not change substantially). The reflectance of the dry film is measured by a reflectometer, for example, a Gardner Instrument Reflectome (BYK-Gardner of Columbia, MD), over the four defined areas. Film thickness is also determined over each of the defined areas using the Ames meter. The BCOP masking factor is calculated for each of the four areas defined as: where R = reflectance; and t = film thickness in mils (1 mil = 25.4 micrometers). The average of four measurements is taken as the BCOP masking factor for the dry film. Preferably, in the invention, the BCOP masking factor is at least 0.1.

80% BCOP Coverage Factor: The procedure and calculation as described for determining the BCOP Coverage Factor are reproduced except that the film is dried overnight at 25 ° C / 80% Relative Humidity in a temperature / humidity (Hotpack, Model # 417532 available from SP Industries, Inc. of Wartminster, PA) and then dried at <40% relative humidity for one hour in a low humidity room / chamber.

BCQP Stability Factor: BCOP Stability Factor = 1 - (80% BCOP Coverage Factor / BCOP Coverage Factor). In the invention, preferably, the stability factor of BCOP is less than 0.5. BCOP Reference Dispersion: The BCOP Reference Dispersion is formed by the following process: 936 g BA, 850.6 g MMA, 23.4 g AA, and 82.7 g of a 30% aqueous solution of Sodium poly (ethylene glycol) lauryl ether sulfate was combined with 674 g of DI water and the mixture was stirred with a hand held homogenate for 30 seconds to form an emulsion. 938 g of DI water and 3.6 g of a 30% aqueous solution of sodium poly (ethylene glycol) lauryl ether sulfate were added to a 5 L 4-neck round bottom glass vessel equipped with temperature controller, condenser, and mechanical stirring. The vessel was heated to 85 ° C under nitrogen while stirring. With the vessel temperature at 85 ° C, a 76 g aliquot of the homogenized monomer emulsion was added to the vessel, immediately followed by 7.2 g of APS dissolved in 20 g of water. The resulting mixture was kept under stirring for 5 min. The remaining monomer emulsion was then fed to the vessel for approximately 80 minutes maintaining the reaction temperature at 85 ° C.

Under completeness of the monomer emulsion feed, the vessel contents were maintained at 85 ° C for an additional 10 min before being allowed to cool to 60 ° C. 20 g of 10 wt% iron sulfate solution was added to the vessel followed by the addition of 3.6 g of 70% t-BHP in 58 g of water and 1.8 g of isoascorbic acid dissolved in 58 g of water for approximately 30 min. The vessel was allowed to cool to room temperature. At 30 ° C, the emulsion pH was adjusted to pH 9 by the addition of ammonium hydroxide. The emulsion was removed from the vessel and filtered. The final latex was 49.0 wt% solids. The particle size was 106 nm.

EXAMPLES EXAMPLE 1. First Polymer Formation: A 5 L four-neck round bottom flask was equipped with paddle stirrer, thermometer, nitrogen inlet, and reflux condenser. Dl water, 1200 g, was added to the vessel and heated to 85 ° C under a nitrogen atmosphere. A solution of monomers (ME) was prepared by mixing 370 g of DI water, 18.0 g of SDS, 24.0 g of MAA, 1056 g of MMA, and 120 g of BA. From this ME, 45 g were removed and set aside. With the vessel water at 85 ° C, 34.0 g of SDS was added to the vessel. This was followed by the addition of 45 g of ME previously set aside in the vessel and the addition of a solution of 5.0 g of SPS in 50 g of Dl water. The contents of the vessel were shaken for 15 min. The remaining ME was fed to the vessel for a period of 2 hours at 85 ° C. After completing the monomer feed the dispersion was maintained at 85 ° C for 15 min, cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 40.0% and an average particle diameter of 55 nm. EXAMPLE 2. Formation of First Polymer: Using the same equipment as in Example 1, D 1 water, 1200 g, was added to the vessel and heated to 85 ° C under a nitrogen atmosphere. ME was prepared by mixing 370 g of DI water, 18.0 g of SDS, 24.0 g of MAA, 1056 g of MMA, and 120 g of BA. From this ME, 45 g were removed and set aside. With the vessel water at 85 ° C, 18.0 g of SDS was added to the vessel. This was followed by the addition of 45 g of ME previously set aside in the vessel and the addition of a solution of 5.0 g of SPS in 50 g of Dl water. The contents of the vessel were shaken for 15 min. The remaining ME was fed to the vessel for a period of 2 hours at 85 ° C. After completing the monomer feed the dispersion was maintained at 85 ° C for 15 min, cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 40.0% and an average particle diameter of 70 nm. EXAMPLE 3. Formation of First Polymer: Using the same equipment as in Example 1, water DI, 1900 g, was added to the vessel and heated to 85 ° C under a nitrogen atmosphere. ME was prepared by mixing 550 g of DI water, 28.0.0 g of SDS, 18.0 g of MAA, and 1782 g of styrene. From this ME, 65 g were removed and set aside. With the vessel water at 85 ° C, 110.0 g of SDS was added to the vessel. This was followed by the addition of 65 g of ME previously set aside in the vessel and the addition of a solution of 6.7 g of SPS in 50 g of Dl water. The contents of the vessel were shaken for 15 min. The remaining ME was fed to the vessel for a period of 2 hours at 85 ° C. After completing the monomer feed the dispersion was maintained at 85 ° C for 15 min, cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 39.7% and an average particle diameter of 58 nm. EXAMPLE 4. Formation of First Polymer: Using the same equipment as in Example 1, water DI, 1900 g, was added to the vessel and heated to 85 ° C under a nitrogen atmosphere. ME was prepared by mixing 550 g of DI water, 28.0 g of SDS, 18.0 g of MAA, and 1782 g of styrene. With the vessel water at 85 ° C, 110.0 g of SDS was added to the vessel. Next, a solution of 6.7 g of SPS in 50 g of Dl water was added to the vessel. The ME was fed to the vessel for a period of 2 hours at 85 ° C. After completing the monomer feed the dispersion was maintained at 85 ° C for 15 min, cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 40.0% and an average particle diameter of 50 nm. EXAMPLE 5. First Polymer Formation: Using the same apparatus as in Example 1, D 1 water, 1200 g, was added to the vessel and heated to 85 ° C under a nitrogen atmosphere. ME was prepared by mixing 370 g Dl water, 18.2 g SDS, 12.0 g MAA, and 1188 g styrene. From this ME, 45 g were removed and set aside. With the vessel water at 85 ° C, 18.2 g of SDS was added to the vessel. This was followed by the addition of 45 g of ME previously set aside in the vessel and the addition of a solution of 5.0 g of SPS in 50 g of Dl water. The contents of the vessel were shaken for 15 min. The remaining ME was fed to the vessel for a period of 2 hours at 85 ° C. After completing the monomer feed the dispersion was maintained at 85 ° C for 15 min, cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 38.8% and an average particle diameter of 101 nm. EXAMPLE 6. Formation of First Polymer: Using the same equipment as in Example 1, water D1, 1200 g, was added to the vessel and heated to 85 ° C under a nitrogen atmosphere. ME was prepared by mixing 370 g Dl water, 18.2 g SDS, 12.0 g MAA, and 1188 g styrene. From this ME, 45 g were removed and set aside. With the vessel water at 85 ° C, 7.8 g of SDS was added to the vessel. This was followed by the addition of 45 g of ME previously set aside in the vessel and the addition of a solution of 5.0 g of SPS in 50 g of Dl water. The contents of the vessel were shaken for 15 min. The remaining ME was fed to the vessel for a period of 2 hours at 85 ° C. After completing the monomer feed the dispersion was maintained at 85 ° C for 15 min, cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 39.5% and an average particle diameter of 145 nm. EXAMPLE 7. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, water D1, 800 g, was added to the vessel along with 375 g of first polymer of Example 1 and adjusted to 25 ° C under an atmosphere of nitrogen. ME was prepared by mixing 340 g of DI water, 22.0 g of SDS, 13.5 g of MAA, 553.5 g of MMA, and 783.0 g of BA. With the vessel temperature at 25 ° C, a solution of 20 g 0.1% iron sulfate and 2 g ethylene diamino tetraacetic acid, 1% sodium salt (versene) were added to the vessel. 2 min later # 1 co-feed consisting of 3.9 g of t-BHP dissolved in 90 g of Dl water, and # 2 co-feed consisting of 2.7 g of isoascophobic acid dissolved in 90 g of Dl water were fed to the reactor at a flow rate of 0.5 g / min. 2 min later ME feeding was started at a flow rate of 5.0 g / min. The ME feed flow was gradually increased so that the ME feed ended in 180 min and the temperature was allowed to rise without any external heating or cooling. The temperature at the end of ME was ~ 65 ° C. With the completion of ME feeding the co-feeds were continued for another 30 min. With the completion of the co-feeds 12 g of ammonium hydroxide (28%) was added to the vessel. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 43.5% and an average particle diameter of 117 nm. EXAMPLE 8. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, water D1, 800 g, was added to the vessel along with 373 g of first polymer of Example 2 and adjusted to 25 ° C under an atmosphere of nitrogen. ME was prepared by mixing 340 g of DI water, 22.0 g of SDS, 13.5 g of MAA, 553.5 g of MMA, and 783.0 g of BA. With the vessel temperature at 25 ° C, a solution of 20 g of 0.1% iron sulfate and 2 g of 1% versene were added to the vessel. 2 min later co-feed # 1 consisting of 3.9 g of t-BHP dissolved in 90 g of Dl water, and co-feed # 2 consisting of 2.7 g of isoascorbic acid dissolved in 90 g of Dl water were fed to the reactor at a flow rate of 0.5 g / min. 2 min later ME feeding was started at a flow rate of 5.0 g / min. The feed rate of ΜΕ was gradually increased so that the ME supply ended in 180 min and the temperature was allowed to rise without any external heating or cooling. The temperature at the end of the ME was ~ 65 ° C. With the completion of ME feeding the co-feeds were continued for another 30 min. With the completion of the co-feeds 12 g of ammonium hydroxide (28%) was added to the vessel. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 43.5% and an average particle diameter of 148 nm. EXAMPLE 9. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, water D1, 1000 g, was added to the vessel together with 377.8 g of first polymer of Example 3 and adjusted to 22 ° C under a nitrogen atmosphere. ME was prepared by mixing 340 g of DI water, 22.0 g of SDS, 13.5 g of MAA, 553.5 g of MMA, and 783.0 g of BA. With the vessel temperature at 25 ° C, a solution of 20 g 0.1% iron sulphate and 2 g of 1% versene were added to the vessel. 2 min later co-feed # 1 consisting of 3.9 g of t-BHP dissolved in 90 g of Dl water, and co-feed # 2 consisting of 2.7 g of isoascorbic acid dissolved in 90 g of Dl water were fed to the reactor at a flow rate of 0.5 g / min. 2 min later ME feeding was started at a flow rate of 5.0 g / min. The ME feed flow was gradually increased so that the ME feed ended in 180 min and the temperature was allowed to rise without any external heating or cooling. The temperature at the end of ME was ~ 65 ° C. With the completion of ME feeding the co-feeds were continued for another 30 min. With the completion of the co-feeds 12 g of ammonium hydroxide (28%) was added to the vessel. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 40.9% and an average particle diameter of 135 nm. EXAMPLE 10. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, water D1, 800 g, was added to the vessel along with 375 g of first polymer of Example 4 and adjusted to 25 ° C under an atmosphere of nitrogen. ME was prepared by mixing 340 g of DI water, 22.0 g of SDS, 13.5 g of MAA, 553.5 g of MMA, and 783.0 g of BA. With the vessel temperature at 25 ° C, a solution of 20 g 0.1% iron sulphate and 2 g of 1% versene were added to the vessel. 2 min later # 1 co-feed consisting of 3.9 g of t-BHP dissolved in 90 g of Dl water, and # 2 co-feed consisting of 2.7g of isoascorbic acid dissolved in 90 g of Dl water were fed to the reactor at a flow rate of 0.5 g / min. 2 min later ME feeding was started at a flow rate of 5.0 g / min. The ME feed flow was gradually increased so that the ME feed ended in 180 min and the temperature was allowed to rise without any external heating or cooling. The temperature at the end of ME was ~ 65 ° C. With the completion of ME feeding the co-feeds were continued for another 30 min. With the completion of the co-feeds 12 g of ammonium hydroxide (28%) was added to the vessel. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 40.3% and an average particle diameter of 118 nm. EXAMPLE 11. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, D1 water, 800 g, was added to the vessel along with 580 of first polymer core from Example 5 and adjusted to 25 ° C under an atmosphere. of nitrogen. ME was prepared by mixing 280 g of DI water, 18.5 g of SDS, 11.2 g of MAA, 461.3 g of MMA, and 652.5 g of BA. With the vessel temperature at 25 ° C, a solution of 20 g 0.1% iron sulphate and 2 g of 1% versene were added to the vessel. 2 min later # 1 co-feed consisting of 3.2 g of t-BHP dissolved in 80 g of Dl water, and # 2 co-feed consisting of 2.25 g of isoascorbic acid dissolved in 80 g of Dl water were fed to the reactor at a flow rate of 0.5 g / min. 2 min later ME feeding was started at a flow rate of 5.0 g / min. The ME feed flow was gradually increased so that the ME feed ended in 120 min and the temperature was allowed to rise without any external heating or cooling. The temperature at the end of ME was ~ 60 ° C. With the completion of ME feeding the co-feeds were continued for another 30 min. With the completion of the co-feeds 12 g of ammonium hydroxide (28%) was added to the vessel. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 43.2% and an average particle diameter of 173nm. EXAMPLE 12. Formation of aqueous polymer particle dispersion: Using the same apparatus as in Example 1, water D1, 800 g, was added to the vessel together with 569.6 g of first polymer of Example 6 and adjusted to 25 ° C under a nitrogen atmosphere. ME was prepared by mixing 280 g of DI water, 18.5 g of SDS, 11.2 g of MAA, 461.3 g of MMA, and 652.5 g of BA. With the vessel temperature at 25 ° C, a solution of 20 g 0.1% iron sulphate and 2 g of 1% versene were added to the vessel. 2 min later # 1 co-feed consisting of 3.2 g of t-BHP dissolved in 80 g of Dl water, and # 2 co-feed consisting of 2.25 g of isoascorbic acid dissolved in 80 g of Dl water were fed to the reactor at a flow rate of 0.5 g / min. 2 min later ME feeding was started at a flow rate of 5.0 g / min. The ME feed flow was gradually increased so that the ME feed ended in 120 min and the temperature was allowed to rise without any external heating or cooling. The temperature at the end of ME was ~ 60 ° C. With the completion of ME feeding the co-feeds were continued for another 30 min. With the completion of the co-feeds 12 g of ammonium hydroxide (28%) was added to the vessel. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 42.7% and an average particle diameter of 247 nm. COMPARATIVE EXAMPLE A. Formation of aqueous dispersion of polymeric particles: Using the same apparatus as in Example 1, D1 water, 1000 g, was added to the vessel and heated to 90 ° under a nitrogen atmosphere. ME was prepared by mixing 340 g of DI water, 22.0 g of SDS, 13.5 g of MAA, 553.5 g of MMA, and 783.0 g of BA. With the vessel temperature at 90 ° C, a solution of 4.4 g of SPS in 40 g of D1 water was added to the vessel. Next, 373 g of first polymer from Example 2 was added to the vessel. Starting at 78 ° C above ME together with a solution of 1.0 g SPS in 90 g Dl water were co-fed to the vessel over a period of three hours. The vessel temperature was allowed to rise to 85 ° C. With the completeness of ME feeding and co-feeding the batch was kept at 85 ° C for another 15 m. 12 g of ammonium hydroxide (28%) was added to the vessel. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 44.7% and an average particle diameter of 157 nm. COMPARATIVE EXAMPLE B. Formation of aqueous dispersion of polymeric particles: Using the same apparatus as in Example 1, D1 water, 1000 g, was added to the vessel and heated to 90 ° under a nitrogen atmosphere. ME was prepared by mixing 340 g of DI water, 22.0 g of SDS, 13.5 g of MAA, 553.5 g of MMA, and 783.0 g of BA. With the vessel temperature at 90 ° C, a solution of 4.4 g of SPS in 40 g of D1 water was added to the vessel. Next, 377.8g of first polymer from Example 3 was added to the vessel. Starting at 78 ° C above ME together with a solution of 1.0 g SPS in 90 g Dl water were co-fed to the vessel over a period of three hours. The vessel temperature was allowed to rise to 85 °. With the completion of ME feeding and co-feeding the batch was kept at 85 ° C for another 15 min. 12 g of ammonium hydroxide (28%) was added to the vessel. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 44.8% and an average particle diameter of 144 nm. EXAMPLE 13. Preparation of polymer cores for first polymer preparation: A 66 MMA / 34 MAA% w polymer core was prepared according to the teachings of Examples 1-16 of U.S. Patent 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 14. Preparation of First (Neutralized) Polymer: Using the same apparatus as in Example 1, D1 water, 1000 g, was added to the vessel and heated to 89 ° C under a nitrogen atmosphere. To the heated vessel water was added 3.7g of SPS in 30g of DI water. This was immediately followed by 219.4g of Core # 1 (Example 1). A solution of monomers I (ΜΕ 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. in the vessel for a period of 60 min at 78 ° C. With the completeness of ΜΕ I, a second monomer emulsion (ΜΕ 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 flaxseed oil fatty acid, and 2.1 g ALMA. Monomer emulsion II (ΜΕ II) was added to the vessel along with a separate mixture of 0.93 g of SPS dissolved in 60 g of DI water for 60 min. The temperature of the reaction mixture was allowed to rise to 92 ° C. With the completion of ΜΕ II and co-feed, 22 g of a 0.1% iron sulfate solution and 1% versene in water were added to the vessel. Next, a third monomer emulsion (ΜΕ III) which was prepared by mixing 54.0 g Dl water, 2.0 g SDS, 168 g styrene, and 2.0 g 4-hydroxy TEMPO was added. in the vase. This was followed by the addition of 500 g hot (90 ° C) DI water. With the vessel temperature at ~ 85 ° C, a solution of 31.0 g of 50% sodium hydroxide dissolved in 600 g hot Dl water was added to the vessel for 10 min. 10 min after completion of the sodium hydroxide addition, a solution of 1.0 g SPS mixed with 20 g Dl water was added to the vessel and the batch was maintained 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 15. Preparation of First (Non-Neutralized) Polymer: Using the same equipment as in Example 1, D 1 water, 1200 g, was added to the vessel and heated to 89 ° C under a nitrogen atmosphere. To the heated vessel water was added 5.25 g of SPS dissolved in 30 g of Dl water. This was immediately followed by 314.5 g of Core # 2 (Example 1). A ΜΕ I, which was prepared by mixing 100 g Dl water, 6.7 g SDS, 100 g styrene, 88.0 g MMA, and 12 g MAA, was added to the pot over a period of 60 min. at 78 ° C. With the completeness of ΜΕ I, an ΜΕ II was prepared by mixing 400 g Dl water, 18 g SDS, 1179 g styrene, 18.0 g MAA, 6 g flaxseed fatty acid, and 3, 0 g of SOUL. II was added to the vessel together with a separate mixture of 1.3 g of SPS dissolved in 90 g of D1 water for 60 min. The temperature of the reaction mixture was allowed to rise to 92 ° C. With the completeness of ΜΕ II and co-feed, the reaction mixture was kept for 30 min at 85 ° C and then cooled to room temperature and filtered to remove any formed clot. The final non-neutralized latex had a solids content of 39.9 wt%, an average particle diameter of 375 nm, and a pH of 2.2. EXAMPLE 16. Preparation of First (Non-Neutralized) Polymer: A first polymer was prepared using 315.0 g of Core # 1 (Ex.13) following the procedure used in Example 15. The final non-neutralized latex had a solids content of 39.8 wt%, an average particle diameter of 315 nm, and a pH of 2.1, EXAMPLE 17. Preparation of first (non-neutralized) polymer: A first polymer was prepared using 315.0 g of Core # 3 ( Ex. 13) following the procedure used in Example 15. The final non-neutralized latex had a solids content of 40.1 wt%, an average particle size of 350 nm, and a pH of 2.2. EXAMPLE 18. Preparation of First (Non-Neutralized) Polymer: Using the same equipment as in Example 1, D 1 water, 1200 g, was added to the vessel and heated to 89 ° C under a nitrogen atmosphere. To the heated vessel water was added 5.25 g of SPS dissolved in 30 g of DI water. This was immediately followed by 314.5 g of Core # 3 (Example 13). ΔI, which was prepared according to Example 3, was added to the vessel over a period of 60 min at 78 ° C. At the completeness of ΜΕ I, ΜΕ II was prepared according to Example 3. ΜΕ II was added to the vessel along with a separate mixture of 1.3 g SPS dissolved in 90 g DI water for 60 min. The temperature of the reaction mixture was allowed to rise to 92 ° C. With the completeness of ΜΕ II and co-feed, the reaction mixture was kept for 30 min at 85 ° C and then cooled to room temperature and filtered. The final non-neutralized latex had a solids content of 40.0 wt%, an average particle diameter of 380 nm, and a pH of 2.2. EXAMPLE 19. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, DI water, 700 g, was added to the vessel and heated to 85 ° under a nitrogen atmosphere. 1704g of first polymer from Example 14 was added to the vessel and the temperature was adjusted to 60 ° C. ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 378 g MMA, and 522 g BA. With the vessel temperature at 60 ° C, a solution of 20 g of 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds, including a solution of 2.3 g t-BHP mixed with 80 g Dl water, together with a separate solution of 1.8 g isoascorbic acid mixed with 80 g Dl water, were both added. in the vessel at a flow rate of 0.5g / min. 2 min after initiation of the co-feed solutions, the previously prepared ME was added to the vessel for 120 min. There was no external heating applied in the reaction. The vessel temperature was maintained at 60 ° C throughout the duration of ME feeding. With the completion of ME feeding, the co-feeding 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 20. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, D1 water, 700 g, was added to the vessel and heated to 85 ° C under a nitrogen atmosphere. 1704g of first polymer from Example 14 was added to the vessel and the temperature was adjusted to 50 ° C. An ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 378 g MMA, and 522 g BA. With the vessel temperature at 50 ° C, a solution of 20 g of 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds, including a solution of 2.3 g t-BHP mixed with 80 g Dl water, together with a separate solution of 1.8 g isoascorbic acid mixed with 80 g Dl water, were both added. in the vessel at a flow rate of 0.5g / min. 2 min after starting the feed solutions, the previously prepared ΜΕ was added to the vessel for 120 min. There was no external heating applied in the reaction. The vessel temperature was maintained at 50 ° throughout the duration of ME feeding. With the completion of ME feeding, the co-feeding 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 21. Aqueous Dispersion Formation of Polymeric Particles: Example 20 was repeated, except that D 1 water, 700 g, was added to the vessel and heated to 76 ° C under a nitrogen atmosphere. After 1704 g of the polymer of Ex. 14 was added to the vessel the temperature was adjusted to 40 ° C. The vessel temperature was maintained at 40-44 ° C over the duration of alimentação feeding. The filtered dispersion had a solids content of 34.6%, and an average particle size of 508 nm. The Kubelka-Munk scattering coefficient (S / Mil) was measured on the dry polymer film and was found to be 0.89. EXAMPLE 22. Aqueous Dispersion Formation of Polymeric Particles: Example 20 was repeated, except that D 1 water, 700 g, was added to the vessel and heated to 66 ° C under a nitrogen atmosphere. After 1704 g of the polymer of Ex. 14 was added to the vessel the temperature was adjusted to 30 ° C. The vessel temperature was allowed to rise to 58 ° C over the duration of the ΜΕ feed. The filtered dispersion had a solids content of 34.5%, and an average particle size of 490 nm. The Kubelka-Munk scattering coefficient (S / Mil) was measured on the dry polymer film and was found to be 1.07. EXAMPLE 23. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 17 were added to the vessel and the temperature was adjusted to 25 ° C. ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the vessel temperature at 25 ° C, a solution of 20 g 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were added together. vessel at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 40 min the ME feed rate was increased to 10 g / min. With 90% completeness of ME feeding, ME and co-feeds were stopped and the reaction was maintained for 5 min. The reaction temperature at this point was 68 ° C. Then 900 g hot Dl water (90 ° C) was added to the vessel. ME feeding was then continued at a flow rate of 30 g / min to completeness. Immediately after the completion of ME feeding, 32 g of ammonium hydroxide (28%) were added to the vessel. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 38.3%, and an average particle diameter of 446 nm. The Kubelka-Munk scattering coefficient (S / Mil) was measured on the dry polymer film and was found to be 0.92. EXAMPLE 24. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 17 were added to the vessel and the temperature was adjusted to 30 ° C. ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the vessel temperature at 30 ° C, a solution of 20 g 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were both added into the mixture. vessel at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 40 min the ME feed rate was increased to 10 g / min. With 90% completeness of ME feeding, ME and co-feeds were stopped and the reaction was maintained for 5 min. The reaction temperature at this point was 72 ° C. Then 900 g hot (90 ° C) DI water was added to the vessel. ME feeding was then continued at a flow rate of 30 g / min to completeness. Immediately after the completion of ME feeding, 32 g of ammonium hydroxide (28%) were added to the vessel. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 38.5%, and an average particle diameter of 461 nm. The Kubelka-Munk scattering coefficient (S / Mil) was measured on the dry polymer film and was found to be 0.85. EXAMPLE 25. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 17 were added to the vessel and the temperature was adjusted to 40 ° C. ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the vessel temperature at 40 ° C, a solution of 20 g 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Subsequently, feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were both added to the mixture. vessel at a flow rate of 0.5 g / min. 2 min after the initiation of the feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 40 min the ME feed rate was increased to 10 g / min. With 90% completeness of ME feeding, ME and co-feeds were stopped and the reaction was maintained for 5 min. The reaction temperature at this point was 73 ° C. Then 900 g hot (90 ° C) DI water was added to the vessel. ME feeding was then continued at a flow rate of 30 g / min to completeness. Immediately after the completion of ME feeding, 32 g of ammonium hydroxide (28%) were added to the vessel. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 38.5%, and an average particle diameter of 466 nm. The Kubelka-Munk scattering coefficient (S / Mil) was measured on the dry polymer film and was found to be 0.83. EXAMPLE 26. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 17 were added to the vessel and the temperature was adjusted to 50 ° C. ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the vessel temperature at 50 ° C, a solution of 20 g 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were both added into the mixture. vessel at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 40 min the ME feed rate was increased to 10 g / min. With 90% completeness of ME feeding, ME and co-feeds were stopped and the reaction was maintained for 5 min. The reaction temperature at this point was 77 ° C. Then 900 g hot Dl water (90 ° C) was added to the vessel. ME feeding was then continued at a flow rate of 30 g / min to completeness. Immediately after the completion of ME feeding, 32 g of ammonium hydroxide (28%) were added to the vessel. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 38.4%, and an average particle diameter of 466 nm. The Kubelka-Munk scattering coefficient (S / Mil) was measured on the dry polymer film and found to be 0.63. EXAMPLE 27. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 17 was added to the vessel and the temperature was adjusted to 60 ° C. ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the vessel temperature at 60 ° C, a solution of 20 g 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were added together. vessel at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 40 min the ME feed rate was increased to 10 g / min. With 90% completeness of ME feeding, ME and co-feeds were stopped and the reaction was maintained for 5 min. The reaction temperature at this point was 79 ° C. Then 900 g hot (90 ° C) DI water was added to the vessel. ME feeding was then continued at a flow rate of 30 g / min to completeness. Immediately after the completion of ME feeding, 32 g of ammonium hydroxide (28%) were added to the vessel. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 38.5%, and an average particle diameter of 461 nm. The Kubelka-Munk scattering coefficient (S / Mil) was measured on the dry polymer film and found to be 1.44. However, this polymer film showed evidence of porosity or dry masking. Porosity was confirmed by wetting of the polymeric film with Isopar L. Shrinkage decreased in the polymeric film under the area moistened by Isopar L. COMPARATIVE EXAMPLE C. Formation of aqueous dispersion of polymeric particles: Using the same equipment as in Example 1, 1125 of first polymer Example 17 were added to the vessel and the temperature was adjusted to 85 ° C. ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the vessel temperature at 85 ° C, a solution of 2.7 g of SPS mixed with 90 g of D1 water was added to the vessel over a 2 hour period together with the previously prepared ME. The vessel temperature was maintained at 85 ° C over the duration of ME feeding. At 85% ME, without interruption of ME or co-feeding, 900 g of hot water was added to the vessel along with 32 g of ammonium hydroxide. After the remaining 15% ME and co-feed were fed into the vessel, the reaction was maintained for 15 min at 85 ° C. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 39.1%, and an average particle diameter of 519 nm. The Kubelka-Munk scattering coefficient (S / Mil) could not be determined because the polymer did not form a suitable film when dry. EXAMPLE 28. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 15 was added to the vessel and the temperature was adjusted to 25 ° C. ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the vessel temperature at 25 ° C, a solution of 20 g 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were both added into the mixture. vessel at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 40 min the ME feed rate was increased to 10 g / min. At 85% completion of the ME feed, ME and co-feeds were interrupted and the reaction was maintained for 5 min. The reaction temperature at this point was 68 ° C. Then 900 g hot (90 ° C) DI water was added to the vessel. ME feeding was then continued at a flow rate of 30 g / min to completeness. Immediately after the completion of ME feeding, 32 g of ammonium hydroxide (28%) were added to the vessel. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered. The filtered dispersion had a solids content of 37.2%, and an average particle diameter of 530 nm. The Kubelka-Munk scattering coefficient (S / Mil) was measured on the dry polymer film and found to be 1.39. EXAMPLE 29. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, D1 water, 350 g, was added to the vessel and heated to 30 ° C under a nitrogen atmosphere. 1125 g of first polymer from Example 16 was added to the vessel and the temperature was adjusted to 19 ° C. ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 378 g MMA, and 522 g BA. From this ME, 227.5 g were removed and added in a separate container. Then 7.2 g MAA was added in 227.5 g ME removed. This additional ME was called ME2. With the vessel temperature at 19 ° C, a solution of 20 g 0.1% iron sulfate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.3 g of t-BHP mixed with 75 g of Dl water, together with a separate solution of 1.80 g of isoascorbic acid mixed with 75 g of Dl water were both added to the mixture. vessel at a flow rate of 0.5 g / min. 2 min after the start of the co-feed solutions, previously prepared ME2 were added to the vessel at a flow rate of 5 g / min. The vessel temperature was allowed to increase over the duration of ME2 feeding. When the ME2 feed reached completion, 32 g of ammonium hydroxide was added to the vessel. The original ME was then fed to the vessel at a flow rate of 10 g / min. At 85% completion of the ME feed, ME and co-feeds were interrupted and the reaction was maintained for 2 min. Next, 600 g of warm (90 ° C) DI water was added to the vessel. The remaining 15% of the ME feed was then added to the vessel at once. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 37.6%, and an average particle diameter of 471 nm. The Kubelka-Munk scattering coefficient (S / Mil) was measured on the dry polymer film and found to be 1.24. EXAMPLE 30. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 18 was added to the vessel and the temperature was adjusted to 25 ° C. ME was prepared by mixing 270 g Dl water, 15.0 g SDS, 369 g MMA, 9.0 g MAA, and 522 g BA. With the vessel temperature at 25 ° C, a solution of 20 g 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were both added into the mixture. vessel at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 40 min the ME feed rate was increased to 10 g / min. At 85% completion of the ME feed, ME and co-feeds were interrupted and the reaction was maintained for 5 min. The reaction temperature at this point was 68 ° C. Next, 800 g of warm (90 ° C) DI water was added to the vessel. ME feeding was then continued at a flow rate of 30 g / min to completeness. Immediately after the completion of ME feeding, 32 g of ammonium hydroxide (28%) were added to the vessel. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 39.4%, and an average particle diameter of 505 nm. The Kubelka-Munk scattering coefficient (S / Mil) was measured on the dry polymer film and found to be 1.52. EXAMPLE 31. Formation and Evaluation of Aqueous Coating Compositions: Coating compositions including the following ingredients were prepared.

Table 31.1 Aqueous Coating Compositions Table 31.2. Evaluation of Dry Aqueous Coating Compositions Example of Aqueous Dispersion # Ink Frets 7 1083 8 1110 9 1515 10 1603 11 1343 12 1253 Comp.A 715 Comp.B 1025 Aqueous Dry Coating Compositions Including Aqueous Dispersion of Polymeric Particles of Examples 7-12 of the invention exhibit superior film integrity as measured by frictional resistance to corresponding coatings including aqueous dispersions, Comparative Examples A and B. EXAMPLE 32. Formulation and Evaluation of Aqueous Coating Compositions: Aqueous compositions including the following ingredients have been prepared.

Table 32.1 Aqueous Coating Compositions Table 32.2. Evaluation of Examples and Dry Aqueous Coating Compositions Aqueous Dispersion Example Dry Density Fractions # S / Thousand g / cm3 w / Texa 19 Without Film 0.986 598 20 Without Film 0.8679 705 21 0.89 0.8806 65 5 22 1 .07 0.8876 700 23 0.92 1.0135 24 0.85 1.0194 1067 25 0.83 1.0042 962 26 0.63 1.0075 923 27 1.44 * 1.0092 832Λ Comp. C without film 1.0756 813Λ 28 1.39 0.9337 908 29 1.24 0.94 506 30® 1.52 0.8994 821 * porosity Λ unsatisfactory films; Misleading frictions. @ formulated with 2% TEXANOL ™. to friction data for aqueous coating compositions using the examples in formulations according to Ex. 32.

The aqueous dry coating compositions including the aqueous dispersion of polymeric particles of Examples 19-30 of the invention exhibited lower dry density, and as a result of this, polymer and energy mass savings to prepare the polymer with a useful level of film integrity as per Measured by Friction Resistance to Corresponding Coatings Including Aqueous Dispersion, Comparative Example C. EXAMPLE 33. Formulation and Evaluation of Aqueous Traffic Paint Coating Composition: An aqueous dispersion of polymer particles of this invention (33.3% by weight 66.7% if first encapsulating polymer having Tg = 10 ° C) (Example 33) and a commercial traffic paint binder (Ex. Comp. D) were formulated into a quick-drying traffic paint as in Table 33.1 Table 33.1 - Traffic Ink Compositions ________________________ The traffic ink from Example 33 was about half the titanium dioxide level of the comparative traffic paint (Ex. Comp. D) and further exhibited enhanced masking and total reflectance as shown in Table 33.2.

Table 33.2 - Evaluation of Dry Traffic Ink COMPARATIVE EXAMPLE D. U.S. Patent Example 8 of No. 4,427,836 was reproduced. The BCOP masking factor verified was 0.038. COMPARATIVE EXAMPLE E. Example # 1 of U.S. Patent No. 6,139,961 was reproduced. The BCOP masking factor verified was 0.060. EXAMPLE 34. Preparation of First Polymer: Using the same equipment as in Example 1, 1200 g of D1 water are added to the vessel and heated to 89 ° C under a nitrogen atmosphere. 5.25g of sodium persulfate dissolved in 30g of DI water are added to the heated vessel. This is immediately followed by the addition of 314.5g of Core # 3 (Ex. 13). Prepare the monomer emulsion (ΜΕ I) by mixing 100 g DI water, 6.7 g SDS (23%), 100.0 g styrene, 88.0 g methyl methacrylate, and 12.0 g methacrylic acid and add to the pot for a period of 60 min at a temperature of 78 ° C. With the completeness of ΜΕ I, prepare a second monomer emulsion (ΜΕ II) by mixing 400 g Dl water, 18,0 g SD $ (23%), 1182 g styrene, 18,0 g methacrylic acid, and 6.0 g of linseed fatty acid (LOFA). Add the emulsion of monomers II (ΜΕ II) to the vessel together with a separate mixture of 1.3 g of sodium persulfate dissolved in 90 g of D1 water for 60 min. Allow the temperature of the reaction mixture to rise to 92 ° C. With the completeness of ΜΕ II and the co-feed keep the reaction mixture for 30 min at 85 ° C. Cool the batch to room temperature and filter to remove any clot formed. The final non-neutralized latex will have a solids content of -40.0%, an average particle size of -380 nm, and a pH of -2.2. EXAMPLE 35. Preparation of First Polymer: Using the same equipment as in Example 1.1200 g of D1 water is added to the vessel and heated to 89 ° C under a nitrogen atmosphere. 5.25g of sodium persulfate dissolved in 30g of DI water are added to the heated vessel. This is immediately followed by the addition of 314.5g of Core # 3 (Ex. 13). Prepare the monomer emulsion (ΜΕ I) by mixing 100 g DI water, 6.7 g SDS (23%), 100.0 g styrene, 88.0 g methyl methacrylate, and 12.0 g methacrylic acid and add to the pot for a period of 60 min at a temperature of 78 ° C. With the completeness of ΜΕ I prepare a second monomer emulsion (ΜΕ II) by mixing 400 g Dl water, 18,0 g SDS (23%), 1181,4 g styrene, 18,0 g methacrylic acid , 6.0 g flaxseed oil fatty acid (LOFA) and 0.6 g ALMA. Add the emulsion of monomers II (ΜΕ II) to the vessel together with a separate mixture of 1.3 g of sodium persulfate dissolved in 90 g of D1 water for 60 min. Allow the temperature of the reaction mixture to rise to 92 ° C. With the completeness of ΜΕ II and the co-feed keep the reaction mixture for 30 min at 85 ° C. Cool the batch to room temperature and filter to remove any clot formed. The final non-neutralized latex will have a solids content of -40.0%, an average particle size of -380 nm, and a pH of -2.2. EXAMPLE 36. Preparation of First Polymer: Using the same equipment as in Example 1.1200 g of D1 water is added to the vessel and heated to 89 ° C under a nitrogen atmosphere. 5.25g of sodium persulfate dissolved in 30g of DI water are added to the heated vessel. This is immediately followed by the addition of 314.5g of Core # 3 (Ex. 13). Prepare monomer ΜΕ I by mixing 100 g DI water, 6.7 g SDS (23%), 100.0 g styrene, 88.0 g methyl methacrylate, and 12.0 g methacrylic acid and add to vessel for a period of 60 min at a temperature of 78 ° C. With the completeness of ΜΕ I, prepare a second monomer emulsion (ΜΕ II) by mixing 400 g of water Dl, 18,0 g of SDS (23%), 582,0 g of styrene, 18,0 g of acid methacrylic acid, 6.0 g flaxseed oil fatty acid (EOFA) and 600.0 g BGDMA. Add the emulsion of monomers II (ΜΕ II) to the vessel together with a separate mixture of 1.3 g of sodium persulfate dissolved in 90 g of D1 water for 60 min. Allow the temperature of the reaction mixture to rise to 92 ° C. With the completeness of ΜΕ II and co-feed maintain the reaction mixture for 30 min at 85 ° C. Cool the batch to room temperature and filter to remove any clot formed. The final non-neutralized latex will have a solids content of -40.0%, an average particle size of -380 nm, and a pH of -2.2. EXAMPLE 37. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125g of first polymer of Example # 34 is added to the vessel and the temperature is adjusted to 25 ° C. Prepare the ME by mixing 270 g DI water, 15.0 g SDS, 369 g methyl methacrylate, 9.0 g methacrylic acid, and 522 g butyl acrylate. With the vessel temperature at 25 ° C, a solution of 20 g of 0.1% iron sulphate mixed with 2 g of 1% versene is added to the vessel. Next, co-feeds including a solution of 2.8 g t-BHP mixed with 80 g Dl water, together with a separate solution of 2.0 g isoascorbic acid mixed with 80 g Dl water are both added to the vessel. at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME is added to the vessel at a flow rate of 5 g / min. Do not apply external heating to the reaction. The vessel temperature is allowed to increase over the duration of ME feeding. After 45min the ME feed rate is increased to 10 g / min. At 90% completion of ME feed, stop ME and co-feeds and maintain reaction for 5 min. The reaction temperature at this point will be ~ 72 ° C. Then add 900 g of hot (90 ° C) DI water to the pot. Continue feeding ME at a flow rate of 30 g / mir to completion. Immediately after completion of ME feeding, add 32 g of ammonium hydroxide (28%) to the vessel. Keep the reaction for 5 min. Continue the co-feed solutions at a flow rate of 1.0 g / min until complete. Cool the dispersion to 25 ° C and filter to remove any clots. The filtered dispersion will have a solids content of -38.0%, and an average particle size of ~ 450 nm. The S / Mil factor will be> 0.1 and the collapse factor <0.5. EXAMPLE 38. Formation of aqueous dispersion of polymeric particles: An aqueous dispersion is prepared following the procedure of Example 37, but substituting 1125g of a first polymer made by Example 35. The filtered dispersion will have a solids content of -38.0%, and an average particle size of -450 nm. The S / Mil factor will be> 0.1 and the collapse factor <0.5. EXAMPLE 39. Aqueous dispersion formation of polymeric particles: An aqueous dispersion is prepared following the procedure of Example 37, but substituting 1125 g of a first polymer made by Example 36. The filtered dispersion will have a solids content of -38.0%. , and an average particle size of -450 nm. The factor S / Mil will be> 0.1 and the collapse factor <0.5. EXAMPLE 40. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125g of first polymer from Example 17 were added to the vessel and the temperature was adjusted to 25 ° C. 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 vessel temperature at 25 ° C, a solution of 20 g of 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were both added into the mixture. vessel at a flow rate of 0.5 g / min. 2 min after initiation of the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 40 min, the ME feed rate was increased to 10 g / min. At 85% completion of the ME feed, ME and co-feeds were interrupted and the reaction was maintained for 5 min. The reaction temperature at this point was 72 ° C. Then 600 g of hot (90 ° C) DI water was added to the vessel. 2 g of an inhibitor, 4-hydroxy TEMPO, was added in remaining ME and this mixture was fed to the vessel at a flow rate of 30 g / min to completion. Immediately after completion of the ME feed, 32 g of ammonium hydroxide (28%) mixed with 30 g of Dl water were added to the vessel. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 41.2%, and an average particle size of 485 nm. The BCOP masking factor was 0.43 with a BCOP stability factor of 0.39. In this example, when 20% of ME had been added to the vessel, an aliquot was removed from the reaction mixture. Gas chromatographic analysis of this aliquot determined that the reaction mixture contained 1.6% by weight of unpolymerized monomers, based on the weight of the total reaction mixture when the aliquot was removed. EXAMPLE 41. Formation of aqueous dispersion of polymeric particles: An aqueous dispersion was prepared following the recipe and procedure of Example 40, except that the first polymer was added to the vessel and adjusted to 40 ° C. The filtered dispersion had a solids content of 41.2%, and an average particle size of 495 nm. The BCOP masking factor was 0.40 with a BCOP stability factor of 0.43. EXAMPLE 42. Formation of aqueous polymer particle dispersion: An aqueous dispersion was prepared following the recipe and procedure of Example 40, except that the first polymer was added to the vessel and adjusted to 50 ° C. The filtered dispersion had a solids content of 41.3%, and an average particle size of 498 nm. The BCOP masking factor was 0.37 with a BCOP stability factor of 0.39. EXAMPLE 43. Formation of aqueous dispersion of polymeric particles: An aqueous dispersion was prepared following the recipe and procedure of Example 40 except that the first polymer was added to the vessel and adjusted to 60 ° C. The filtered dispersion had a solids content of 41.2%, and an average particle size of 505 nm. The BCOP masking factor was 0.18 with a BCOP stability factor of 0.65. COMPARATIVE EXAMPLE 44. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 17 were added to the vessel and the temperature was adjusted to 78 ° C. 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 vessel temperature at 78 ° C, a solution of 3.0 g of sodium persulfate mixed with 30 g of DI water was added to the vessel. Subsequently, the previously prepared ME was added to the vessel at a flow rate of 5 g / min and a solution of 1.0 g of sodium persulfate mixed with 60 g of DI water was added to the vessel at a flow rate of 0.5 g. / min The vessel temperature was allowed to rise to 83 ° C over the duration of ME feeding. After 45 min, the ME feed rate was increased to 10 g / min. At 85% ME feed completeness and catalyst co-feed completeness, the ME feed was stopped and the reaction was maintained for 5 min. A solution of 20 g of 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. The reaction temperature at this point was 83 ° C. Then 600 g of hot (90 ° C) DI water was added to the vessel. 2 g of an inhibitor, 4-hydroxy TEMPO, was added in remaining ME and this mixture was fed to the vessel at a flow rate of 30 g / min to completion. Immediately after completion of the ME feed, 32 g of ammonium hydroxide (28%) mixed with 30 g of Dl water were added to the vessel. The reaction was held for 5 min. Next, co-feeds including a 2.0 g t-BHP solution mixed with 50 g Dl water, together with a separate solution of 1.0 g isoascorbic acid mixed with 50 g Dl water were both added to the vessel at a flow rate of 1.0 g / min to completeness. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 41.4%, and an average particle size of 501 nm. The BCOP masking factor was 0.05 with a BCOP stability factor of 0.60.

COMPARATIVE EXAMPLE 45. Formation of aqueous dispersion of polymeric particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 17 were added to the vessel and the temperature was adjusted to 25 ° C. 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 vessel temperature at 25 ° C, a solution of 20 g of 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were both added into the mixture. vessel at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 40 min the ME feed rate was increased to 10 g / min. At 85% completion of the ME feed, the co-feeds were stopped and the reaction was maintained for 5 min. The reaction temperature at this point was 62 ° C. Then 900 g of hot (90 ° C) DI water was added to the vessel. The remaining portion of ME was then added to the vessel at a flow 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 continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 38.1%, and an average particle size of 546 nm. BCOP masking factor was <0.1. In this example, when 20% of ME had been added to the vessel, an aliquot was removed from the reaction mixture. Gas chromatographic analysis of this aliquot determined that the reaction mixture contained 6.5% by weight of unpolymerized monomers, based on the total reaction mixture weight when the aliquot was removed. EXAMPLE 46, Preparation of First Polymer: Using the same apparatus as in Example 1, D 1 water, 1200 g, was added to the vessel and heated to 89 ° C under a nitrogen atmosphere. To the heated vessel water was added 5.25 g of sodium persulfate dissolved in 30 g of DL water. This was immediately followed by 314.5 g of core # 3 (Ex. 13). A solution of monomers (ΜΕ I) which was prepared by mixing 100 g Dl water, 6.7 g SDS, 100.0 g styrene, 88.0 g methyl methacrylate, and 12.0 g acid Methacrylic acid were added to the pot over a period of 60 min at a temperature of 78 ° C. With the completeness of ΜΕ I, a second monomer emulsion (ΜΕ II) was prepared by mixing 400 g Dl water, 18.0 g SDS (23%), 1170 g styrene, 18.0 g methacrylic acid , 6.0 g flaxseed oil fatty acid (LOFA), and 21.8 g divinyl benzene (55% active). Monomer emulsion II (ME) was added to the vessel along with a separate mixture of 1.3 g of sodium persulfate dissolved in 90 g of D1 water for 60 min. The temperature of the reaction mixture was allowed to rise to 92 ° C. With the completeness of ΜΕ II and co-feed, the reaction mixture was kept for 30 min at 85 ° C and then cooled to room temperature and filtered to remove any formed clot. The final non-neutralized latex had a solids content of 40.0%, an average particle size of 375 nm, and a pH of 2.2. EXAMPLE 47. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 46 was added to the vessel and the temperature was adjusted to 25 ° C. 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 vessel temperature at 25 ° C, a solution of 20 g of 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were added together. vessel at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 45 min, the ME feed rate was increased to 10 g / min. At 85% completion of the ME feed, ME and co-feeds were interrupted and the reaction was maintained for 5 min. The reaction temperature at this point was 72 ° C. Then 600 g of hot (90 ° C) DI water was added to the vessel. 2 g of an inhibitor, 4-hydroxy TEMPO, was added in remaining ME and this mixture was fed to the vessel at a flow rate of 30 g / min to completion. Immediately after the completion of ME feeding, 32 g of ammonium hydroxide (28%) mixed with 30 g of Dl water were added to the vessel. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 41.2%, and an average particle size of 489 nm. The BCOP masking factor was 0.54 with a BCOP stability factor of 0.06. In this example, when 20% of ME had been added to the vessel, an aliquot was removed from the reaction mixture. Gas chromatographic analysis of this aliquot determined that the reaction mixture contained 1.0 wt% unpolymerized monomers, based on the total reaction mixture weight when the aliquot was removed. EXAMPLE 48. Aqueous Dispersion Formation of Polymeric Particles: An aqueous dispersion was prepared following the recipe and procedure of Example 47, except that the first polymer was added to the vessel and adjusted to 50 ° C. The filtered dispersion had a solids content of 41.3%, and an average particle size of 490 nm. The BCOP masking factor was 0.53 with a BCOP stability factor of 0.11. EXAMPLE 49. Formation of aqueous dispersion of polymeric particles: An aqueous dispersion was prepared following the recipe and procedure of Example 47 except that the first polymer was added to the vessel and adjusted to 60 ° C. The filtered dispersion had a solids content of 41.4%, and an average particle size of 487 nm. The BCOP masking factor was 0.55 with a BCOP stability factor of 0.13. EXAMPLE 50. Aqueous Dispersion Formation of Polymeric Particles: An aqueous dispersion was prepared following the recipe and procedure of Example 44 above, except that 1125 g of the first polymer prepared in Ex. 46 was used. The filtered dispersion had a solids content of 41.5%, and an average particle size of 503nm. The BCOP masking factor was 0.51 with a BCOP stability factor of 0.34. EXAMPLE 51. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 46 was added to the vessel and the temperature was adjusted to 25 ° C. 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 vessel temperature at 25 ° C, a solution of 20 g of 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were both added into the mixture. vessel at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of the three hour ME feeding. With the completion of the ME feed, the co-feeds were interrupted and the reaction was maintained for 5 min. The reaction temperature at this point was 61 ° C. Then 600 g of hot (90 ° C) DI water was added to the vessel. Then 32 g of ammonium hydroxide (28%) was added to the vessel and the reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 46.1%, and an average particle size of 495 nm. The BCOP masking factor was 0.40 with a BCOP stability factor of 0.90. In this example, when 20% of ME had been added to the vessel, an aliquot was removed from the reaction mixture. Gas chromatographic analysis of this aliquot determined that the reaction mixture contained 6.3% by weight of unpolymerized monomers, based on the total reaction mixture weight when the aliquot was removed. EXAMPLE 52. Formation of bimodal aqueous dispersion of polymer particles; Using the same apparatus as in Example 1, 1125 g of the first polymer of Example 46 was added to the vessel along with 125 g of another first polymer of Example 3 and the temperature was adjusted to 25 ° C. 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 vessel temperature at 25 ° C, a solution of 20 g of 0.1% iron sulphate mixed with 2 g of 1% versene was added to the vessel. Subsequently, feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water were both added to the mixture. vessel at a flow rate of 0.5 g / min. 2 min after starting the co-feed solutions, the previously prepared ME was added to the vessel at a flow rate of 5 g / min. There was no external heating applied in the reaction. The vessel temperature was allowed to increase over the duration of ME feeding. After 45 min, the ME feed rate was increased to 10 g / min. At 85% completion of the ME feed, ME and co-feeds were interrupted and the reaction was maintained for 5 min. The reaction temperature at this point was 67 ° C. Then 600 g of hot (90 ° C) DI water was added to the vessel. 2 g of an inhibitor, 4-hydroxy TEMPO, was added in remaining ME and this mixture was fed to the vessel at a flow rate of 30 g / min to completion. Immediately after the completion of the alimentação feed, 32 g of ammonium hydroxide (28%) mixed with 30 g of Dl water were added to the vessel. The reaction was held for 5 min. The co-feed solutions were then continued at a flow rate of 1.0 g / min to completion. The dispersion was then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion had a solids content of 41.0%. The dispersion has been found to have 2 particle size modes. The large mode had a size of 471 nm while it was found that small mode was 99 nm with a weight ratio of 81% large / 19% small. The BCOP masking factor was 0.50 with a BCOP stability factor of 0.14. EXAMPLE 53. Aqueous Dispersion Formation of Polymeric Particles: Using the same apparatus as in Example 1, 1125 g of first polymer of Example 46 is added to the vessel and the temperature adjusted to 25 ° C. ME is prepared by mixing 270 g of DI water, 15.0 g of SDS, 171 g of 2-ethylhexyl acrylate, 9.0 g of methacrylic acid, and 720 g of butyl acrylate. With the vessel temperature at 25 ° C, a solution of 20 g of 0.1% iron sulphate mixed with 2 g of 1% versene is added to the vessel. Next, co-feeds including a solution of 2.8 g of t-BHP mixed with 80 g of Dl water, together with a separate solution of 2.0 g of isoascorbic acid mixed with 80 g of Dl water are both added to the mixture. vessel at a flow rate of 0.5 g / min. 2 min after initiation of the co-feed solutions, the previously prepared ME are added to the vessel at a flow rate of 5 g / min. There is no external heating applied in the reaction. The vessel temperature is allowed to increase over the duration of ME feeding. After 45 min, the ME feed rate is increased to 10 g / min. At 85% completion of the ME feed, ME and co-feeds are interrupted and the reaction is maintained for 5 min. The reaction temperature at this point will be ~ 72 ° C. Then 600 g of hot (90 ° C) DI water is added to the vessel. 2 g of an inhibitor, 4-hydroxy TEMPO, is added in a remaining ME and this mixture is fed to the vessel at a flow rate of 30 g / min to completion. Immediately after completion of the ME feed, 32 g of ammonium hydroxide (28%) mixed with 30 g of Dl water are added to the vessel. The reaction is held for 5 min. The co-feed solutions are then continued at a flow rate of 1.0 g / min to completion. The dispersion is then cooled to 25 ° C and filtered to remove any clots. The filtered dispersion will have a solids content of -41.0%, and an average particle size of ~ 485 nm. The BCOP masking factor will be> 0.1 with a BCOP stability factor of <0.50. EXAMPLE 54. Aqueous Dispersion Formation of Polymeric Particles: An aqueous dispersion is prepared following the recipe and procedure of Example 53, except that the ME used is prepared by mixing 270 g of D1 water, 15.0 g of SDS, 612 g of methyl methacrylate, 9.0 g of methacrylic acid, and 279 g of butyl acrylate. The filtered dispersion will have a solids content of -41.0%, and an average particle size of -485 nm. The BCOP masking factor will be> 0.1 with a BCOP stability factor of <0.50. EXAMPLE 55. Aqueous Dispersion Formation of Polymeric Particles: An aqueous dispersion is prepared following the recipe and procedure of Example 53, except that the ME used is prepared by mixing 270 g of DI water, 15.0 g of SDS, 675. grams of methyl methacrylate, 9.0 g of methacrylic acid, and 216 g of butyl acrylate. The filtered dispersion will have a solids content of -41.0%, and an average particle size of -485 nm. The BCOP masking factor will be> 0.1 with a BCOP stability factor of <0.50.

Table 55.1 shows the polymerization temperature, in ° C, when a given amount of ME was introduced into the reaction vessel in Examples 40-45 and 4-51.

Table 55.1 EXAMPLE 56 Comparison of Binders; Dry films resulting from two pigmented coating formulations, Formulation 1 and Formulation 2 are described. Formulation 1 uses particles of Example 47 as the binder. Formulation 2 uses Dispersion X particles as the binder. The percentages expressed in this comparison and in Table 56.1 are% by volume based on the combined volume of binder, pigment, and diluent. Ti02 and Ropaque ™ Ultra are used as examples of pigments. CaCO3, silica, and clay are used as examples of diluents. The dry film of Formulation 1 comprises 45% polymeric particles of Example 47, 5% coating grade rutile Ti02, and 50% CaCO3 having an average particle size of 5 micrometers. The dry film of Formulation 2 comprises, by volume, based on the total volume of binder, pigment, and diluent, 32% Dispersion X polymeric particles, 8% of the same T1O2 used in Formulation 1, and 60% of the same CaC03 employed in Formulation 1. Dispersion X is an aqueous dispersion of non-empty polymeric particles having an average particle diameter of 489 nm formed by emulsion polymerization of a monomer mixture consisting of by weight 41% methyl methacrylate, 58% methanol. butyl acrylate, and 1% methacrylic acid. Formulation 1 dry film exhibits opacity equal to or greater than Formulation 2 dry film.

Table 56.1 similarly compares the opacity of dry films resulting from the formulations using Example 47 and Dispersion X as binding agents at various levels of pigments and diluents.

Table 56.1 Film opacity of the formulations using the polymers of the invention and not of the invention as binders.

Dry films resulting from coating formulations, such as those described for Formulation 1, Formulation 2, and Table 56.1, will typically also comprise from 0.5% to 20% by volume, based on the total dry film volume of dispersants. , coalescing agents, solvents, defoamers, thickeners, wetting agents, surfactants, waxes, biocides, colored pigments, and other adjuvants commonly found in coatings. The dispersions of the invention may also be used in formulations with non-void binder polymers to obtain varying balances of binding and opacity characteristics.

Claims (10)

Aqueous dispersion, characterized in that it comprises polymeric particles, particles comprising: from 10% to 80% by weight, based on the total polymer weight when dry of a first polymer, the first polymer comprising, when dried, by least one void having a diameter of 100 nm to 1200 nm; and from 20% to 90% by weight, based on the weight of the polymeric particles when dried, of at least one second polymer comprising as polymerized units at least one ethylenically unsaturated monomer, the second polymer substantially encapsulating the first polymer and having a Tg of from -60 ° C to 50 ° C; wherein the second polymer is formed by a polymerization of at least one monoethylenically unsaturated monomer in the presence of the first polymer, and wherein at least 10% of the second polymer is formed by polymerization at a temperature of 5 ° C to 65 ° C, the temperature being at least 30 ° C below the calculated Tg of the first polymer, Aqueous dispersion according to claim 1, characterized in that it further comprises a core stage polymer comprising as polymerized units from 5% to 100% by weight based on the stage weight of at least a hydrophilic monoethylenically unsaturated monomer, and from 0% to 95% by weight, of at least one nonionic monoethylenically unsaturated monomer, wherein the aqueous dispersion has a BCOP masking factor of at least 0.1. Aqueous dispersion according to claim 2, characterized in that it comprises a BCOP stability factor of less than 0.5. Aqueous dispersion according to claim 1, characterized in that the first polymer is formed by polymerization of at least one monoethylenically unsaturated monomer and from 0% to 50% based on the total weight of the first polymer of at least one multiethylenically unsaturated monomer; and has a Tg of 50 ° C or higher. Aqueous dispersion according to claim 4, characterized in that it comprises a BCOP stability factor of less than 0.5. Aqueous dispersion according to claim 4, characterized in that at any time (T) during the polymerization of the first 20% of the second polymer, no more than 6% by weight of the unpolymerized monomers, based on a weight of total reaction mixture at one time (T) are present in a reaction vessel. Aqueous dispersion according to claim 1, characterized in that it further comprises from 5% to 95% by weight, based on a total polymeric dispersion content, of non-empty particles comprising polymer having a Tg of -55 ° C. at 50 ° C. Aqueous coating composition comprising particles as defined in claim 1 having a Volumetric Pigment Concentration of 0 to 85. A process for forming an aqueous dispersion of polymer particles comprising: providing an aqueous dispersion of polymer in multistage emulsion comprising a core stage polymer and a first shell stage polymer, the stage polymer comprising as polymerized units 5% to 100% by weight based on the weight of a core stage polymer of hydrophobic monoethylenically unsaturated monomer and 0% to 95% by weight based on a core stage of at least one nonionic monoethylenically unsaturated monomer, the first shell stage polymer having a calculated Tg of at least 50 ° C and comprising as polymerized units at least 50% by weight of non-ionic monoethylenically unsaturated monomer -ionic; form a second shell stage polymer by encapsulating the first shell stage polymer by adding in the aqueous dispersion of at least one monoethylenically unsaturated monomer and causing at least 10% of the monoethylenically unsaturated monomer to polymerize at a temperature of 5 ° C to 65 ° C, the temperature being at least 30 ° C below the calculated Tg of the first shell stage polymer in a multistage polymer presence; and adding a swelling agent to the aqueous dispersion prior to, during, or after polymerization of the monoethylenically unsaturated monomers of the second shell stage polymer. Process according to claim 9, characterized in that the swelling agent is added to the dispersion at a time when the dispersion comprises at least 0.5% by weight based on the total polymer content of the dispersion of unpolymerized monomer under conditions in which no substantial polymerization of the monomer occurs; and subsequent reduction of a monomer level by at least 50%.