Core-Shell Polymeric Particles

The present invention relates to core-shell polymer particles that are suitable for use in aqueous compositions and that can exhibit binding function and a useful level of opacity in dry compositions. More specifically, the present invention is a polymer particle comprising a core, a first shell and a second shell, wherein the core contains at least one void when dried; the first shell polymer has a glass transition above 50 ° C. Select from the group consisting of acrylonitrile, methacrylonitrile, acrylamide, methacrylicamide and a mixture thereof having a temperature (Tg) and 15% to 60% by weight based on the weight of the first shell polymer as a polymerization unit. Contains 0.3% to 10% by weight of polyethylene unsaturated monomer based on the weight of the first shell polymer; and the second shell polymer has a Tg of -60 ° C to 50 ° C. The total weight ratio of the second shell polymer to all other structures of the polymer particles is from 0.5: 1 to 3: 1; with respect to the polymer particles. Furthermore, the present invention relates to a method for forming the polymer particles and a method for imparting opacity to a dry composition containing the polymer particles.

U.S. Patent Application Publication No. 20070043159 discloses an aqueous dispersion of polymer particles and methods for forming them. The particles include first polymer particles that contain at least one void when dried and at least one second polymer that substantially encapsulates the first polymer. The method of forming the polymer particles is to form the second shell polymer in the presence of the first polymer particles, including the core polymer and the first shell polymer, at a temperature at least 30 ° C lower than the calculated Tg of the first stage shell polymer. Including forming. In order to produce such polymer particles in a sequential process, it was necessary to cool the particles after the first shell process was completed, or wait for it to cool. This is inefficient and costly. There was a need for a method of forming such particles at higher temperatures, especially between 30 ° C and 100 ° C below the Tg of the first shell polymer. Not all of the wide range of core-shell polymers already disclosed meet this need.

<p num="0003"><patcit num="1"><text>U.S. Patent Application Publication No. 2007/0043159</text></patcit></p>

<p num="0004"> The present invention provides core-shell polymer particles having a selected composition that meets this need. The polymer particles of the present invention can exhibit a binding function in a composition, such as a coating composition, i.e., can contribute to the integrity of the membrane containing the particles, and are useful in dry compositions. It can show the level of opacity. Moreover, the polymer particles of the present invention provide energy savings compared to polymer particle binders that do not contain at least one void when dried, because the polymer or other material that typically occupies its void space. This is because it must be manufactured with a minute of energy consumption.</p>

<p num="0005"> In a first aspect of the invention, the polymer particles include a core, a first shell, and a second shell; the core contains at least one void when dried; the first shell polymer is at 50 ° C. Acrylonitrile, methacrylonitrile, acrylamide, methacrylicamide and mixtures thereof having a calculated glass transition temperature (Tg) exceeding 15% by weight to 60% by weight based on the weight of the first shell polymer as a polymerization unit. Containing monomers selected from the group consisting of, and 0.3% to 10% by weight polyethylene unsaturated monomers based on the weight of the first shell polymer ; and the second shell polymer at -60 ° C. It has a Tg of ~ 50 ° C; the total weight ratio of the second shell polymer to all other structures of the polymer particles is from 0.5: 1 to 3: 1; polymer particles are provided. ..</p><p num="0006"> In the second aspect of the present invention, there is a method of forming polymer particles containing a core, a first shell and a second shell. As a polymerization unit, the core containing at least one hydrophilic monoethylene unsaturated monomer of 5% by weight to 100% by weight based on the weight of the core is formed; It has a Tg of more than 50 ° C and consists of 15% to 60% by weight of acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and a mixture thereof as a polymerization unit based on the weight of the first shell polymer. The first shell polymer containing a monomer selected from the group and a polyethylene unsaturated monomer of 0.3% by weight to 10% by weight based on the weight of the first shell polymer was formed in the presence of the core. ; And The second shell polymer having a Tg of -60 ° C to 50 ° C, in the presence of the first shell polymer, is between a temperature 30 ° C lower than the Tg of the first shell polymer and 100 ° C. Formed at temperature; the total weight ratio of said second shell polymer to all other structures of said polymer particles is from 0.5: 1 to 3: 1; A method including that is provided.</p><p num="0007"> In the third aspect of the present invention, (a) A composition comprising polymer particles comprising a core, a first shell and a second shell, wherein the core contains at least one void when dried; the first shell polymer has a calculated glass transition above 50 ° C. From the group consisting of 15% to 60% by weight of acrylonitrile, methacrylonitrile, acrylamide, methacrylicamide and a mixture thereof as a polymerization unit having a temperature (Tg) and based on the weight of the first shell polymer. It contains the monomer selected and 0.3% to 10% by weight of the polyethylene unsaturated monomer based on the weight of the first shell polymer; and the second shell polymer is -60 ° C to 50 ° C. To form a composition in which the total weight ratio of the second shell polymer to the total weight ratio of all other structures of the polymer particles is from 0.5: 1 to 3: 1. (b) Apply the composition to a substrate; (c) The applied composition is dried or dried; A method of imparting opacity to the dry composition, including the above, is provided.</p>

The present invention is a core-shell polymer particle comprising a core, a first shell and a second shell; the core contains at least one void upon drying; the first shell polymer has a glass transition temperature greater than 50 ° C. It has Tg) and is selected as a polymerization unit from the group consisting of 15% by weight to 60% by weight of acrylonitrile, methacrylonitrile, acrylamide, methacrylicamide and a mixture thereof based on the weight of the first shell polymer. Contains 0.3% to 10% by weight of polyethylene unsaturated monomer based on the weight of the monomer and the first shell polymer; and the second shell polymer has a Tg of -60 ° C to 50 ° C. The total weight ratio of the second shell polymer to all other structures of the polymer particles is from 0.5: 1 to 3: 1; with respect to the core-shell polymer particles.

The core of a core-shell polymer particle comprises a core having at least one void capable of scattering visible light upon drying, i.e., providing opacity to the composition in which it is contained. Core-shell particles containing one or more voids upon drying are limited to swelling of the core polymer with acid, base or nonionic organics, for example by complete or partial hydrolysis and dissolution of the core polymer. It has been disclosed that voids were formed due to the subsequent collapse of particles and the like. In a preferred embodiment, core-shell particles are formed by aqueous multi-step emulsion polymerization followed by base swelling. Such a multi-step process is described in US Pat. Nos. 4,427,836; 4,468,498; 4,469,825; 4,594,363; 4,677,003; 4,910,229; 4,920,160; 4,970,241; 5,157,084; 5,494,971; It is disclosed in 5,510,422; 6,139,961; 6,632,531; and 6,896,905, as well as European Patent Application Publications 267,726, 331,421 and 915,108.

The preferred stages of the multistage polymer of the present invention are the core stage polymer (core), the first shell stage polymer (first shell) and the second shell stage polymer (second shell). )including. Each core and shell can independently contain more than one stage. There may be one or more intermediate stages. The intermediate stage polymer, if present, partially or completely encapsulates the core, and itself is partially or completely encapsulated by the first shell. An intermediate step, referred to herein as a "tiecoat," can be produced by emulsion polymerization in the presence of a core. The first shell polymer partially or completely encloses the core polymer and, if present, the tie coat polymer. The second shell polymer partially or completely encapsulates the first shell. The total weight ratio of the second shell polymer to all other structures of the polymer particles is from 0.5: 1 to 3: 1; here "total of all other structures of the polymer particles" is Means the sum of optional seed polymers, core polymers, optional tie coats, and first-stage polymers, each of which optionally comprises multiple stages or compositions.

A preferred multi-step polymer core is at least one of 5% to 100% by weight, preferably 20% to 60% by weight, more preferably 30% to 50% by weight, based on the weight of the core, as the polymerization unit. An emulsion polymer comprising a species of hydrophilic monoethylene unsaturated monomer and at least one nonionic monoethylene unsaturated monomer of 0-95% by weight based on the weight of the core stage polymer. Cores containing at least 5 weight percent of at least one hydrophilic monoethylene unsaturated monomer relative to the total weight of the core polymer will generally result in a suitable degree of swelling. The core polymer can be produced in a single step or in a multi-step polymerization step, or in multiple successive steps. This method is hydrophobic as an alternative to hydrophilic monoethylene unsaturated monomers in hydrophilic core polymers, as described in US Pat. No. 4,880,842, under the term "hydrophilic monoethylene unsaturated monomers". It also includes and is intended for the use of non-polymeric compounds containing at least one carboxylic acid group that are absorbed by the core polymer before, during or after polymerization of the shell polymer. Further, the present invention does not include the hydrophilic monoethylenically unsaturated monomer in the term "hydrophilic monoethylenically unsaturated monomer" as described in US Pat. No. 5,157,084, but to a hydrophilic core polymer. Includes and is intended for the use of potential hydrophilic core polymers that are swellable upon hydrolysis.

Suitable hydrophilic monoethylene unsaturated monomers useful for producing core polymers include monoethylene unsaturated monomers containing acid functional groups such as crotonic acid, methacrylic acid, acrylicoxypropionic acid, (meth). Monomers containing at least one carboxylic acid group, including acrylic oxypropionic acid, itaconic acid, aconitic acid, maleic acid or maleic anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, monomethyl itaconic acid, etc. Can be mentioned. Acrylic acid and methacrylic acid are preferred. Suitable non-polymeric compounds containing at least one carboxylic acid group include C₆-C₁₂Aliphatic or aromatic monocarboxylic acids and dicarboxylic acids such as benzoic acid, m-toluic acid, p-chlorobenzoic acid, o-acetoxybenzoic acid, azelaic acid, sebacic acid, octanoic acid, cyclohexanecarboxylic acid, lauric acid and Examples include monobutyl phthalate. Nonionic monoethylene unsaturated monomers suitable for producing hydrophilic core polymers include styrene, alpha-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, ethylene, vinyl acetate and vinyl chloride. , Vinylidene Chloride, (Meta) Acrylonitrile, (Meta) Styrene, (Meta) Acrylic Acid (C)₁-C₂₀) Alkyl or (C₃-C₂₀) Alkenyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxy (meth) acrylate. Examples thereof include propyl, benzyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate.

The core has an average particle size of 50 nm to 1.0 micron, preferably 100 nm to 300 nm in diameter in the non-swelling state, whether obtained by a single-step process or a multi-step process. If the core is obtained from a preformed or seed polymer, the seed polymer preferably has an average particle size of 30 nm to 200 nm.

The core may optionally contain from 0.1% to 20% by weight, or 0.1% to 10% by weight of polyethylenically unsaturated monomers based on the total weight of the core, and the amount used is generally In other words, as the relative amount of hydrophilic monomer increases, it is permissible to increase the amount of polyethylenically unsaturated monomer. Alternatively, the core polymer can contain from 0.1% to 60% by weight of butadiene based on the total weight of the core polymer.

Suitable polyethylene unsaturated monomers include comonomer containing at least two addition-polymerizable vinylidene groups, and alpha betaethyl unsaturated monocarboxylic acid esters of polyhydric alcohols containing 2-6 ester groups. There is. Such comonomer includes diacrylic acid and alkylene glycol dimethacrylic acid, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol diacrylic acid, 1,4-butylene glycol diacrylate, propylene diacrylate. Glycol and triethylene glycol dimethacrylate; 1,3-glycerol dimethacrylic acid; 1,1,1-trimethylolpropane dimethacrylic acid; 1,1,1-trimethylolethane diacrylic acid; pentaerythritol trimethacrylate; tri Acrylic acid 1,2,6-hexane; sorbitol pentamethacrylate; methylenebisacrylamide, methylenebismethacrylicamide, divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinyl acetylene, trivinylbenzene, triaryl cyanurate, Divinyl acetylene, divinyl ethane, divinyl sulfide, divinyl ether, divinyl sulfone, diallyl cyanamide, ethylene glycol divinyl ether, diallyl phthalate, divinyl dimethyl silane, glycerol trivinyl ether, divinyl adipate; (meth) dicyclopentenyl acrylate; (meth) ) Dicyclopentenyloxy acrylate; unsaturated ester of glycol monodicyclopentenyl ether; allyl esters of alpha, beta-unsaturated mono- and dicarboxylic acids with terminal ethylenic unsaturated, such as allyl methacrylate, allyl acrylate, Examples thereof include diallyl maleate, diallyl fumarate, and diallyl itacone.

The first shell polymer of the multistage polymer has a Tg of more than 50 ° C, and as a polymerization unit, 15% by weight to 60% by weight, preferably 20% by weight to 50% by weight based on the weight of the first shell polymer. , More preferably 20% to 40% by weight, a monomer selected from the group consisting of acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and mixtures thereof, and 0.3% by weight based on the weight of the first shell polymer. It contains ~ 10% by weight, preferably 0.5% by weight to 10% by weight of polyethylene unsaturated monomer. Preferred is (meth) acrylonitrile. Styrene is the preferred comonomer. Other suitable monomers that can be used to form the first shell polymer include monoethylene unsaturated monomers such as hydrophilic and nonionic, which are disclosed herein for the production of core polymers. Be done. If more than one first shell stage is used, the composition of the first shell here is considered here as the overall composition of all the first shells. The first shell polymer is a polyethylene unsaturated monomer having a polymerization unit of 0.3% by weight to 10% by weight, preferably 0.5% by weight to 10% by weight based on the weight of the first shell (MEUM in the present specification. ) Is further included. Suitable polyethylene unsaturated monomers are those disclosed herein for optional use in core polymers.

The second shell polymer of the multistage polymer has a Tg of -60 ° C to 50 ° C, preferably -40 ° C to 30 ° C, more preferably -20 ° C to 20 ° C. Monomers suitable for the production of second shell polymers include monoethylene unsaturated monomers such as hydrophilic and nonionic, which are disclosed herein for the production of core polymers. The second shell optionally further comprises 0.05% to 10% by weight of the polyethylenically unsaturated monomer as a polymerization unit relative to the weight of the second shell; the amount substantially impairs film formation. It must be selected so that it does not, i.e., substantially impair the contribution of the second stage polymer to the function of the polymer particles as a binder. Suitable polyethylene unsaturated monomers are disclosed herein for optional use in core polymers.

The Tg of the polymer herein is the Fox formula (TG Fox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, p. 123 (1956)), ie, for example, the Tg of a copolymer of monomers M1 and M2. To calculate<maths num="1"><img id="000002" he="5" wi="159" file="JP5214540B2_D0001.tif" img-format="tif" img-content="drawing" /></maths>In the equation, Tg (calculated) is the calculated glass transition temperature for the copolymer. w (M1) is the weight fraction of the monomer M1 in the copolymer, w (M2) is the weight fraction of the monomer M2 in the copolymer, Tg (M1) is the glass transition temperature of the homopolymer of M1 Tg (M2) is the glass transition temperature of the homopolymer of M2, All temperatures are in ° K units; Is calculated here using.

The glass transition temperature of homopolymers can be found, for example, in the "Polymer Handbook" edited by J. Brandrup and EHImmergut, Interscience Publishers.

The monomers used in the shell and their relative proportions should be such that they are permeable to aqueous or gaseous volatile or non-volatile basic swelling agents capable of swelling the core. The shell is a monoethylene property containing 0% by weight to 35% by weight, preferably 0% by weight to 10% by weight, more preferably 0.1% by weight to 10% by weight of an acid functional group as a polymerization unit based on the weight of the shell. One or more unsaturated monomers such as (meth) acrylic acid, (meth) acrylic oxypropionic acid, itaconic acid, aconitic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, It may include monomethyl itaconic acid and the like. (Meta) acrylic acid is preferred. Preferably, the proportion of acid-functional monoethylenically unsaturated monomers in the shell polymer does not exceed one-third of that proportion in the core polymer.

In the method of forming polymer-based core-shell polymer particles of the present invention, water-soluble free radical initiators are typically used in aqueous emulsion polymerization. Suitable water-soluble free radical initiators include hydrogen peroxide; tert-butylperoxide; alkali metal persulfate salts such as sodium persulfate, potassium persulfate and lithium persulfate; ammonium persulfate; and such initiators. Examples include a mixture with a reducing agent. Reducing agents include sulfites such as alkali metal pyrosulfites, alkali metals hydrosulfites and alkali metals hyposulfates; sodium formaldehyde sulfoxylates; and reducing sugars such as ascorbic acid and isoascorbic acid. The amount of the initiator is preferably 0.01% by weight to 3% by weight based on the total amount of the monomers, and in the redox system, the amount of the reducing agent is preferably 0.01% by weight to 3% by weight based on the total amount of the monomers. Is. The type and amount of initiator may be the same or different at the various stages of multi-step polymerization. Temperatures during the various stages of multistage polymerization typically range from about 10 ° C to 100 ° C. In the case of persulfate systems, the temperature is typically in the range of 60 ° C to 90 ° C. In the redox system, the temperature is typically in the range of 30 ° C to 70 ° C. In the method of the present invention, the temperature during the polymerization of the second stage polymer is between 30 ° C and 100 ° C, which is lower than the Tg of the first shell polymer. "Temperature during polymerization of the second stage polymer" as used herein means the maximum temperature of the reaction mixture during the polymerization of the second stage polymer. The product formed by the method of forming polymer-based core-shell polymer particles of the present invention is also an embodiment of the present invention.

One or more nonionic or anionic emulsifiers, or surfactants, can be used alone or together. Examples of suitable nonionic emulsifiers include tert-octylphenoxyethyl poly (39) -ethoxyethanol, dodecyloxypoly (10) ethoxyethanol, nonylphenoxyethyl-poly (40) ethoxyethanol, polyethylene glycol monooleate 2000. , Ethoxylation castor oil, fluorinated alkyl esters and alkoxylates, polyoxyethylene monolaurate (20) sorbitan, monopalm oil fatty acid sucrose, di (2-butyl) phenoxypoly (20) ethoxyethanol, hydroxyethyl cellulose polyacrylic acid butyl graft copolymer , Dimethylsilicone polyalkylene oxide graft copolymer, poly (ethylene oxide) poly (butyl acrylate) block copolymer, block copolymer of propylene oxide and ethylene oxide, 2,4,7,9-tetramethyl ethoxylated with 30 mol of ethylene oxide -5-decin-4, Examples thereof include 7-diol, N-polyoxyethylene (20) lauramide, N-lauryl-N-polyoxyethylene (3) amine, and poly (10) ethylene glycol dodecylthioether. Examples of suitable anionic emulsifiers include sodium lauryl sulphate, sodium dodecylbenzene sulfonate, potassium stearate, sodium dioctyl sulfosuccinate, sodium dodecyldiphenyloxide disulfonate, nonylphenoxyethyl poly (1) ammonium ethoxyethyl sulphate, styrene sulfone. Sodium acid, sodium dodecylallyl sulfosuccinate, flaxseed oil fatty acid, sodium or ammonium salt of phosphate ester of ethoxylated nonylphenol, sodium octoxinol-3-sulfonate, sodium cocoyl sarcocinate, 1-alkoxy- Sodium 2-hydroxypropyl sulfonate, alpha-olefin (C₁₄-C₁₆) Sodium sulfonate, sulphate of hydroxyalkanol, N- (1,2-dicarboxyethyl) -N-octadecylsulfosuccinamate 4 sodium, disodium N-octadecylsulfosuccinamate, alkylamide Examples include disodium polyethoxysulfosuccinate, nonylphenol halfester ethoxylated sulfosuccinic acid disodium, and sodium salts of tert-octylphenoxyethoxypoly (39) -ethoxyethylsulfate. One or more surfactants are generally used in an amount of 0-3% based on the weight of the multi-step polymer. One or more surfactants may be added prior to the addition of the monomer feed, during the addition of the monomer feed, or in combination.

The overall size of the multi-step polymer particles is typically 70 nm to 4.5 microns, preferably 100 nm to 3.5 microns, more preferably in the non-swelling state (ie, before neutralization that raises the pH to about 6 or higher). It is 200 nm to 2.0 microns. If the hydrophilic core polymer is completely encapsulated, it will not be titrated with alkali metal bases for 1 hour under analytical conditions at room temperature. The degree of encapsulation can be determined by taking the sample during the shell polymerization process and titrating it with sodium hydroxide.

The voids of the latex polymer particles are preferably an aqueous basic swelling agent that penetrates the shell and swells the core and is produced by swelling the acid-containing core. This expansion may involve partial fusion of the outer surface of the core with holes in the inner surface of the shell, as well as partial enlargement or blistering of the shell and the entire particle. When the swelling agent is removed by drying, shrinkage of the core creates microvoids, the degree of which depends on the shell's resistance to restoration to its previous size. Suitable swelling agents for the core include, for example, ammonia, ammonium hydroxide, alkali metal hydroxides (eg sodium hydroxide), aminoalcohols, volatile lower aliphatic amines (eg trimethylamine and triethylamine), and Examples thereof include mixtures thereof. The swelling step can occur during any multi-step shell polymerization step, during any step-growth polymerization step, or at the end of the multi-step polymerization method. In the case of multi-step emulsion polymers, the monomers and swelling agents in the absence of substantial polymerization of the monomers are of the swelling of the multi-step emulsion polymer, as taught in US Pat. Nos. 6,020,435 and 6,252,004. The degree can be increased.

The weight ratio of core to intermediate or tie coat, if present, typically ranges from 1: 0.5 to 1:10, preferably from 1: 1 to 1; 7. The core-to-first shell weight ratio typically ranges from 1: 5 to 1:20, preferably from 1: 8 to 1:15. The total weight of the second shell pair, all previous stages of polymer particles or previously formed structures, eg, optional seeds, cores, optional tie coats, and first shell. The ratio is 0.5: 1 to 3: 1, preferably 0.75: 1 to 2.5: 1. The lower the total weight ratio of the second shell to all previous steps, the more difficult it will be for the composition containing the polymer particles to form a film without the additional binder present; Those skilled in the art will recognize that the formation will be particularly affected by the use of film-forming aids or plasticizers and the temperature during the film-forming process.

In certain embodiments of the present invention, there is provided a method of imparting opacity to a dry composition comprising the polymer particles of the present invention. In certain embodiments of the invention, certain aqueous compositions comprising the core-shell polymer particles of the invention and, in some cases, inorganic particles are provided, the composition of which may be, for example, as a sunscreen composition or as a coating composition. Can be found to be useful as. The amount of inorganic particles contained in the aqueous coating composition is 0% by volume to 95% by volume based on the total dry volume of the composition and the inorganic particles. Typically, the coating composition, when used to produce a dry coating, has a solid in an amount in the range of 20-50% by volume, relative to the volume of the composition. A suitable viscosity range for such a composition is 50 to 130 Krebs units (KU), preferably 70 to 120 KU, more preferably 90 to 110 KU.

Inorganic particles include metal oxides such as zinc oxide, cerium oxide, tin oxide, antimony oxide, zirconium oxide, chromium oxide, iron oxide, lead oxide, aluminum oxide, silicon oxide, titanium dioxide; zinc sulfide, lithopon, carbon dioxide. Included are calcium, calcium sulfate, barium sulfate, mica, clay, calcined clay, feldspar, hazestone flash, ashstone, diatomaceous soil, alumina silicate and talc. Inorganic particles can have a particle size of 10 to 1000 nm, preferably 10 to 500 nm. Examples of preferred inorganic particles having a particle size of less than 1000 nm include zinc oxide, silicon oxide, titanium dioxide and iron oxide.

The composition may optionally include organic pigment particles. Suitable organic pigments also include plastic pigments such as microspheres and solid bead pigments that are not of the present invention and contain voids or vesicles. Examples of solid bead pigments include polystyrene and polyvinyl chloride beads. Microspherical pigments contain polymer particles containing one or more voids, for example Ropaque.^(trademark)Opaque Polymers and US Patents 4,427,835, 4,920,160, 4,594,363, 4,469,825, 4,468,498, 4,880,842, 4,985,064, 5,157,084, 5,041,464, 5,036,109, 5,409,6 And vesicular polymer particles as disclosed in Nos. 5,510,422. Other suitable pigments include, for example, Expancel^(trademark)551 DE20 Acrylonitrile / PVC Expansion Particles (Expancel Inc., Duluth, Georgia); Sil-Cell^(trademark)35/34 Sodium Hydrosilicate Aluminum Particles (Silbrico Corporation, Hodgkins, Illinois); Dualite^(trademark)27 CaCO₃Polyvinylidene chloride copolymer coated with (Pierce and Stevens Corporation, Buffalo, NY); Fillitte^(trademark)150 Ceramic Spherical Particles (Trelleborg Fillite Inc., Norcross, Georgia); Microbeads^(trademark)4A Soda Lime Particles (Cataphote Inc.); Sphericell^(trademark)Hollow glass particles (Potter Industries Inc., Valley Forge, PA); Ecosphere^(trademark)Hollow glass sphere (New Metals &amp; Chemicals Ltd. in Essex, UK); Z-light^(trademark)SphereW-1200 Ceramic Hollow Sphere (3M, St. Paul, Minnesota); Scotchlite^(trademark)K46 Glass Bubble (3M, St. Paul, Minnesota); Vistamer^(trademark)UH1500 polyethylene particles; and Vistamer^(trademark)HD1800 polyethylene particles (Fluoro-Seal Inc., Houston, Texas).

Compositions containing inorganic particles are produced by techniques well known in the field of coating technology. First, inorganic particles are typically COWLES.^{(Registered trademark)}) Well dispersed in the medium under high shear as provided by the mixer. Core-shell polymer particles are then added with other coating adjuvants, if desired, under low shear agitation. The compositions include film-forming or non-film-forming solution polymers as well as conventional coating adjuvants such as desiccants, plasticizers, hardeners, neutralizers, thickeners, rheology modifiers, biocidal agents, defoamers. Agents, UV absorbers, optical brighteners, light or heat stabilizers, chelating agents, dispersants, colorants, waxes, water repellents and antioxidants can be further included.

Conventional coating application methods, such as brushing, rolling, and spraying methods, such as air spray, air assist spray, airless spray, high volume low pressure spray, and air assist airless spray, are applied to the compositions of the invention. Can be used to In addition, for some systems, other applied techniques such as cork guns, roll coaters and curtain coaters may be used to apply the composition. Aqueous polymer compositions can be used as substrates, such as plastics, wood, metals, primed surfaces, already painted surfaces, weathered painted surfaces, glass, paper, cardboard, leather, composites and cemented materials. It can be advantageously applied to substrates and the like. Drying can typically proceed under ambient conditions, for example 0 ° C to 35 ° C, but at higher temperatures, airflow, low humidity, chemical ray energy, eg electron beam, ultraviolet light, visible light, infrared light or It can be accelerated, such as by microwave radiation, or using sonic energy.

<p num="0031"> Abbreviation SDS = sodium dodecylbenzene sulfonate (23%) Fes-32 = Disponil Fes-32 (30%) LOFA = flaxseed oil fatty acid ALMA = allyl methacrylate DVB = Divinylbenzene (80%) STY = Styrene AN = acrylonitrile AA = acrylic acid MAA = methacrylic acid MMA = methyl methacrylate BA = butyl acrylate EDTA = ethylenediaminetetraacetic acid tetrasodium salt t-BHP = tert-butyl hydroperoxide IAA = isoascorbic acid NaPS = sodium persulfate NH4OH = ammonium hydroxide (28%) NaOH = sodium hydroxide (50% in water) DI water = deionized water</p><p num="0032"> Core 1: The core polymer was manufactured according to the procedure of Example 1-16 of US Pat. No. 6,020,435. The filtered dispersion had a solid content of 32.0% and an average particle size of 135 nm. Core 2: The core polymer was manufactured according to the procedure of Example 1-16 of US Pat. No. 6,020,435. The filtered dispersion had a solid content of 31.9% and an average particle size of 95 nm.</p><p num="0033"> Polymer 1: Manufacture of core / tie coat / (first) shell polymer particles. A 5-liter four-necked round-bottom flask was equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser. 950 grams of DI water was added to the kettle and heated to 89 ° C in a nitrogen atmosphere. To the heated kettle water was added 6.0 grams of NaPS dissolved in 40 grams of DI water. Immediately after this was 390.6 grams of Core 1. A monomer emulsion (MEI) made by mixing 125 grams of DI water, 8.3 grams of SDS, 125.0 grams of STY, 110.0 grams of MMA, and 15.0 grams of MAA at a temperature of 78 ° C for 60 minutes. Added to the kettle. Upon completion of the MEI, a second monomer emulsion (MEII) is produced by mixing 500 grams of DI water, 22.5 grams of SDS, 1462.5 grams of STY, 22.5 grams of MAA, 7.5 grams of LOFA and 18.8 grams of DVB. It was. Monomer emulsion II (MEII) was added to the kettle over 60 minutes with a separate mixture of 1.6 grams of NaPS dissolved in 90 grams of DI water. The temperature of the reaction mixture was allowed to rise to 92 ° C. Upon completion of MEII and cofeed, the reaction mixture was kept at 85 ° C for 30 minutes, then cooled to room temperature and filtered to remove the aggregates formed. The final unneutralized latex had a solid content of 46.2%, an average particle size of 375 nm and a pH of 2.2.</p><p num="0034"> Comparative Example A: A 5-liter four-necked round-bottom flask was equipped with a paddle stirrer, a thermometer, a nitrogen inlet and a reflux condenser. 1298.7 grams of primary polymer # 1 was added to the kettle with 220 grams of DI water and the temperature was adjusted to 25 ° C. A monomer emulsion (MEI) was produced by mixing 150 grams of DI water, 8.0 grams of SDS, 208.0 grams of MMA, 6.0 grams of MAA, and 296.0 grams of BA. At a kettle temperature of 25 ° C, a solution of 20 grams of 0.1% ferrous sulfate mixed with 2 grams of 1% EDTA was added to the kettle. Cofeed, which is then a solution of 1.90 grams of t-BHP mixed with 50 grams of DI water and another solution of 1.3 grams of IAA mixed with 50 grams of DI water, both 1.0 grams / min. Was added to the kettle at the rate of. Two minutes after the start of the cofeed solution, the already produced MEI was added to the kettle at a rate of 15 grams / min. At this point no external heat was applied to the reaction. The kettle temperature allowed a slow rise over the first 15 minutes of MEI supply. After 15 minutes, the ME feed rate was increased to 30 grams / min and external heat was applied to the reaction. Upon completion of MEI supply, cofeed was stopped and the reaction was retained for 5 minutes. The temperature of the reaction at this point was 70 ° C. 300 grams of heated DI water (90 ° C) was then added to the kettle along with a mixture of 5.0 grams of NH4OH mixed with 5.0 grams of DI water. At this point, MEII, which had been preformed by mixing 25.0 grams of DI water, 2.0 grams of SDS, 52.0 grams of BA, 38.0 grams of MMA, and 2.5 grams of 4-hydroxy TEMPO, was placed in the kettle for 5 minutes. Supplied. Immediately after the MEII supply was completed, 30.0 grams of NH4OH mixed with 30 grams of DI water was added to the kettle for 2 minutes. When the NH4OH supply was completed, the batch was held for 5 minutes. Then the cofeed solution is 1. It resumed to completion at a rate of 0 grams / minute. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 40.6%. The S / Mil was 0.81 and was measured to be accompanied by an 8% decay.</p><p num="0035"> Comparative Example B: A 5-liter four-necked round-bottom flask was equipped as in Comparative Example A. 560 grams of DI water was added to the kettle and heated to a temperature of 89 ° C under a nitrogen atmosphere. To the heated kettle water, 2.6 grams of NaPS dissolved in 20 grams of DI water was added. Immediately after this was a 173.3 gram core # 1 (135 nm). A monomer emulsion (MEI) made by mixing 55.0 grams of DI water, 3.7 grams of SDS, 55.0 grams of STY, 48.4 grams of MMA, and 6.6 grams of MAA at a temperature of 78 ° C for 60 minutes. Added to the kettle. Upon completion of the MEI, a second monomer emulsion (MEII) is produced by mixing 220.0 grams of DI water, 9.9 grams of SDS, 643.5 grams of STY, 9.9 grams of MAA, 3.3 grams of LOFA and 8.3 grams of DVB. Was done. Monomer emulsion II (MEII) was then added to the kettle over 60 minutes with a separate mixture of 0.70 grams of NaPS dissolved in 40 grams of deionized water. The temperature of the reaction mixture was allowed to rise to 92 ° C. Upon completion of MEII and NaPS cofeed, the reaction was cooled to 60 ° C. When the kettle temperature reached 60 ° C, a solution of 20 grams of ferrous sulfate mixed with 2 grams of 1% EDTA was added to the kettle. Cofeed, then a solution of 2.6 grams of t-BHP mixed with 70 grams of DI water and another solution of 1.8 grams of IAA mixed with 70 grams of DI water, both 0.80 grams / min. Was added to the kettle at the rate of. Two minutes after the start of the cofeed solution, 210 grams of DI water, 11.7 grams of SDS, 406.5 grams of BA, 286.2 grams of MMA, and 8. MEIII, already produced by mixing 3 grams of MAA, was added to the kettle for 60 minutes, allowing the temperature to rise to 78 ° C without providing any external heat. Upon completion of MEIII, the Coffford solution was stopped and the batch was held at 78 ° C for 5 minutes. A solution of 5.0 grams of NH4OH mixed with 5.0 grams of DI water was then added to the kettle with 600 grams of heated DI water (90 ° C). At this point, pre-made MEIV by mixing 37.0 grams of DI water, 2.1 grams of SDS, 72.0 grams of BA, 52.0 grams of MMA, and 2.5 grams of 4-hydroxy TEMPO in the kettle for 7 minutes. Supplied. Immediately after the MEIV supply was completed, 40.0 grams of NH4OH mixed with 40 grams of DI water was added to the kettle for 2 minutes. When the NH4OH supply was completed, the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.0 g / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 41.5%. The S / Mil was 0.84 and was measured to be associated with an 18% decay. 0 grams of NH4OH was added to the kettle for 2 minutes. When the NH4OH supply was completed, the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.0 g / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 41.5%. The S / Mil was 0.84 and was measured to be associated with an 18% decay. 0 grams of NH4OH was added to the kettle for 2 minutes. When the NH4OH supply was completed, the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.0 g / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 41.5%. The S / Mil was 0.84 and was measured to be associated with an 18% decay.</p><p num="0036"> Example 1: In Example 1, the composition of MEI consisted of 55.0 grams of DI water, 3.7 grams of SDS, 81.4 grams of STY, 22.0 grams of AN, and 6.6 grams of MAA; and of MEII. Manufactured according to the method of Comparative Example B, except that the composition consisted of 220.0 grams of DI water, 9.9 grams of SDS, 521.4 grams of STY, 132.0 grams of AN, 3.3 grams of LOFA and 8.3 grams of DVB. It was. The filtered dispersion had a solid content of 40.6%. The S / Mil was 0.70 and was measured to be associated with a 7% decay.</p><p num="0037"> Comparative Example C: 660 grams of DI water heated to a temperature of 89 ° C under a nitrogen atmosphere was added to a 5-liter four-necked round-bottom flask equipped as in Comparative Example A. To the heated kettle water, 2.6 grams of NaPS dissolved in 20 grams of DI water was added. Immediately after this was a 171.8 gram core # 1 (135 nm). Monomer emulsion (MEI) made by mixing 275.0 grams of DI water, 13.6 grams of SDS, 754.6 grams of STY, and 3.9 grams of LOFA reacts at a temperature of 78 ° C at a rate of 40 grams / minute. It was supplied to the vessel. Two minutes after the start of MEI, a solution of 7.7 grams of AA mixed with 40 grams of DI water was added to the reactor. 40 minutes after MEI feeding, at a temperature of 78 ° C, the feeding rate was increased to 9 grams / min and 0.7 grams of NaPS cofeed solution in 50 grams of DI water started in the reactor at a rate of 1.0 grams / min. Was done. At this point, 9.6 grams of DVB was added to the MEI. After an additional 15 minutes, the MEI feed rate was increased again to 18 grams / min, allowing the reaction temperature to rise to 92 ° C. Upon completion of the MEI and NaPS cofeeds, the reaction was cooled to 62 ° C. While cooling, a solution of 20 grams of 0.1% ferrous sulfate mixed with 2 grams of 1% EDTA was added to the kettle at a temperature of 75 ° C. Cofeed, then at a temperature of 70 ° C, is a solution of 2.6 grams of t-BHP mixed with 70 grams of DI water and another solution of 1.8 grams of IAA mixed with 70 grams of DI water. Both were added to the kettle at a rate of 0.80 g / min. Three minutes after the start of the cofeed solution, 210 grams of DI water, 11.7 grams of SDS, 406.5 grams of BA, 286.2 grams of MMA, and 8. MEII, which had already been produced by mixing 3 grams of MAA, was added to the kettle for 60 minutes, allowing the temperature to rise to 78 ° C without providing any external heat. Upon completion of MEII, the cofeed solution was stopped and the batch was held at 78 ° C for 5 minutes. A solution of 5.0 grams of NH4OH mixed with 5.0 grams of DI water was then added to the kettle with 500 grams of heated DI water (90 ° C). At this point, MEIII, pre-made by mixing 37.0 grams of DI water, 2.1 grams of SDS, 72.0 grams of BA, 52.0 grams of MMA, and 2.5 grams of 4-hydroxy TEMPO, was added to the kettle for 7 minutes. Supplied. Immediately after the MEIII supply was completed, 40.0 grams of NH4OH mixed with 40 grams of DI water was added to the kettle for 2 minutes. When the NH4OH supply was completed (temperature 73 ° C), the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.0 g / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 41.25. The S / Mil was 0.63 and was measured to be associated with a 54% decay. 0 grams of NH4OH was added to the kettle for 2 minutes. When the NH4OH supply was completed (temperature 73 ° C), the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.0 g / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 41.25. The S / Mil was 0.63 and was measured to be associated with a 54% decay. 0 grams of NH4OH was added to the kettle for 2 minutes. When the NH4OH supply was completed (temperature 73 ° C), the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.0 g / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 41.25. The S / Mil was 0.63 and was measured to be associated with a 54% decay.</p><p num="0038"> Comparative Example D: Comparative Example D was compared except that the MEI composition consisted of 275.0 grams of DI water, 13.6 grams of SDS, 677.6 grams of STY, 77.0 grams of AN, and 3.9 grams of LOFA. Manufactured according to the method of Example C. The filtered dispersion had a solid content of 41.1%. The S / Mil was 0.97 and was measured to be associated with a 43% decay.</p><p num="0039"> Example 2: Example 2 is a comparison, except that the composition of MEI was composed of 275.0 grams of DI water, 13.6 grams of SDS, 600.6 grams of STY, 154 grams of AN, and 3.9 grams of LOFA. Manufactured according to the method of Example C. The filtered dispersion had a solid content of 41.2%. The S / Mil was 0.87 and was measured with a 6% decay.</p><p num="0040"> Comparative Example E: Comparative Example E was compared except that the composition of MEI consisted of 275.0 grams of DI water, 13.6 grams of SDS, 754.6 grams of STY, 9.6 grams of DVB, and 3.9 grams of LOFA. Manufactured according to the method of Example C. DVB was first added to the MEI composition and not added during the MEI supply. The filtered dispersion had a solid content of 40.75. The S / Mil was 0.82 and was measured with a 15% decay.</p><p num="0041"> Example 3: In Example 3, the MEI composition consisted of 275.0 grams of DI water, 13.6 grams of SDS, 600.6 grams of STY, 154 grams of AN, 9.6 grams of DVB, and 3.9 grams of LOFA. Except for that, it was produced according to the method of Comparative Example E. DVB was first added to the MEI composition and not added during the MEI supply. The filtered dispersion had a solid content of 41.5%. The S / Mil was 0.69 and was measured to be accompanied by a 0% decay.</p><p num="0042"> Example 4: Example 4 was manufactured according to the method of Example 3, except that the reaction was cooled to 78 ° C after MEI feeding and cofeeding was completed. A monomer emulsion (MEII) having the same composition as MEII in Example 2 was fed to the reactor for 60 minutes. A solution of 2.0 grams of NaPS mixed with 60.0 grams of DI water was co-fed into the reactor at a rate of 1 gram / min. The temperature was allowed to rise to 86 ° C during supply. The filtered dispersion had a solid content of 41.7%. The S / Mil was 0.77 and was measured to be accompanied by a 0% decay.</p><p num="0043"> Comparative Example F: Comparative Example F was manufactured according to the method of Comparative Example E, except that 172.4 grams of Core 2 was used. The filtered dispersion had a solid content of 41.2%. The S / Mil was 0.25 and was measured to be accompanied by a 75% decay.</p><p num="0044"> Example 5: Example 5 was manufactured according to the method of Example 3, except that 172.4 grams of core 2 was used. The filtered dispersion had a solid content of 41.4%. The S / Mil was 0.46 and was measured to be accompanied by a 9% decay.</p><p num="0045"> Example 6: Evaluation of opacity (S / mil) and void collapse in Comparative Examples A to F and Examples 1 to 5. A 7 mil wet film was drawn down on a black vinyl scrub chart (Leneta # P121010N). Black vinyl scrub charts were measured for thickness (in mills) in four specific regions, for example, using an Ames gauge (# 2-212C) available from Ames Corporation in Waltham, Massachusetts. Membranes were dried for 2 hours in a chamber or room with low relative humidity (&lt;30% relative humidity, if the relative humidity is less than 30% during drying, the opacity does not change substantially). The reflectance of the dry film was measured on its four specific regions by a reflectance meter, the Gardner Instrument Reflectometer (BYK-Gardner, Columbia, Maryland). Ames gauges were also used to determine and average the thickness of the membrane over each of its particular regions. This procedure involves a temperature / humidity chamber with a membrane of 25 ° C / 80% relative humidity (SP in Warminster, PA). It was dried overnight in a Hotpack, Model # 417532) available from Industries, and then repeated in a low humidity chamber / room for 1 hour, except that it was dried at a relative humidity of less than 40%. .. % Collapse was calculated based on S / Mil (opacity) at 80% RH vs. S / mil scattering at &lt;30% RH. In Example 6, 7.0 grams (solid) film-forming binder RHOPLEX^(trademark)S / mil was determined using a blend of 3.0 grams (solid) polymer particles mixed with AC-264. Comparative Examples A to F and Examples 1 to 5 have a weight ratio of 1: 1 to the total weight of the second shell to all the other constituents of the polymer particles, which are neat under test conditions. Does not form a film.</p><p num="0046"><tables num="1"><img id="000003" he="98" wi="159" file="JP5214540B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0047"> Comparative Example A was produced by the method of US Patent Application Publication No. 20070043159. The second polymer shell was formed in the presence of the first polymer at a second shell feed temperature of 25-70 ° C, resulting in excellent disintegration, ie, a polymer showing excellent retention of void volume. Produced particles. Comparative Example B at a second shell feed temperature of 60-78 ° C resulted in more disintegration compared to Comparative Example A, i.e. resulting in polymer particles exhibiting inferior void volume retention than Comparative Example A. It was. Incorporating 20% AN into the first polymer shell results in better disintegration resistance compared to Comparative Example B when the polymerization temperature range of the second polymer shell is increased to 60-78 ° C. Produced polymer particles with.</p><p num="0048"><tables num="2"><img id="000004" he="94" wi="159" file="JP5214540B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0049"> The examples and comparative examples in Table 6.2 were formed without a tie coat, with the polymerization of the second shell in the high temperature range (60-78 ° C). Comparative Examples C and D (incorporating 0 and 10% AN in the first polymer shell, respectively) had poor disintegration resistance. Example 2 containing 20% AN in the first polymer shell had excellent disintegration resistance to Comparative Examples C and D.</p><p num="0050"><tables num="3"><img id="000005" he="94" wi="159" file="JP5214540B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0051"> The polyethylenically unsaturated monomer in Comparative Example C (MEUM herein) was placed in the last 12 parts of the first polymer shell. The addition of DVB to the entire first polymer shell (Comparative Example E) improved the disintegration resistance compared to Comparative Example C. Example 3 incorporating 20% AN into a first polymer shell entirely containing 1% DVB resulted in excellent disintegration resistance compared to Comparative Example E. Example 4 also shows excellent collapse resistance when a high temperature (78-86 ° C) second shell feed temperature is used.</p><p num="0052"><tables num="4"><img id="000006" he="81" wi="159" file="JP5214540B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0053"> Comparative Example F and Example 5 were manufactured using Core 2 (95 nm). Example 5 containing 20% AN in the first stage polymer had excellent disintegration resistance to Comparative Example F.</p><p num="0054"> Comparative Example G: A 5-liter four-necked round-bottom flask was equipped with a paddle stirrer, a thermometer, a nitrogen inlet and a reflux condenser. 1299.0 grams of Polymer 1 was added to the kettle and the temperature was adjusted to 25 ° C. A monomer emulsion (MEI) was produced by mixing 306 grams of DI water, 17.0 grams of SDS, 416.4 grams of MMA, 12.0 grams of MAA, and 591.60 grams of BA. At a kettle temperature of 25 ° C, a solution of 20 grams of 0.1% ferrous sulfate mixed with 2 grams of 1% EDTA was added to the kettle. Cofeed, then a solution of 3.7 grams of t-BHP mixed with 100 grams of DI water and another solution of 2.6 grams of IAA mixed with 100 grams of DI water, both 1.2 grams / min. Was added to the kettle at the rate of. Two minutes after the start of the cofeed solution, the already produced MEI was added to the kettle for 60 minutes. No external heat was applied to the reaction during the MEI supply. The kettle temperature was allowed to rise to 78 ° C. Upon completion of MEI supply, cofeed was stopped and the reaction was retained for 5 minutes. The temperature of the reaction at this point was 77 ° C. A solution of 5.0 grams of NH4OH mixed with 5.0 grams of DI water was then added to the kettle with 400 grams of heated DI water (90 ° C). At this point, MEII, pre-made by mixing 54.0 grams of DI water, 3.0 grams of SDS, 104.4 grams of BA, 75.6 grams of MMA, and 2.5 grams of 4-hydroxy TEMPO, was placed in the kettle for 5 minutes. Supplied. Immediately after the MEII supply was completed, 35.0 grams of NH4OH mixed with 35 grams of DI water was added to the kettle for 2 minutes. When the NH4OH supply was completed, the batch was held for 5 minutes. Then the cofeed solution is 1. It resumed to completion at a rate of 2 grams / minute. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 45.4%. The S / Mil was 1.88 and was measured to be associated with a 16% decay.</p><p num="0055"> Comparative Example H: Comparative Example H was produced according to the method of Comparative Example G, except that the temperature was adjusted to 60 ° C. after polymer 1 was added to the kettle. The filtered dispersion had a solid content of 45.6%. The S / Mil was 1.66 and was measured to be associated with a 67% decay.</p><p num="0056"> Comparative Example I: To a 5-liter four-necked round-bottom flask equipped as in Comparative Example A, 500 grams of DI water heated to a temperature of 89 ° C under a nitrogen atmosphere was added. To the heated kettle water was added 1.9 grams of NaPS dissolved in 20 grams of DI water. This was followed immediately by 125.0 grams of Core 1 (135 nm). Monomer emulsion (MEI) produced by mixing 200 grams of DI water, 10.0 grams of SDS, 548.8 grams of STY, 2.8 grams of LOFA, and 7.0 grams of DVB at a rate of 78 ° / min. It was fed to the reactor at a temperature of C. Two minutes after the start of MEI, a solution of 5.6 grams of AA mixed with 25 grams of DI water was added to the reactor. After 40 minutes of MEI feeding at a temperature of 78 ° C, the feeding rate was increased to 6.5 grams / min and 0.5 grams of NaPS cofeed solution in 30 grams of DI water was added to the reactor at a rate of 0.6 grams / min. The supply was started in. After an additional 15 minutes, the MEI feed rate was increased again to 13 grams / min and the reaction temperature was allowed to rise to 92 ° C. Upon completion of the MEI and NaPS cofeeds, the reaction was cooled to 62 ° C. While cooling, a solution of 20 grams of 0.1% ferrous sulfate mixed with 2 grams of 1% EDTA was added to the kettle at a temperature of 75 ° C. Then, at a temperature of 70 ° C, a cofeed is a solution of 3.7 grams of t-BHP mixed with 100 grams of DI water and another solution of 2.6 grams of IAA mixed with 100 grams of DI water. Both were added to the kettle at a rate of 1.20 g / min. Two minutes after the start of the cofeed solution, 306 grams of DI water, 17.0 grams of SDS, 591.6 grams of BA, 416.4 grams of MMA and 12. MEII, pre-made by mixing 0 grams of MAA, was added to the kettle for 60 minutes, allowing the temperature to rise to 78 ° C without providing any external heat. Upon completion of MEII, the cofeed solution was stopped and the batch was held at 78 ° C for 5 minutes. A solution of 5.0 grams of NH4OH mixed with 5.0 grams of DI water was then added to the kettle with 400 grams of heated DI water (90 ° C). At this point, MEIII, pre-made by mixing 54.0 grams of DI water, 3.0 grams of SDS, 104.4 grams of BA, 75.6 grams of MMA, and 2.5 grams of 4-hydroxy TEMPO, was placed in the kettle for 7 minutes. Supplied. Immediately after the MEIII supply was completed, 35.0 grams of NH4OH mixed with 35 grams of DI water was added to the kettle for 2 minutes. When the NH4OH supply was completed (temperature 72 ° C), the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.2 grams / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 45.2%. The S / Mil was 1.54 and was measured to be associated with a 26% decay. 0 grams of NH4OH was added to the kettle for 2 minutes. When the NH4OH supply was completed (temperature 72 ° C), the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.2 grams / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 45.2%. The S / Mil was 1.54 and was measured to be associated with a 26% decay. 0 grams of NH4OH was added to the kettle for 2 minutes. When the NH4OH supply was completed (temperature 72 ° C), the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.2 grams / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 45.2%. The S / Mil was 1.54 and was measured to be associated with a 26% decay.</p><p num="0057"> Example 7: Example 7 shows that the composition of MEI was composed of 200 grams of DI water, 10.0 grams of SDS, 464.8 grams of STY, 84.0 grams of AN, 7.0 grams of DVB and 2.8 grams of LOFA. Except, it was produced according to the method of Comparative Example I. The filtered dispersion had a solid content of 41.1%. The S / Mil was 1.51 and was measured to be accompanied by a 2% decay.</p><p num="0058"> Example 8: Example 8 shows that the composition of MEI was composed of 200 grams of DI water, 10.0 grams of SDS, 436.8 grams of STY, 112.0 grams of AN, 7.0 grams of DVB and 2.8 grams of LOFA. Except, it was produced according to the method of Comparative Example I. The filtered dispersion had a solid content of 45.5%. The S / Mil was 1.60 and was measured to be associated with a 12% decay.</p><p num="0059"> Example 9: Example 9 was manufactured according to the method of Example 8 except that the reaction was cooled to 84 ° C. after MEI feeding and cofeeding was completed. A solution of 3.5 grams of NaPS mixed in 90.0 grams of DI water was fed to the reactor at a rate of 1.7 grams / min. A monomer emulsion (MEII) having the same composition as MEII in Example 12 was fed to the reactor for 60 minutes. During supply, the temperature was allowed to rise to 86 ° C. The filtered dispersion had a solid content of 46.2%. The S / Mil was 1.75 and was measured to be associated with a 10% decay.</p><p num="0060"> Comparative Example J: Comparative Example J is an example except that the composition of MEI was composed of 200 grams of DI water, 10.0 grams of SDS, 548.8 grams of STY, 7.0 grams of DVB and 2.8 grams of LOFA. Manufactured according to 9 methods. The filtered dispersion had a solid content of 46.0%. The S / Mil was 1.59 and was measured to be accompanied by a 70% decay.</p><p num="0061"> Comparative Example K: Comparative Example K shows that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 385.0 grams of STY, 168.0 grams of AN, 1.4 grams of ALMA and 2.8 grams of LOFA. Except for, it was produced according to the method of Example 10. The filtered dispersion had a solid content of 47.6%. The S / Mil was 1.80 and was measured to be associated with a 24% decay.</p><p num="0062"> Example 10: Example 10 shows that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 380.8 grams of STY, 168.0 grams of AN, 7.0 grams of DVB and 2.8 grams of LOFA. Except for, it was produced according to the method of Comparative Example I. The composition of MEII was also composed of 240 grams of DI water, 17.0 grams of SDS, 591.6 grams of BA, 416.4 grams of MMA, and 12.0 grams of MAA. The filtered dispersion had a solid content of 47.4%. The S / Mil was 1.28 and was measured to be accompanied by a 2% decay.</p><p num="0063"> Example 11: Example 11 shows that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 383.6 grams of STY, 168.0 grams of AN, 3.5 grams of DVB and 2.8 grams of LOFA. Except for, it was produced according to the method of Example 10. The filtered dispersion had a solid content of 47.2%. The S / Mil was 1.70 and was measured to be associated with a 7% decay.</p><p num="0064"> Example 12: Evaluation of opacity (S / Mil) and void collapse in Comparative Examples G to K and Examples 7 to 11. S / Mil (opacity) was determined as in Example 6 with polymer particles without the use of any co-binder. Comparative Examples G to K and Examples 7 to 11 have a total of all other structures of the polymer particles: a weight ratio of the second shell of 1: 2, which alone forms a film under test conditions.</p><p num="0065"><tables num="5"><img id="000007" he="111" wi="159" file="JP5214540B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0066"> Comparative Example G was produced by the method of US Patent Application Publication No. 20070043159. A second polymer shell was added to the first polymer in the temperature range of 25-78 ° C, resulting in comparison with polymer particles produced at a second shell feed temperature of 60-78 ° C as in Comparative Example H. As a result, polymer particles showing increased disintegration resistance were produced. Polyethylene unsaturated monomers (MEUM) in Comparative Examples G and H were used in the last 12 parts of the first polymer shell. The addition of DVB throughout the first polymer shell (Comparative Example I) improved disintegration resistance as compared to Comparative Example H. However, incorporating 15% AN in the first polymer shell as in Example 7 results in Comparative Example H when the polymerization temperature range of the second polymer shell is raised to 60-78 ° C. And I produced polymer particles with excellent disintegration resistance.</p><p num="0067"><tables num="6"><img id="000008" he="75" wi="159" file="JP5214540B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0068"> At the increased second shell polymerization temperature (84-86 ° C), Example 9 incorporating 20% AN in the first polymer shell showed excellent disintegration resistance to Comparative Example J.</p><p num="0069"><tables num="7"><img id="000009" he="100" wi="158" file="JP5214540B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0070"> Examples 10 and 11 (incorporating 1% and 0.5% DVB, respectively) had excellent disintegration resistance to Comparative Example K, which contained a small amount of MEUM (0.25% ALMA) in the first polymer shell. showed that.</p><p num="0071"> Example 13: To a 5-liter four-necked round-bottom flask equipped as in Comparative Example A, 500 grams of DI water heated to a temperature of 89 ° C under a nitrogen atmosphere was added. To the heated kettle water was added 1.9 grams of NaPS dissolved in 20 grams of DI water. This was followed immediately by 125.0 grams of Core 1 (135 nm). 3.0 grams / min of monomeric emulsion (MEI) produced by mixing 125 grams of DI water, 10.0 grams of SDS, 436.8 grams of STY, 112.0 grams of AN, 2.8 grams of LOFA, and 7.0 grams of DVB. It was fed to the reactor at a rate of 78 ° C. Two minutes after the start of MEI, a solution of 5.6 grams of AA mixed with 25 grams of DI water was added to the reactor. After 40 minutes of MEI feeding at a temperature of 78 ° C, the feeding rate was increased to 6.5 grams / min and 0.5 grams of NaPS cofeed solution in 30 grams of DI water was added to the reactor at a rate of 0.6 grams / min. The supply was started in. After an additional 15 minutes, the MEI feed rate was increased again to 13 grams / min and the reaction temperature was allowed to rise to 92 ° C. Upon completion of the MEI and NaPS cofeeds, the reaction was cooled to 72 ° C. While cooling, a solution of 20 grams of 0.1% ferrous sulfate mixed with 2 grams of 1% EDTA was added to the kettle at a temperature of 80 ° C. Then, at a temperature of 76 ° C, a solution of 1.9 grams of t-BHP and 2.6 grams of NaPS mixed with 100 grams of DI water and another solution of 2.6 grams of IAA mixed with 100 grams of DI water. Cofeed was added to the kettle at a rate of 1.20 g / min. Two minutes after the start of the cofeed solution at a temperature of 72 ° C, 240 grams of DI water, 17.0 grams of SDS, 591.6 grams of BA, 416.4 grams of MMA and 12. MEII, pre-made by mixing 0 grams of MAA, was added to the kettle for 60 minutes, allowing the temperature to rise to 80 ° C without providing any external heat. Upon completion of MEII, the cofeed solution was stopped and the batch was held at 80 ° C for 5 minutes. A solution of 5.0 grams of NH4OH mixed with 5.0 grams of DI water was then added to the kettle with 400 grams of heated DI water (90 ° C). At this point, MEIII, pre-made by mixing 54.0 grams of DI water, 3.0 grams of SDS, 104.4 grams of BA, 75.6 grams of MMA, and 2.5 grams of 4-hydroxy TEMPO, was placed in the kettle for 7 minutes. Supplied. Immediately after the MEIII supply was completed, 35.0 grams of NH4OH mixed with 35 grams of DI water was added to the kettle for 2 minutes. When the NH4OH supply was completed (temperature 72 ° C), the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.2 grams / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 47.4%. The S / Mil was 1.52 and was measured to be associated with a 6% decay. 0 grams of NH4OH was added to the kettle for 2 minutes. When the NH4OH supply was completed (temperature 72 ° C), the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.2 grams / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 47.4%. The S / Mil was 1.52 and was measured to be associated with a 6% decay. 0 grams of NH4OH was added to the kettle for 2 minutes. When the NH4OH supply was completed (temperature 72 ° C), the batch was held for 5 minutes. The cofeed solution was then restarted at a rate of 1.2 grams / min until its completion. The dispersion was then cooled to 25 ° C and filtered to remove agglomerates. The filtered dispersion had a solid content of 47.4%. The S / Mil was 1.52 and was measured to be associated with a 6% decay.</p><p num="0072"> Example 14: Example 14 shows that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 380.3 grams of STY, 168.0 grams of AN, 7.0 grams of DVB and 2.8 grams of LOFA. Except for, it was produced according to the method of Example 13. The filtered dispersion had a solid content of 47.3%. The S / Mil was 1.32 and was measured to be associated with a 4% decay.</p><p num="0073"> Example 15: Example 15 shows that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 383.6 grams of STY, 168.0 grams of AN, 3.5 grams of DVB and 2.8 grams of LOFA. Except for, it was produced according to the method of Example 13. The filtered dispersion had a solid content of 47.4%. The S / Mil was 1.64 and was measured to be associated with an 11% decay.</p><p num="0074"> Comparative Example L: Comparative Example L shows that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 385.0 grams of STY, 168.0 grams of AN, 1.75 grams of DVB and 2.8 grams of LOFA. Except for, it was produced according to the method of Example 13. The filtered dispersion had a solid content of 47.7%. The S / Mil was 1.82 and was measured to be associated with a 33% decay.</p><p num="0075"> Example 16: Example 16 shows that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 327.6 grams of STY, 224.0 grams of AN, 3.5 grams of DVB and 2.8 grams of LOFA. Except for, it was produced according to the method of Example 13. The filtered dispersion had a solid content of 47.9%. The S / Mil was 1.32 and was measured to be accompanied by a 0% decay.</p><p num="0076"> Comparative Example M: Comparative Example M shows that the composition of MEI consisted of 125 grams of DI water, 10.0 grams of SDS, 329.0 grams of STY, 224.0 grams of AN, 1.75 grams of DVB and 2.8 grams of LOFA. Except for, it was produced according to the method of Example 13. The filtered dispersion had a solid content of 47.9%. The S / Mil was 1.63 and was measured to be associated with a 33% decay.</p><p num="0077"> Example 17: Example 17 shows that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 271.6 grams of STY, 280.0 grams of AN, 3.5 grams of DVB and 2.8 grams of LOFA. Except for, it was produced according to the method of Example 13. The filtered dispersion had a solid content of 48.0%. The S / Mil was 1.35 and was measured to be associated with an 11% decay.</p><p num="0078"> Comparative Example N: Comparative Example N shows that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 273.0 grams of STY, 280.0 grams of AN, 1.75 grams of DVB and 2.8 grams of LOFA. Except for, it was produced according to the method of Example 13. The filtered dispersion had a solid content of 47.9%. The S / Mil was 1.42 and was measured to be accompanied by a 37% decay.</p><p num="0079"> Comparative Example O: Comparative Example O is Example except that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 274.4 grams of STY, 280.0 grams of AN and 2.8 grams of LOFA. Manufactured according to 13 methods. The filtered dispersion had a solid content of 47.9%. The S / Mil was 1.33 and was measured to be associated with a 49% decay.</p><p num="0080"> Example 18: Example 18 shows that the composition of MEI was composed of 125 grams of DI water, 10.0 grams of SDS, 243.6 grams of STY, 308.0 grams of AN, 3.5 grams of DVB and 2.8 grams of LOFA. Except for, it was produced according to the method of Example 13. The filtered dispersion had a solid content of 47.6%. The S / Mil was 1.15 and was measured to be associated with a 9% decay.</p><p num="0081"> Example 19: In Example 19, the composition of MEI is composed of 125 grams of DI water, 10.0 grams of Fes-32, 215.6 grams of STY, 336.0 grams of AN, 3.5 grams of DVB and 2.8 grams of LOFA. And MEII was produced according to the method of Example 13 except that MEII was composed of 240 grams of DI water, 17.0 grams of Fes-32, 591.6 grams of BA, 416.4 grams of MMA, and 12.0 grams of MAA. The filtered dispersion had a solid content of 47.5%. The S / Mil was 1.00 and was measured with a 7% decay.</p><p num="0082"> Example 20: Evaluation of opacity (S / mil) and void collapse in Examples 13-19 and Comparative Examples L-O. S / Mil (opacity) was determined as in Example 6 with polymer particles without the use of any co-binder. Examples 13-19 and Comparative Examples L-O have a weight ratio of the second shell of 1: 2 to the sum of all other structures of the polymer particles, which alone form a film under test conditions.</p><p num="0083"><tables num="8"><img id="000010" he="96" wi="159" file="JP5214540B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0084"> The proportion of all stages is 1 part core polymer / 14 parts 1st shell polymer // 30 parts 2nd shell polymer. All second shell supply temperature ranges are 70-80 ° C.</p><p num="0085"> Examples 13 to 19 incorporating 0.5 to 1% MEUM in the first shell polymer show excellent disintegration resistance to Comparative Examples L to O incorporating 0 to 0.25% MEUM.</p>