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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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  • C08F2/00—Processes of polymerisation
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  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/06—Polystyrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/24—Polymer with special particle form or size

Definitions

• the present invention relates to polymer particles obtained by modifying the surface of polymer particles obtained by a polymerization reaction with a surfactant, and uses thereof.
• polymer particles preferably used as raw materials for optical members such as light diffusing films and antiglare films, and applications of the polymer particles (optical members, paint additives and antiblocking agents: films and resin moldings containing these. Body), and a method for producing the polymer particles.
• Polymer particles having a volume average particle diameter of 1 to 100 ⁇ m are, for example, additives for coating agents such as paints (matting agents, etc.), additives for inks (matting agents, etc.), main components of adhesives, or Additives, additives for artificial marble (low shrinkage agents, etc.), paper treatment agents, fillers for external preparations such as cosmetics (fillers for improving slipperiness), column fillers used for chromatography, static charge Used as an additive for toner used for image development, an anti-blocking agent for film, a light diffusing agent for optical members (optical diffusing film, optical film such as antiglare film, light diffusing body, etc.) ing.
• additives for coating agents such as paints (matting agents, etc.), additives for inks (matting agents, etc.), main components of adhesives, or Additives, additives for artificial marble (low shrinkage agents, etc.), paper treatment agents, fillers for external preparations such as cosmetics (fillers for improving slipperiness), column fillers used
• Such polymer particles can be produced by polymerizing a polymerizable monomer.
• Suspension polymerization, seed polymerization, emulsion polymerization and the like are known as polymerization methods for polymerizing polymerizable monomers.
• a surfactant is usually used so that the polymerization reaction can be stably carried out and the generation of coarse particles can be suppressed.
• Patent Document 1 describes polymer particles composed of at least one of a (meth) acrylic polymer, a styrene polymer, and a (meth) acrylic-styrene copolymer.
• the polymer particles have a variation coefficient of particle size of 15.0% or less, and the content of the surfactant having the polyoxyalkylene chain per unit surface area of the polymer particles is 2.0 to 15.0 ⁇ 10. -3 g / m 2 , the content of other surfactants per unit surface area of the polymer particles is 10.0 ⁇ 10 -5 g / m 2 or less.
• Patent Document 2 it is used as a light diffusing agent obtained by polymerizing a vinyl-based monomer in a medium containing a surfactant (in the example, another surfactant having no polyoxyalkylene chain). Polymer particles are described. The amount of the residual surfactant in the polymer particles is 0.05 parts by mass or less (0.005 to 0.036 parts by mass in the example) with respect to 100 parts by mass of the resin fine particles.
• a surfactant in the example, another surfactant having no polyoxyalkylene chain.
• an optical film such as a light diffusing film or an antiglare film
• a resin composition containing polymer particles, a binder and an organic solvent is known to be coated on a film base material.
• the polymer particles need to be uniformly and stably dispersed in the resin composition and the dry coating film obtained from the resin composition so that stable optical characteristics can be obtained. ..
• the time required for the polymer particles to be uniformly and stably dispersed in the resin composition is preferably short from the viewpoint of productivity.
• the polymer particles disclosed in Patent Document 1 have a resin composition depending on the type of other surfactant contained in the polymer particles, the amount of surface residue thereof, and the amount of surface residue of non-volatile components contained in the polymer particles. In some cases, the time required for the polymer particles to be uniformly and stably dispersed in the material was lengthened.
• the polymer particles disclosed in Patent Document 2 are non-uniform because the dispersed state of the polymer particles in the resin composition is not stable when the resin composition is applied onto the film substrate to form a coating film. As a result, it sometimes aggregated locally. As a result, the polymer particles may not spread uniformly over the entire coating film formed on the film substrate, the optical characteristics of the optical film may become non-uniform, and the desired optical characteristics may not be obtained for the entire optical film. rice field.
• the present invention has been made in view of the above circumstances, and the polymer particles are uniformly and stably dispersed (excellent in dispersibility and dispersion stability) in the resin composition and the dry coating film obtained from the resin composition. It is an object of the present invention to provide polymer particles in which the time required for the polymer particles to be uniformly and stably dispersed in the resin composition is short.
• the present inventors have found that in a resin composition containing polymer particles, the dispersion stability of the polymer particles correlates with the change in viscosity with time. Then, in order to have high dispersion stability and shorten the time until the dispersion becomes stable, the type and solubility parameter (SP value) of the surfactant contained in the polymer particles, their surface residue amount, and non-volatile components It is important to optimize the amount of surface residue, thereby uniformly and stably dispersing in the resin composition containing the polymer particles and in the dry coating film obtained from the polymer particles (for dispersibility and dispersion stability). We have found that polymer particles (excellent) can be obtained, and have completed the present invention.
• SP value solubility parameter
• the solubility parameter (SP value) is 9.0 to 12.0, and the content of the surfactant having a polyoxyalkylene chain is 1.0 ⁇ 10 -3 to 6 per unit surface area of the polymer particles. 0 ⁇ 10 -3 g / m 2 ,
• the solubility parameter (SP value) is 9.0 to 12.0, and the amount of the surfactant having no polyoxyalkylene chain is 5.0 ⁇ 10 -5 to 13. Per unit surface area of the polymer particles.
• the amount of surface residue of the non-volatile component is 2.0 ⁇ 10 -3 g / m 2 or less per unit surface area of the polymer particles.
• Polymer particles. [2] The polymer particle of [1], wherein the volume average particle diameter is 1 to 20 ⁇ m, and the coefficient of variation (CV value) of the particle diameter of the following polymer particles is 15% or less.
• Coefficient of variation (CV value) of particle size of polymer particles (standard deviation of particle size distribution based on volume of polymer particles ⁇ volume average particle size of polymer particles) ⁇ 100
• the polymer particles of the present invention are excellent in dispersibility and dispersion stability in the resin composition when a resin composition containing the polymer particles, a binder and an organic solvent is formed, and are also in the resin composition.
• the time required for the polymer particles to be uniformly and stably dispersed is shortened, and the workability is excellent.
• the dispersibility and dispersion stability of the polymer particles are maintained, so that excessive aggregation of the polymer particles during coating film formation is suppressed. be able to. Therefore, the polymer particles uniformly spread over the entire coating film formed on the film base material, and impart optical properties such as uniform and stable light diffusivity and antiglare to the coating film. can.
• the type of surfactant contained in the polymer particles for example, the presence or absence of a polyoxyalkylene chain, the solubility parameter (SP value) of the surfactant, etc.
• the amount of the surfactant per unit surface area of the polymer particles can be adjusted by adjusting the amount of the surface residue of the non-volatile component per unit surface area of the polymer particles. Therefore, it is not necessary to change the monomer composition of the polymer particles for adjusting the dispersibility of the polymer particles and to adjust the refractive index accordingly, which has been conventionally performed, and the workability can be further improved.
• the polymer particles of the present invention have a small difference in surface state between the polymer particles, they are uniformly dispersed in the resin composition when mixed with a resin binder and an organic solvent to form a resin composition. It will be excellent in sex.
• the time change of the surface state of the polymer particles and the difference in the surface state between the production lots of the polymer particles can be reduced, the quality stability is excellent, and the dispersed state of the resin composition between the production lots. The difference is small and the dispersion stability is excellent.
• the solubility parameter (SP value) is described in Toshinao Okizu, "Adhesion", Polymer Publishing Association, Vol. 40, No. 8 (1996), pp. 342-350, and various atomic groups by Okizu described in Table 1 below. It means the solubility parameter ⁇ calculated by the following formula (1) using the ⁇ F and ⁇ v values of. In the case of a mixed solvent or a copolymer, it means the solubility parameter ⁇ calculated by the following formula (2).
• ⁇ ⁇ F / ⁇ v (1)
• ⁇ mix ⁇ 1 ⁇ 1 + ⁇ 2 ⁇ 2 + ⁇ ⁇ ⁇ ⁇ n ⁇ n (2)
• ⁇ F represents ⁇ F in Table 1 below
• ⁇ v represents the molar volume ⁇ v in Table 1 below.
• solubility parameter calculated as described above may be simply referred to as an SP value.
• SP value the solubility parameter calculated as described above
• the polymer constituting the polymer particles of the present invention is not particularly limited, and is, for example, a vinyl-based polymer (acrylic polymer, styrene-based polymer, acrylic styrene-based polymer, olefin-based polymer, vinyl halide-based polymer). Polymers, etc.), polyester-based polymers, polyamide-based polymers, polyurethane-based polymers, and the like, and one or more selected from the group consisting of them.
• a vinyl-based polymer acrylic polymer, styrene-based polymer, acrylic styrene-based polymer, olefin-based polymer, vinyl halide-based polymer.
• Polymers, etc. polyester-based polymers, polyamide-based polymers, polyurethane-based polymers, and the like, and one or more selected from the group consisting of them.
• a vinyl polymer which is a copolymer of a monofunctional vinyl-based monomer having one ethylenically unsaturated group and a polyfunctional vinyl-based monomer having two or more ethylenically unsaturated groups. Is preferable.
• Examples of the monofunctional vinyl-based monomer include (meth) acrylic acid ester-based monomer, aromatic vinyl-based monomer, fatty acid vinyl ester-based monomer, halogenated olefin-based monomer, and cyanide. From vinyl-based monomers, unsaturated carboxylic acid-based monomers, unsaturated polycarboxylic acid ester-based monomers, unsaturated carboxylic acid amide-based monomers, unsaturated carboxylic acid amides methylolates-based monomers, etc. One or more types selected from the group can be used.
• the (meth) acrylic acid ester-based monomer means an acrylic acid ester-based monomer or a methacrylic acid ester-based monomer.
• examples of the (meth) acrylic acid ester-based monomer include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-butyl (meth) acrylic acid, isobutyl (meth) acrylic acid, and (meth) acrylic acid.
• Alkyl (meth) acrylate monomers such as 2-ethylhexyl, n-octyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) (Meta) acrylic acid ester having an epoxy group (glycidyl group) such as acrylate, 2-hydroxyethyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 2-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) Examples thereof include one or more selected from the group consisting of (meth) acrylic acid esters having an amino group such as acrylate and diethylaminoethyl (meth) acrylate.
• aromatic vinyl-based monomer examples include one or more selected from the group consisting of styrene, ⁇ -methylstyrene, vinyltoluene, ethylvinylbenzene and the like.
• fatty acid vinyl ester-based monomer for example, one or more kinds selected from the group consisting of vinyl acetate, vinyl propionate, vinyl versatic acid and the like can be used.
• halogenated olefin-based monomer for example, one or more kinds selected from the group consisting of vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylidene fluoride and the like can be used.
• the vinyl cyanide-based monomer for example, one or more kinds selected from the group consisting of (meth) acrylonitrile and the like can be used.
• the unsaturated carboxylic acid-based monomer contains an unsaturated carboxylic acid, a salt thereof, or an anhydride thereof, and includes, for example, (meth) acrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, fumaric acid, and the like.
• One or more kinds selected from the group consisting of those ammoniums, metal salts, maleic anhydride and the like can be used.
• the unsaturated polycarboxylic acid ester-based monomer includes an unsaturated dicarboxylic acid monoester, a salt thereof, and an unsaturated dicarboxylic acid diester, and examples thereof include monobutylmaleic acid, ammonium and metal salts thereof, and maleic acid.
• One or more kinds selected from the group consisting of dimethyl and the like can be used.
• the unsaturated carboxylic acid amide-based monomer for example, one or more kinds selected from the group consisting of (meth) acrylamide, diacetone (meth) acrylamide and the like can be used.
• Examples of unsaturated carboxylic acid amide methylolated monomers include N-methylolacrylamide, N-methylolmethacrylamide, methylolated diacetoneacrylamide, and alcohols having 1 to 8 carbon atoms.
• One or more selected from the group consisting of etherified products (for example, N-isobutoxymethylacrylamide) and the like can be used.
• the polyfunctional vinyl-based monomer is not particularly limited as long as it is a monomer having two or more ethylenically unsaturated groups.
• One or more kinds selected from the group consisting of acrylate, trimethylolpropantri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like can be used.
• the polymer particles of the present invention are preferably composed of at least one polymer of (meth) acrylic polymer, styrene polymer, and (meth) acrylic-styrene copolymer.
• the (meth) acrylic polymer is a polymer of a (meth) acrylic acid ester-based monomer, or a (meth) acrylic acid ester-based monomer, a (meth) acrylic acid ester-based monomer, and a styrene-based polymer. It is a copolymer with a vinyl-based monomer other than the monomer.
• the styrene-based polymer is a polymer of a styrene-based monomer, or a common weight of the styrene-based monomer and a vinyl-based monomer other than the (meth) acrylic acid ester-based monomer and the styrene-based monomer. It is a coalescence.
• the (meth) acrylic-styrene copolymer is a copolymer of a (meth) acrylic acid ester-based monomer and a styrene-based monomer, or a (meth) acrylic acid ester-based monomer and a styrene-based copolymer. It is a copolymer of a monomer and a vinyl-based monomer other than them.
• polymer particles composed of a (meth) acrylic-styrene copolymer are preferable in terms of light diffusivity and antiglare property, and a polymer having a specific gravity of the polymer particles exceeding 1.0 is more preferable. ..
• the specific gravity of the polymer particles is a measured value obtained by measuring according to the method A in JIS K5101-11-1. Specifically, the specific gravity was measured in a constant temperature room at 20 ° C. as follows. A Wardon-type pycnometer having a content of 50 ml was completely filled with ethanol, and the mass of the pycnometer including the contents at this time was weighed to give A (g).
• the polymer constituting the polymer particles is preferably a copolymer (crosslinked polymer) of a monofunctional vinyl-based monomer and a polyfunctional vinyl-based monomer.
• the polymer constituting the polymer particles is a (meth) acrylic-styrene crosslinked polymer in terms of light diffusivity and antiglare property.
• the amount of the structural unit derived from the polyfunctional vinyl-based monomer in the crosslinked polymer is 1 to 70% by mass, preferably 3 to 60% by mass, and more preferably 5 to 50% by mass with respect to 100% by mass of the crosslinked polymer. It is in the range of%.
• the degree of cross-linking of the polymer is low. Therefore, when the polymer particles are mixed with the binder and the solvent to obtain a resin composition, the polymer particles may swell, the viscosity of the resin composition may increase, and the coating workability may decrease. Further, as a result of lowering the degree of cross-linking of the polymer, in the application of mixing the polymer particles with a binder and molding (so-called kneading application), when the polymer particles are heated during mixing or molding, the polymer is formed. Particles are more likely to dissolve or deform. If the amount of the structural unit derived from the polyfunctional vinyl-based monomer is more than 70% by mass, the improvement of the effect corresponding to the amount of the polyfunctional vinyl-based monomer used may not be observed, and the production cost may increase. be.
• the more preferable range of the SP value is 9.1 to 11.9, and further preferably 9.3 to 11.7. , Most preferably 9.6 to 11.2.
• the alkylene group in the polyoxyalkylene chain include an alkylene group having 2 to 6 carbon atoms, preferably an ethylene group, a propylene group, a trimethylene group and a butylene group, and particularly preferably an ethylene group.
• a surfactant having a polyoxyalkylene chain having an SP value of 9.0 to 12.0 if the SP value is in the range of 9.0 to 12.0, it is anionic, cationic, nonionic and amphoteric. It may be any of the sex surfactants.
• anionic surfactant having a polyoxyalkylene chain all known anionic surfactants such as fatty acid salt type, sulfate ester salt type, sulfonate type, phosphoric acid ester salt type, and phosphoric acid ester type are used. Can be used.
• polyoxyethylene alkyl ether sulfate such as polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene alkyl sulfate, polyoxyethylene styrenated phenyl ether sulfate ammonium, and the like.
• Polyoxyethylene alkyl phenyl ether phosphates such as ethylene styrenated phenyl ether sulfate, polyoxyethylene nonyl phenyl ether phosphate (eg sodium polyoxyethylene nonyl phenyl ether phosphate), polyoxyethylene styrene phenyl ether phosphorus
• ethylene styrenated phenyl ether sulfate polyoxyethylene nonyl phenyl ether phosphate (eg sodium polyoxyethylene nonyl phenyl ether phosphate), polyoxyethylene styrene phenyl ether phosphorus
• acid esters polyoxyethylene alkyl ether phosphates and the like can be used.
• nonionic surfactant having a polyoxyalkylene chain any known nonionic surfactant such as an ester type, an ether type, or an ester ether type can be used.
• polyoxyethylene alkyl ethers such as polyoxyethylene tridecyl ether
• polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene styrene phenyl ethers, polyoxyethylene fatty acid esters, and polyoxyethylene monolaurate.
• polyoxyethylene sorbitan fatty acid ester such as sorbitan, polyoxyethylene alkylamine, oxyethylene-oxypropylene block polymer and the like can be used.
• polyoxyethylene alkylphenyl ether phosphate such as polyoxyethylene nonylphenyl ether phosphate (for example, sodium polyoxyethylene nonylphenyl ether phosphate), polyoxyethylene styrene phenyl ether phosphate, and polyoxy.
• phosphate ester-based anionic surfactants such as ethylene alkyl ether phosphate ester.
• a phosphate ester-based anionic surfactant include Prysurf (AL, A210G, A208F, etc.) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. and Phosphanol (LO-529, etc.) manufactured by Toho Chemical Industry Co., Ltd.
• Prysurf AL, A210G, A208F, etc.
• Phosphanol LO-529, etc.
• One or more kinds selected from commercially available products such as and salts thereof and salts thereof can be used.
• the content of the surfactant having a polyoxyalkylene chain having an SP value of 9.0 to 12.0 is 1.0 ⁇ 10 -3 to 6.0 ⁇ 10 -3 g / m 2 per unit surface area of the polymer particles. It is preferably 1.1 ⁇ 10 -3 to 4.25 ⁇ 10 -3 g / m 2 , and more preferably 1.4 ⁇ 10 -3 to 2.8 ⁇ 10 -3 g / m 2 .
• the present inventors have determined that the content of the surfactant having a polyoxyalkylene chain having an SP value of 9.0 to 12.0 is 4.4 ⁇ 10 -3 to 6.0 per unit surface area of the polymer particles. Even when it is ⁇ 10 -3 g / m 2 , the dispersibility and dispersion stability of the polymer particles can be enhanced when the resin composition containing the polymer particles is formed, and the polymer particles It has been found that the dispersibility and dispersion stability can be adjusted without changing the monomer composition.
• the means for incorporating the surfactant having a polyoxyalkylene chain having an SP value of 9.0 to 12.0 into the polymer particles is not particularly limited.
• a method of mixing the polymer particles and the surfactant, a method of coexisting the surfactant at the time of forming the polymer particles, and the like can be mentioned.
• the polyoxyalkylene chain is added to the polymer particles. It is preferable to use a method of containing (remaining) a surfactant having.
• the polymer particles obtained by seed polymerization have little variation in particle size, and when used for optical members such as antiglare films and light diffusing films, the optical properties such as antiglare and light diffusing properties of the optical members are improved. Can be made to.
• the more preferable range of the SP value is 9.0 to 11.8, and further preferably 9.1 to 11.5. Yes, most preferably 9.2 to 11.4.
• the SP value is in the range of 9.0 to 12.0, it is anionic, cationic, nonionic and both. It may be any of ionic surfactants.
• the dispersion of the vinyl-based monomer in the liquid medium can be more stably secured, and the particle size can be increased. It is more preferable to use at least one of an anionic surfactant and a nonionic surfactant because a uniform polymer particle can be obtained. As a result, the occurrence of agglutination during the polymerization reaction can be prevented, and dispersion stability can be ensured.
• any known anionic surfactant such as fatty acid salt type, sulfate ester salt type, sulfonate type, and phosphate ester salt type can be used. ..
• fatty acid soaps such as sodium oleate and potash oil soap
• alkyl sulfate esters such as sodium lauryl sulfate and ammonium lauryl sulfate
• alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, alkylnaphthalene sulfonates, and alkane sulfonates.
• Dialkyl sulfosuccinates such as sodium di (2-ethylhexyl) sulfosuccinate, sodium dioctyl sulfosuccinate, alkenyl succinates such as alkenyl succinate (mono or di) sodium, alkyl phosphate ester salts, sodium naphthalene sulfonate formalin condensates
• alkenyl succinates such as alkenyl succinate (mono or di) sodium, alkyl phosphate ester salts, sodium naphthalene sulfonate formalin condensates
• any known nonionic surfactant such as an ester type, an ether type, or an ester ether type can be used.
• a group consisting of polyoxyalkylene alkyl ethers such as polyoxyalkylene tridecyl ether having 3 or more carbon atoms, sorbitan fatty acid esters, glycerin fatty acid esters, isopropyl palmitate, and fatty acid esters such as sorbitan trioleate.
• polyoxyalkylene alkyl ethers such as polyoxyalkylene tridecyl ether having 3 or more carbon atoms
• sorbitan fatty acid esters such as polyoxyalkylene tridecyl ether having 3 or more carbon atoms
• sorbitan fatty acid esters glycerin fatty acid esters
• isopropyl palmitate isopropyl palmitate
• fatty acid esters such as sorbitan trioleate.
• One or more types selected from can be used.
• any known cationic surfactant such as an amine salt type or a quaternary ammonium salt type can be used, and in particular, a water-soluble cationic surfactant can be used.
• Activators are advantageous in terms of their handling.
• alkylamine salts such as laurylamine acetate and stearylamine acetate
• alkyltrimethylammonium chlorides such as lauryltrimethylammonium chloride, hexadecyltrimethylammonium chloride, cocoyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyldimethylbenzylammonium chloride, lauryl.
• alkyldimethylbenzyl chlorides such as dimethylbenzylammonium chloride can be used.
• amphoteric surfactant having no polyoxyalkylene chain for example, one or more kinds selected from the group consisting of lauryldimethylamine oxide, phosphoric acid ester-based surfactant, phosphite ester-based surfactant and the like are used. Can be used.
• dialkyl sulfosuccinates such as sodium di (2-ethylhexyl) sulfosuccinate
• alkenyl succinates such as alkenyl succinate (mono or di) sodium
• alkyl phosphates alkyl sulfates
• sodium lauryl sulfate alkyl sulfates
• polyoxy selected from the group consisting of anionic surfactants having no polyoxyalkylene chain selected from the group consisting of salts, fatty acid esters such as isopropyl palmitate and sorbitan trioleate, and the like. It is preferable to use one or more nonionic surfactants having no alkylene chain.
• the content of the surfactant having an SP value of 9.0 to 12.0 and having no polyoxyalkylene chain is 5.0 ⁇ 10-5 to 13.0 ⁇ 10-5 g / m per unit surface area of the polymer particles. It is 2 , preferably 5.2 ⁇ 10 -5 to 12.7 ⁇ 10 -5 g / m 2 , and particularly preferably 7.3 ⁇ 10 -5 to 10.4 ⁇ 10 -5 g / m. It is 2.
• the means for incorporating the surfactant having an SP value of 9.0 to 12.0 and having no polyoxyalkylene chain in the polymer particles is not particularly limited.
• a method of mixing the polymer particles and the surfactant, a method of coexisting the surfactant at the time of forming the polymer particles, and the like can be mentioned.
• the vinyl-based polymer is polymerized in the presence of a surfactant, and the content is adjusted as necessary to allow the polymer particles to contain (remain) the surfactant. It is preferable to use the method.
• the polymer particles obtained by seed polymerization have little variation in particle size, and when used for optical members such as antiglare films and light diffusing films, the optical properties such as antiglare and light diffusing properties of the optical members are improved. Can be made to.
• the non-volatile component in the polymer particles of the present invention means a non-volatile component contained in the supernatant liquid after the polymer particles are dispersed in water and centrifuged to separate the polymer particles into the supernatant liquid. Specifically, 15.0 g of water is added to 5.0 g of the polymer particles, and the dispersion treatment is performed for 60 minutes using an ultrasonic cleaner to disperse the polymer particles in water and put them in a centrifuge tube having an inner diameter of 24 mm. It is a non-volatile component contained in the supernatant liquid recovered after centrifugation under the conditions of K factor 6943 and a rotation time of 30 minutes using a centrifuge.
• Such a non-volatile component is a component that does not diverge and remains even after heating at 110 ° C. and 1 atm for 10 hours.
• a by-product such as a polymerization product obtained by polymerizing a monomer not absorbed by the seed particles corresponds to the polymer particles.
• a minute component having a diameter of 1 ⁇ m or less contained in the polymer particles can be mentioned.
• the surface residue amount of the non-volatile component the content of the non-volatile component in the polymer particles and the specific surface area of the polymer particles are used, and the surface of the non-volatile component per unit surface area of the polymer particles is calculated by the following formula. The amount of residue is calculated.
• the amount of surface residue of the non-volatile component in the polymer particles of the present invention is 2.0 ⁇ 10 -3 g / m 2 or less, preferably 0.01 ⁇ 10 -3 to 2.0 ⁇ , per unit surface area of the polymer particles.
• the volume average particle size of the polymer particles of the present invention is, for example, 1 to 20 ⁇ m, preferably 1.5 to 15 ⁇ m, and more preferably 1.5 to 10 ⁇ m.
• the volume average particle size of the polymer particles refers to the arithmetic mean of the volume-based particle size distribution measured by the Coulter method, for example, the method described in Examples.
• the coefficient of variation (CV value) of the particle size of the polymer particles of the present invention is calculated by the following formula.
• Coefficient of variation (CV value) of particle size of polymer particles (standard deviation of particle size distribution based on volume of polymer particles ⁇ volume average particle size of polymer particles) ⁇ 100
• the coefficient of variation (CV value) of the particle size in the present invention is preferably 15% or less, more preferably 12% or less, still more preferably 11% or less. Thereby, the dispersion uniformity of the polymer particles can be further improved.
• the gel fraction of the polymer particles of the present invention is 90% or more, preferably 94% or more, more preferably 96% or more, still more preferably 97% or more. If the gel content is less than 90%, sufficient solvent resistance cannot be ensured. Therefore, for example, polymer particles are mixed with an organic solvent together with a binder and coated on a film substrate to provide an antiglare film or light. In the case of using an optical film such as a diffusing film, the polymer particles may be dissolved in an organic solvent, and optical characteristics such as light diffusivity and antiglare may not be sufficiently obtained.
• the gel fraction in the present specification refers to, for example, the gel fraction measured by the method described in Examples.
• the refractive index of the polymer particles of the present invention is preferably 1.490 to 1.600.
• the polymer particles having the above constitution have good optical properties (for example, light transmission, antiglare, light diffusivity, etc.) when used in an optical member such as an antiglare film or a light diffusing film. It is possible to realize an optical member having. So far, polymer particles produced from a monomer having a high refractive index (for example, a styrene-based monomer) of a homopolymer and a monomer having a high hydrophilicity are generally a monomer having a high hydrophilicity.
• the refractive index of the homopolymer is low (for example, 1.488 or less), it has been difficult to realize polymer particles having a refractive index of 1.570 to 1.600.
• the polymer particles of the present invention have a refractive index of 1.570 to 1.600 because hydrophilicity can be imparted to the polymer particles without the need to add a highly hydrophilic monomer. Polymer particles having hydrophilicity can be easily obtained.
• Examples of the method for producing the polymer particles of the present invention include a method of mixing the polymer particles and the surfactant, a method of coexisting the surfactant when forming the polymer particles, and the like.
• the vinyl-based polymer is polymerized in the presence of a surfactant, and the content is adjusted as necessary to allow the polymer particles to contain (remain) the surfactant. It is preferable to use the method.
• a polymerization step of polymerizing a vinyl-based monomer in the presence of a surfactant containing a non-surfactant to obtain a crude product containing the polymer particles containing the surfactant and the medium (ii). ) A solid-liquid separation step in which the crude product is charged into a filter, the medium contained in the crude product is passed through the filter medium of the filter to be removed, and the polymer particles contained in the crude product are retained on the filter medium. (Iii) The cleaning liquid was put into the filter holding the polymer particles on the filter medium, and the polymer particles on the filter medium were brought into contact with the cleaning liquid, and the cleaning liquid was passed through the filter medium to be removed and washed. A method including a washing step of obtaining the polymer particles on the filter medium, and (iv), if necessary, a drying step and / or a classification step, is preferable.
• the polymerization step of the above (i) it is particularly preferable to carry out seed polymerization in the presence of seed particles, a vinyl-based monomer and a surfactant, and adjust the content in a washing step or the like.
• the polymer particles obtained by seed polymerization have little variation in particle size, and when used for optical members such as antiglare films and light diffusing films, the optical properties such as antiglare and light diffusing properties of the optical members are improved. Can be made to.
• the solid-liquid separation step and the washing step may affect the uniformity of the amount of residual components on the surface of the polymer particles and the uniformity of the surface state brought about by the uniformity.
• these steps become unstable, unnecessary components of the surfactant used in the production of the polymer particles (surfactant having a surplus polyoxyalkylene chain that does not contribute to the modification of the surface of the polymer particle and the surfactant and (Other surfactants used as needed) and polymer dispersion stabilizers used as needed are adversely affected, and the amount of residual components on the surface of the polymer particles varies.
• each step of the method for producing polymer particles of the present invention will be described in detail.
• a surfactant having an SP value of 9.0 to 12.0 and having a polyoxyalkylene chain and a surfactant having an SP value of 9.0 to 12.0 and having no polyoxyalkylene chain in a liquid medium are used.
• the liquid medium water, an organic solvent, or a mixture thereof can be used.
• an aqueous medium is preferable, and for example, a lower alcohol having 5 or less carbon atoms such as water, methyl alcohol, and ethyl alcohol, a mixture of water and a lower alcohol, and the like can be used.
• a surfactant having an SP value of 9.0 to 12.0 and having a polyoxyalkylene chain the surfactant having a polyoxyalkylene chain having a ⁇ SP value of 9.0 to 12.0 in the above [polymer particles] is used.
• the surfactant described in Agent> is used.
• surfactant As a surfactant having an SP value of 9.0 to 12.0 and not having a polyoxyalkylene chain, the surfactant does not have a polyoxyalkylene chain having an SP value of 9.0 to 12.0 in the [polymer particles].
• Surfactant> The surfactant described in> is used.
• the vinyl-based monomer and its composition As the vinyl-based monomer and its composition, the vinyl-based monomer and its composition described in ⁇ Polymer> in the [Polymer Particles] are used.
• a surfactant having an SP value of 9.0 to 12.0 and having a polyoxyalkylene chain and a surfactant having an SP value of 9.0 to 12.0 and having no polyoxyalkylene chain is not particularly limited, but the total amount of the surfactant is 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the vinyl-based monomer. Further, it is preferable that the surfactant having an SP value of 9.0 to 12.0 and having a polyoxyalkylene chain is contained in an amount of 50 to 99% by mass, preferably 70 to 99% by mass, based on the whole surfactant.
• the polymerization stability may be lowered, and it may be difficult to set the amount of the surfactant contained in the polymer particles.
• the amount of the surfactant used is larger than the above range, it is uneconomical in terms of cost, and it becomes difficult to adjust the amount of each surfactant contained in the polymer particles to the specified range. There is a risk of becoming.
• the dispersion stability of the vinyl-based monomer during polymerization in a liquid medium can be ensured, and polymer particles having the same particle size can be obtained, so that the SP value is 9.0 to 12
• At least an anionic surfactant having a polyoxyalkylene chain of 0.0 and a nonionic surfactant having an SP value of 9.0 to 12.0 and having a polyoxyalkylene chain are used.
• the method for polymerizing the vinyl-based monomer is not particularly limited as long as it is a known polymerization method using a liquid medium and a surfactant.
• methods such as emulsion polymerization, suspension polymerization, and seed polymerization can be mentioned.
• emulsion polymerization a liquid medium, a vinyl-based monomer that is difficult to dissolve in this medium, and a surfactant (emulsifier) are mixed, and a polymerization initiator that is soluble in the medium is added thereto to carry out polymerization. It is legal.
• emulsion polymerization the variation in particle size of the obtained polymer particles can be reduced.
• Suspension polymerization is a polymerization method in which a vinyl-based monomer and an aqueous medium such as water are mechanically stirred to suspend the vinyl-based monomer in the aqueous medium for polymerization.
• suspension polymerization polymer particles having a small particle size and a relatively uniform particle size can be obtained.
• the seed polymerization is a method in which when the polymerization of a vinyl-based monomer is started, seed particles made of a polymer of a vinyl-based monomer prepared separately are added to carry out the polymerization.
• seed particles made of a polymer of a vinyl-based monomer are used as seed particles, the vinyl-based monomer is absorbed by the seed particles in an aqueous medium, and the vinyl-based monomer is polymerized in the seed particles.
• the seed particles can be grown, and polymer particles having a particle size larger than that of the original seed particles can be obtained.
• an emulsion (suspension) containing an aqueous medium, a vinyl monomer, and a surfactant is prepared.
• the aqueous medium is water or a mixture of water and an organic solvent (for example, a lower alcohol having 5 or less carbon atoms).
• the surfactant has an SP value of 9.0 to 12.0 and has a polyoxyalkylene chain
• a surfactant has an SP value of 9.0 to 12.0 and does not have a polyoxyalkylene chain.
• the amount of the surfactant used is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the vinyl-based monomer.
• a known method can be used for preparing the emulsion (suspension).
• an emulsion can be obtained by adding a vinyl-based monomer and a surfactant to an aqueous medium and dispersing them with a fine emulsifier such as a homogenizer, a sonicator, or a nanomizer (registered trademark). It is preferable that the particle size of the droplets of the vinyl-based monomer present in the obtained emulsion is smaller than the particle size of the seed particles to be added next, because the seed particles efficiently absorb the particles.
• a fine emulsifier such as a homogenizer, a sonicator, or a nanomizer (registered trademark).
• seed particles are added to the obtained emulsion (suspension).
• the seed particles may be added to the emulsion as they are, or may be added to the emulsion in the form of being dispersed in an aqueous medium.
• the vinyl-based monomer is absorbed by the seed particles.
• a method for allowing the seed particles to absorb the vinyl-based monomer a method of stirring the emulsion at room temperature (about 20 ° C.) for 1 to 12 hours is usually mentioned.
• the emulsion may be heated to about 30 to 50 ° C.
• the mixing ratio of the vinyl-based monomer and the seed particles is preferably in the range of 5 to 300 parts by mass, and in the range of 50 to 250 parts by mass, with respect to 1 part by mass of the seed particles. It is more preferable to be inside.
• the mixing ratio of the vinyl-based monomers is smaller than the above range, the increase in particle size due to polymerization is small, so that the production efficiency is lowered.
• the mixing ratio of the vinyl-based monomer becomes larger than the above range, the vinyl-based monomer is not completely absorbed by the seed particles, and the vinyl-based monomer is independently suspended and polymerized in an aqueous medium, resulting in an unintended abnormal particle size.
• Polymer particles may be produced.
• the end of absorption of the vinyl-based monomer into the seed particles can be determined by confirming the enlargement of the particle size by observing with an optical microscope.
• the polymer particles are obtained by polymerizing the vinyl-based monomer absorbed by the seed particles.
• the polymer particles may be obtained by repeating the step of absorbing the vinyl-based monomer into the seed particles and polymerizing the seed particles a plurality of times.
• a polymerization initiator When polymerizing the vinyl-based monomer, a polymerization initiator may be used if necessary.
• the polymerization initiator may be mixed with the vinyl-based monomer in advance and then dispersed in the aqueous medium, or both the polymerization initiator and the vinyl-based monomer may be separately dispersed in the aqueous medium.
• the polymerization initiator used is not particularly limited.
• benzoyl peroxide lauroyl peroxide, o-chlorobenzoyl peroxide, o-methoxy benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, di -Organic peroxides such as tert-butyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2, 3-Dimethylbutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,3,3-trimethylbutyronitrile), 2,2'-azobis (2) -Isobutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), (2-car
• the polymerization temperature and polymerization time of the seed polymerization can be appropriately selected depending on the type of the vinyl-based monomer and the type of the polymerization initiator used as needed.
• the polymerization temperature can be, for example, 25 to 110 ° C, preferably 50 to 100 ° C.
• the polymerization time can be, for example, 1 to 12 hours.
• the polymerization reaction of the seed polymerization may be carried out in an atmosphere of an inert gas (for example, nitrogen) which is inert to the polymerization.
• the polymerization reaction of seed polymerization may be carried out by raising the temperature after the vinyl-based monomer and the polymerization initiator used as necessary are completely absorbed by the seed particles. preferable.
• a polymer dispersion stabilizer may be added to the polymerization reaction system in order to improve the dispersion stability of the polymer particles.
• the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinylpyrrolidone and the like.
• the above-mentioned polymer dispersion stabilizer may be used in combination with an inorganic water-soluble polymer compound such as sodium tripolyphosphate.
• polyvinyl alcohol and polyvinylpyrrolidone are preferably used.
• the amount of the polymer dispersion stabilizer added is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the vinyl-based monomer.
• nitrites such as sodium nitrite, nitrites, hydroquinones, ascorbic acids, and water-soluble vitamins.
• a water-soluble polymerization inhibitor such as Class B, citric acid, and polyphenols may be added to the aqueous medium.
• the amount added is preferably in the range of 0.02 to 0.2 parts by mass with respect to 100 parts by mass of the vinyl-based monomer.
• the method for producing seed particles used for seed polymerization is not particularly limited, and dispersion polymerization, emulsion polymerization, soap-free emulsion polymerization (emulsion polymerization without using a surfactant as an emulsifier), seed polymerization, suspension polymerization and the like are used. Can be done. In order to obtain polymer particles having a substantially uniform particle size by seed polymerization, it is necessary to first use seed particles having a substantially uniform particle size and to grow these seed particles substantially uniformly. Seed particles having a substantially uniform particle size as a raw material can be obtained by emulsion polymerization, dispersion polymerization, or the like of a vinyl-based monomer. Preferably, emulsion polymerization, soap-free emulsion polymerization, seed polymerization and dispersion polymerization are used.
• a polymerization initiator is used as needed during polymerization to obtain seed particles.
• the polymerization initiator include a polymerization initiator that can be used during the seed polymerization.
• the amount of the polymerization initiator used is preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the vinyl-based monomer used to obtain the seed particles.
• the weight average molecular weight of the obtained seed particles can be adjusted by adjusting the amount of the polymerization initiator used.
• a molecular weight modifier may be used to adjust the weight average molecular weight of the seed particles when polymerizing the seed particles.
• the molecular weight modifier include mercaptans such as n-octyl mercaptan and tert-dodecyl mercaptan, ⁇ -methylstyrene dimer; terpenes such as ⁇ -terpinene and dipentene, and halogenated hydrocarbons such as chloroform and carbon tetrachloride.
• One or more types selected from the group can be used.
• the weight average molecular weight of the obtained seed particles can be adjusted by adjusting the amount of the molecular weight adjusting agent used.
• Solid-liquid separation process In the solid-liquid separation step for producing the polymer particles of the present invention, the crude product containing the polymer particles containing the surfactant obtained in the polymerization step and the medium is charged into a filter and used as the crude product. This is a step of passing the contained medium through the filter medium of the filter to remove it, and holding the polymer particles contained in the crude product on the filter medium for solid-liquid separation.
• the amount of the medium passing through the filter medium per unit time is calculated by the following formula (3); X ⁇ 5.50 ⁇ A (3) (In the formula (3), X is the amount of the medium passing through the filter medium per unit time (kg / min), and A is the area of the interface between the filter medium and the object to be filtered (m 2 ).) It is preferable to satisfy.
• the solid-liquid separation step by controlling the amount of the medium passing through the filter medium per unit time so as to satisfy the above formula (3), a by-product (emulsion polymerization product) generated during the polymerization reaction together with the medium ), Excess surfactants, polymer dispersion stabilizers used as needed, additives such as polymerization inhibitors used as needed, and other unnecessary components can be removed. Thereby, the amount of the surfactant and the non-volatile component contained in the polymer particles remaining on the filter medium can be easily adjusted (reduced).
• the filter used in the solid-liquid separation step is not particularly limited.
• a pressure filter provided with a pressure-resistant container having a columnar internal space, a filter medium arranged at the inner bottom of the pressure-resistant container, and a compressed gas feeder for supplying compressed gas into the pressure-resistant container is used. Can be done.
• the area of the bottom surface (filtration area) of the columnar internal space of the pressure-resistant container can be substantially the same as the area of the interface between the filter medium and the object to be filtered (crude product).
• Examples of the solid-liquid separation step using such a pressure filter include the following methods.
• A) The crude product is charged into the pressure-resistant container of the pressure filter in the form of a slurry solution.
• B The crude product is filled on the filter medium in the pressure-resistant container.
• C) The compressed gas supply machine supplies the compressed gas to the upper space of the filter medium in the pressure-resistant container, and pressurizes the upper space of the filter medium inside the pressure-resistant container.
• D Due to the pressurization of the upper space, the crude product is pressed against the filter medium, the liquid medium contained in the crude product passes through the filter medium, is discharged as a filtrate to the outside of the pressure-resistant container, and the polymer is placed on the filter medium. You can get a cake of particles.
• the pressure-resistant container is preferably made of stainless steel and has a pressure resistance of 0.50 MPa or more.
• the filter medium is not particularly limited as long as it can reliably collect the polymer particles.
• the pressurizing condition when pressurizing the upper space of the filter medium in the pressure-resistant container using the pressurizing filter is not particularly limited as long as it satisfies the above formula (3).
• the internal pressure of the pressure-resistant container is preferably kept substantially constant so as to satisfy the above formula (3) from the start of pressurization to the end of the solid-liquid separation step.
• the internal pressure of the pressure-resistant container gradually decreases as the medium contained in the crude product passes through the filter medium. Specifically, when the amount of medium passing through the filter medium is reduced or almost eliminated, the compressed air pressure in the pressure-resistant container is released from the bottom, and it becomes difficult to maintain the internal pressure of the pressure-resistant container at the pressure at the time of pressurization.
• the amount of medium contained in the crude product put into the filter (pressurized filter) (when all the crude products obtained in the polymerization step are put into the filter, in the polymerization step
• the amount of the medium used is 70% by mass or more, preferably 75 to 85% by mass with respect to 100% by mass until the medium passes through the filter medium, and the medium contained in the crude product is preferably removed. ..
• by-products emulsion polymerization products
• surplus surfactants emulsion polymerization products
• polymer dispersion stabilizers used as needed emulsion polymerization inhibitors used as needed, etc.
• Unnecessary components such as additives can be removed.
• the amounts of the surfactant, the non-volatile component and the unnecessary component contained in the polymer particles remaining on the filter medium can be easily adjusted (reduced).
• the amount (discharge amount) of the medium passing through the filter medium is less than 70% by mass with respect to 100% by mass of the amount of the medium contained in the crude product, unnecessary components can be sufficiently removed. It may not be possible, and it may be difficult to adjust (decrease) the amount of the surfactant and the non-volatile component contained in the polymer particles remaining on the filter medium.
• the amount of the medium contained in the crude product charged into the pressure filter is 70% by mass or more with respect to 100% by mass. It is preferable to end the process when the pressure has passed through the filter medium and the internal pressure of the pressure-resistant container becomes 2/3 or less of the pressure at the time of pressurization. As a result, the residual amount of unnecessary components in the polymer particles remaining on the filter medium can be reliably reduced.
• the liquid removal rate at the time of removing the medium from the slurry composed of the crude product containing the polymer particles and the medium is not particularly limited.
• it may be in the range of 0.025 to 0.095 kg / min ⁇ m 2 , preferably 0.025 to 0.08 kg / min ⁇ m 2 , and more preferably 0.028 to 0.075 kg / min ⁇ m 2. can.
• the liquid removal rate is too fast, unnecessary components contained in the polymer particles may not be sufficiently removed, and it is difficult to adjust (reduce) the amounts of the surfactant and non-volatile components contained in the polymer particles. May become.
• the liquid removal rate is too slow, the solid-liquid separation step takes time, the workability deteriorates, and the surfactant contained in the polymer particles may be lost more than necessary.
• the cleaning liquid is put into the filter that holds the polymer particles after the solid-liquid separation step on the filter medium, and the polymer particles and the cleaning liquid on the filter medium are charged.
• the present inventors make the polymer particles (cake of polymer particles) on the filter medium obtained in the solid-liquid separation step 10 times or less, preferably 1 to 9 times the volume of the polymer particles.
• a cleaning treatment is carried out, and if necessary, polymer particles on the cleaned filter medium are further subjected to.
• the cleaning treatment is performed again by immersing the polymer particles in a cleaning solution 10 times or less, preferably 1 to 9 times, more preferably 1.7 to 8 times, still more preferably 1.5 to 7 times the volume of the polymer particles. I found a way to repeat the operation. Then, they have found that the abundance of the surfactant in the polymer particles can be controlled by immersing the cake of the polymer particles in the washing liquid.
• pressure filtration including a pressure-resistant container having a columnar internal space, a filter medium arranged at the inner bottom of the pressure-resistant container, and a compressed gas feeder for supplying compressed gas into the pressure-resistant container.
• a vessel When a vessel is used, the cake of the polymer particles remaining on the filter medium is kept as it is on the filter medium, and the cleaning liquid is supplied into the pressure-resistant container to bring the cake into contact with the cleaning liquid.
• the cake is immersed in the cleaning liquid, and the cake is liquefied, so that the cracks in the cake are self-repaired.
• the short path of the cleaning liquid is eliminated, the amount of the cleaning liquid used is suppressed, and efficient cleaning can be performed.
• the compressed gas is supplied to the upper space of the filter medium in the pressure-resistant container by the compressed gas feeder, and the upper space of the filter medium is pressurized.
• the cake is washed in contact with the washing liquid, and the washing liquid after washing is discharged as a filtrate to the outside of the pressure-resistant container.
• the cleaning liquid supplied into the filter and the cake are mixed and made into a slurry by using a stirrer before pressurization. You may.
• the cracks in the cake may be repaired by using a stirrer before supplying the cleaning liquid for cleaning. As a result, there is no short path of the cleaning liquid, and efficient cleaning can be performed.
• the pressurizing conditions when pressurizing the upper space of the filter medium in the pressure-resistant container using the pressurizing filter are not particularly limited.
• the upper space of the filter medium is preferably pressurized at a rate of 0.01 to 0.30 MPa / min.
• the internal pressure of the pressure-resistant container is kept substantially constant from the start of pressurization to the end of the cleaning step.
• the internal pressure of the pressure-resistant container gradually decreases as the charged cleaning liquid passes through the filter medium after pressurization. Specifically, when the amount of cleaning liquid passing through the filter medium is reduced or almost eliminated, the compressed air pressure in the pressure-resistant container is released from the bottom, and it becomes difficult to maintain the internal pressure of the pressure-resistant container at the pressure at the time of pressurization.
• the amount of the medium contained in the crude product put into the filter (pressurized filter) (when all the crude products obtained in the polymerization step were put into the filter, it was used in the polymerization step.
• the amount of the medium is 70% by mass or more, preferably 90 to 97% by mass with respect to 100% by mass, until the medium passes through the filter medium, and the medium contained in the polymer particles is preferably removed.
• the amount of the surfactant and the non-volatile component contained in the polymer particles remaining on the filter medium can be easily adjusted (reduced).
• the amount of the medium passing through the filter medium is less than 70% by mass with respect to 100% by mass of the amount of the medium contained in the crude product, unnecessary components may not be sufficiently removed. It may be difficult to adjust (decrease) the amount of surfactant and non-volatile components contained in the polymer particles remaining on the filter medium.
• the amount of the medium contained in the crude product charged into the pressure filter is 100% by mass, and the amount of the medium is 70% by mass or more. It is preferable to end the process when the pressure has passed and the internal pressure of the pressure-resistant container becomes 2/3 or less of the pressure at the time of pressurization. As a result, the residual amount of unnecessary components in the polymer particles remaining on the filter medium can be reliably reduced.
• the cleaning liquid used in the cleaning step is preferably an aqueous medium, and examples thereof include water, lower alcohols having 5 or less carbon atoms such as methyl alcohol and ethyl alcohol, and mixtures thereof. In particular, it is preferable to use the same medium as that used in the polymerization step.
• the mass of the cleaning liquid used in the cleaning step is the mass of the polymer particles held on the filter medium (when all the crude products obtained in the polymerization step in the solid-liquid separation step are put into the filter, in the polymerization step. It is preferably 10 times or less, preferably 1 to 9 times, more preferably 1.7 to 8 times, still more preferably 1.5 to 7 times the total amount of the vinyl-based monomer used).
• the cake is liquefied and the cracks in the cake are self-repaired. Therefore, there is no short path of the cleaning liquid, and efficient cleaning can be performed, and it is not necessary to use a large amount of cleaning liquid.
• the mass of the cleaning liquid used in the cleaning step is 10 times or less, it is possible to prevent the surfactant and non-volatile components from being eluted more than necessary in the cleaning step, and the surfactant contained in the polymer particles and The amount of non-volatile components can be easily controlled.
• the mass of the cleaning liquid used in the cleaning step is adjusted to an appropriate amount in consideration of the type of each surfactant used in the polymerization step, thereby further reducing the content of each component adhering to the surface of the polymer particles. Can be done. For example, when the amount of the cleaning liquid exceeds an appropriate amount, the surfactant having an SP value of 9.0 to 12.0 and having a polyoxyalkylene chain is gradually eluted, and the SP value contained in the polymer particles becomes high.
• the amount of the surfactant having a polyoxyalkylene chain of 9.0 to 12.0 may not be a predetermined amount.
• the filtration rate when removing the cleaning liquid from the polymer particles is not particularly limited.
• it may be in the range of 0.025 to 0.095 kg / min ⁇ m 2 , preferably 0.025 to 0.08 kg / min ⁇ m 2 , and more preferably 0.028 to 0.075 kg / min ⁇ m 2. can.
• the liquid removal rate is too fast, unnecessary components contained in the polymer particles may not be sufficiently removed, and it is difficult to adjust (reduce) the amounts of the surfactant and non-volatile components contained in the polymer particles. May become.
• the liquid removal rate is too slow, the solid-liquid separation step takes time, the workability deteriorates, and the surfactant contained in the polymer particles may be lost more than necessary.
• the temperature of the cleaning liquid used for cleaning is a temperature at which the surfactant used at the time of polymerization is sufficiently eluted, for example, 40 to 80 ° C, preferably 50 to 80 ° C.
• a method of heating the cleaning liquid to a temperature for cleaning a method of supplying the heated cleaning liquid to the filter may be used, and after supplying the cleaning liquid to the filter, a heater jacket arranged around the filter may be used. A method of heating the cleaning liquid may be used.
• the conductivity of the cleaning liquid that has passed through the filter medium is 2.0 times or less the conductivity of the cleaning liquid before it is put into the filter (pressurized filter), and the internal pressure of the pressure-resistant container is pressurized. It is preferable to end when the pressure becomes 2/3 or less of the pressure of.
• the polymer particles obtained in the washing step are dried in a known dryer to remove the washing liquid.
• the dryer is not particularly limited, but it is preferable to use a vacuum dryer, for example, a vacuum stirring dryer (crushing dryer) incorporating a stirring blade.
• a vacuum dryer for example, a vacuum stirring dryer (crushing dryer) incorporating a stirring blade.
• classification preferably air flow classification
• the drying conditions in the present invention are appropriately adjusted according to the capacity and capacity of the dryer to be used, and for example, the following conditions can be adopted.
• the degree of vacuum (against atmospheric pressure) can be, for example, in the range of ⁇ 0.001 to ⁇ 0.5 MPa, preferably ⁇ 0.05 to ⁇ 0.1 MPa.
• the drying temperature can be, for example, in the range of 40 to 80 ° C., preferably 50 to 70 ° C.
• the drying time can be, for example, 4 to 10 hours (hr), preferably 7 to 9 hours.
• the operating conditions of the dryer used can be such that the stirring share coefficient calculated by the following formula (4) is in the range of 1800 to 2800, preferably 1900 to 2800, and more preferably 1950 to 2750.
• Stirring share coefficient [total area of stirring blades (m 2 ) x rotation speed (rpm) x time (hr)] / [polymer particle amount (kg) x polymer particle bulk specific gravity (no unit)] (4) (Measurement of bulk specific density is based on JIS Z 8807: 2012) If the value of the stirring share coefficient is larger than 2800, the stirring force acting on the resin becomes excessive, and the particles may be broken. If the value of the stirring share coefficient is less than 1800, the stirring force acting on the resin becomes too small, the separation of non-volatile components from the particles by shearing becomes insufficient, and the remaining amount may become larger than necessary.
• the amount of the polymer particles charged into the dryer can be in the range of 0.1 to 1000 kg, preferably 0.5 to 500 kg.
• the surfactant in the drying step, is eluted from the surface of the polymer particles into water, and then the non-volatile components are scraped from the surface of the particles by the action of stirring and sharing by using a crushing dryer. , Can be sorted by suction. Thereby, the content of the surfactant per unit surface area of the polymer particles and the amount of surface residue in the polymer particles of the non-volatile component can be adjusted.
• the crushing and drying process causes the non-volatile components to be sheared and most of them separated. Then, the surface of the polymer particles is effectively modified by the surfactant, and polymer particles having excellent dispersion uniformity and improved dispersibility can be obtained.
• an appropriate amount of the surfactant adhering to the polymer particles in the polymerization step can be removed together with the medium and the cleaning liquid.
• surfactants having an SP value of 9.0 to 12.0 and having a polyoxyalkylene chain surfactants having an SP value of 9.0 to 12.0 and having no polyoxyalkylene chain, and other interfaces.
• most of the other surfactant can be sufficiently removed together with the medium and the cleaning liquid.
• the SP value per unit surface area of the polymer particles is 9.0 to 12.0
• the surfactant having a polyoxyalkylene chain and the SP value are 9.0 to 12.0
• the polyoxyalkylene chain is obtained.
• the content (residual amount) of the surfactant that does not have can be adjusted to an appropriate amount, the content (residual amount) of other surfactants can be extremely reduced, and the content (residual amount) of the non-volatile component can be made extremely small. Can be adjusted to an appropriate amount.
• the polymer particles of the present invention can be used for various purposes. For example, it can be used as an optical member, a paint additive, and an anti-blocking agent.
• a resin composition containing polymer particles and a resin binder is formed, and the resin composition is used to obtain an optical film such as an antiglare film or a light diffusing film or an optical member such as a light diffusing material, particularly an antiglare member.
• a coating material can be obtained as the polymer particles themselves or a mixture thereof with a binder resin, an additive, or the like.
• a resin molded product can be obtained by molding the polymer particles themselves or a mixture thereof and a resin.
• the polymer particles themselves can be mixed with a resin as an anti-blocking agent to form a resin composition to form a resin molded product such as a film.
• the resin composition of the present invention contains the polymer particles of the present invention described above and a resin binder.
• the binder is appropriately selected according to the required properties such as transparency, polymer particle dispersibility, light resistance, moisture resistance and heat resistance, and is not particularly limited.
• resin binders selected from the group consisting of fluororesins such as polyvinylidene fluoride and fluoroolefin vinyl ether polymers.
• the resin binder is preferably a curable resin capable of forming a crosslinked structure by a crosslinking reaction from the viewpoint of improving the durability of the resin composition.
• the curable resin can be cured under various curing conditions, such as a thermosetting resin, a photocurable resin, an ultraviolet curable resin, an ionizing radiation curable resin such as an electron beam curable resin, and a warm air curable resin.
• a thermosetting resin is one or more selected from the group consisting of a thermosetting urethane resin composed of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicone resin, and the like. Can be given.
• the ionizing radiation curable resin is synthesized from a polyfunctional (meth) acrylate resin such as a polyhydric alcohol polyfunctional (meth) acrylate; a diisocyanate, a polyhydric alcohol, and a (meth) acrylic acid ester having a hydroxy group. Examples thereof include one or more selected from the group consisting of polyfunctional urethane acrylate resins and the like.
• the ionizing radiation curable resin preferably contains a polyfunctional (meth) acrylate resin, and more preferably contains a polyhydric alcohol polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule. preferable.
• Examples of the polyhydric alcohol polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule include trimethylolpropane tri (meth) acrylate, trimethylol ethanetri (meth) acrylate, 1,2.
• Examples thereof include one or more selected from the group consisting of acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate and the like.
• the ionizing radiation curable resin is selected from the group consisting of polyether resins having acrylate-based functional groups, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins and the like.
• the resin binder may contain a thermoplastic resin in addition to the curable resin.
• thermoplastic resin examples include cellulose derivatives such as acetyl cellulose, nitro cellulose, acetyl butyl cellulose, ethyl cellulose, and methyl cellulose, homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of vinyl chloride, and vinylidene chloride alone.
• (Meta) of vinyl resins such as polymers and copolymers, acetal resins such as polyvinyl formal and polyvinyl butyral, homopolymers and copolymers of acrylic acid esters, homopolymers and copolymers of methacrylic acid esters, etc.
• One or more types selected from the group consisting of acrylic resins, polystyrene resins, polyamide resins, linear polyester resins, polycarbonate resins and the like can be mentioned.
• a rubber-based binder such as synthetic rubber or natural rubber, an inorganic binder, or the like can also be used.
• the rubber-based binder resin include one or more selected from the group consisting of ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber and the like.
• the inorganic binder include one or more selected from the group consisting of silica sol, alkaline silicate, silicon alkoxide, phosphate and the like.
• an inorganic or organic-inorganic composite matrix obtained by hydrolyzing and dehydrating and condensing a metal alkoxide or silicon alkoxide can also be used.
• a silicon oxide matrix obtained by hydrolyzing and dehydrating and condensing silicon alkoxide for example, tetraethoxysilane, etc. can be used.
• the amount of the polymer particles in the resin composition is 2 parts by mass or more, preferably 4 parts by mass or more, and more preferably 6 parts by mass or more with respect to 100 parts by mass of the solid content of the resin binder.
• the amount of the polymer particles in the resin composition is 300 parts by mass or less, preferably 200 parts by mass or less, and more preferably 100 parts by mass or less with respect to 100 parts by mass of the solid content of the binder.
• a photopolymerization initiator can be added to the resin binder. Any photopolymerization initiator may be used, but it is preferable to use one suitable for the photocurable resin or ultraviolet curable resin to be used. Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, and peroxides.
• 2,3-Dialkyldione compounds disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, active halogen compounds, ⁇ -acyloxime esters, etc. Can be used.
• the amount of the photopolymerization initiator used is usually in the range of 0.5 to 20% by mass, preferably in the range of 1 to 5% by mass, based on 100% by mass of the binder.
• the resin composition may contain an organic solvent, if necessary.
• the coating can be easily performed by containing an organic solvent.
• the organic solvent include aromatic solvents such as toluene and xylene, alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and propylene glycol monomethyl ether, and acetic acid.
• Ester solvents such as ethyl and butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether and ethylene glycol Glycol ethers such as diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether, 2-methoxyethyl acetate, 2-ethoxyethyl acetate (cellosolve acetate), 2-butoxyethyl acetate, propylene glycol methyl ether acetate, etc.
• ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone
• 2-methoxyethanol 2-ethoxyethanol
• Glycol ether esters chlorine solvents such as chloroform, dichloromethane, trichloromethane, methylene chloride, ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, 1,3-dioxolane, N-methylpyrrolidone, dimethylformamide , Dimethylsulfoxide, dimethylacetamide and the like, and one or more kinds selected from the group consisting of amide-based solvents and the like can be used.
• chlorine solvents such as chloroform, dichloromethane, trichloromethane, methylene chloride
• ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, 1,3-dioxolane, N-methylpyrrolidone, dimethylformamide , Dimethylsulfoxide, dimethylacetamide and the like, and one or more kinds selected from the group consisting of amide-
• the dispersibility (familiarity) of the polymer particles correlates with the value of viscosity.
• the polymer particles of the present invention have a surfactant content having a polyoxyalkylene chain having an SP value of 9.0 to 12.0 of 1.0 ⁇ 10 -3 to 6.0 per unit surface area of the polymer particles.
• the amount of the surfactant having an SP value of 9.0 to 12.0 and having no polyoxyalkylene chain is 5.0 ⁇ 10 -5 to 13.0 ⁇ 10 -5 g, which is ⁇ 10 -3 g / m 2. It is / m 2 , and the amount of surface residue of the non-volatile component is 2.0 ⁇ 10 -3 g / m 2 or less.
• the dispersibility in the resin composition is determined.
• the particles become compatible with the solvent, they are uniformly dispersed and the viscosity value increases, reaching the maximum peak (A value) at a certain time.
• Stabilization of familiarity narrows the dispersion region again and reduces the viscosity value.
• B value stable value
• the maximum peak value (A value) of viscosity, the stable value (B value) of viscosity, and the time h (hr) until the viscosity stabilizes are the following formulas (5) and (6).
• the A value, B value and h were specifically obtained by the following measurement methods.
• I 0.50 g of polymer particles are placed in a 50 cc sample bottle, and 5.0 g of toluene is added. Then, it is dispersed for 5 minutes using an ultrasonic cleaner.
• Ii 0.3 g of an acrylic resin (“Acrydic® A-814” manufactured by DIC Corporation) is added, and then dispersed for 5 minutes using an ultrasonic cleaner to prepare a sample.
• the viscosity of the prepared sample is measured at 10-minute intervals until the rate of change in viscosity is less than 3%. Of the measured viscosities, the maximum peak value is defined as the A value. The value of viscosity (stable value) when the rate of change in viscosity is less than 3% and the viscosity is stable is defined as the B value. Let h be the time until the viscosity stabilizes.
• the optical member of the present invention has a layer of the resin composition on a base material.
• a layer of the resin composition can be formed by applying the resin composition containing the polymer particles of the present invention and a resin binder onto a base material.
• the optical member include a light diffusing film or an antiglare film for light diffusion or antiglare.
• the base material is preferably transparent.
• the transparent substrate include glass, polyester-based polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose (TAC), polycarbonate-based polymers, and polymethyl.
• (Meta) acrylic polymers such as methacrylate, styrene polymers such as polystyrene and acrylonitrile / styrene copolymers, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, olefin polymers such as ethylene / propylene copolymers , Vinyl chloride polymer, amide polymer such as nylon and aromatic polyamide, polyimide polymer, polysulfone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenyl sulfide polymer Combined, vinyl alcohol-based polymer, vinylidene chloride-based polymer, vinyl butyral-based polymer, allylate-based polymer, polyoxymethylene-based polymer, epoxy-based polymer, mixture containing at least one of these polymers, A laminate of these polymers or the like can be used as a base material.
• an easy-adhesion layer such as (meth) acrylic resin, copolymerized polyester resin, polyurethane resin, styrene-maleic acid graft polyester resin, acrylic graft polyester resin, etc. is provided on at least one surface of these base materials.
• the provided material can be used as a base material.
• the thickness of the base material can be appropriately determined, but is generally in the range of 10 to 500 ⁇ m in terms of strength, workability such as handling, thin layer property, and the like. It can be preferably 20 to 300 ⁇ m, more preferably 30 to 200 ⁇ m.
• the base material may contain additives.
• the additive examples include an ultraviolet absorber, an infrared absorber, an antistatic agent, a refractive index adjuster, an enhancer and the like.
• the method of applying the resin composition onto the substrate is not particularly limited.
• known coating methods such as bar coat, blade coat, spin coat, reverse coat, die coat, spray coat, roll coat, gravure coat, micro gravure coat, lip coat, air knife coat, and dip coat method can be used. can.
• the resin composition When the resin binder contained in the resin composition has ionizing radiation curability, the resin composition is applied to form a layer of the resin composition on the substrate, and then the resin binder is irradiated with active energy rays to dry. Can be cured.
• active energy rays include ultraviolet rays and infrared rays emitted from light sources such as LEDs, xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps, and Cockcroft Walton, usually 20 to 2000 KeV.
• the layer thickness (dry thickness) of the resin composition is not particularly limited, and is appropriately determined by the particle size of the polymer particles. For example, it can be 1 to 10 ⁇ m, preferably 3 to 7 ⁇ m.
• the polymer particles of the present invention can be used alone or mixed with other resins to prepare a resin molded product by various molding methods.
• a transparent resin can be preferably used, and the polymer particles can function as light diffusing particles in the resin molded body.
• the resin molded body functions as a light diffuser such as a light diffuser and can be used as an LED lighting cover or the like.
• the transparent resin is selected from the group consisting of, for example, (meth) acrylic resin, polycarbonate resin, polystyrene resin, (meth) acrylic-styrene resin (copolymer of (meth) acrylic) acid ester and styrene) and the like.
• One or more types can be used. Among them, polystyrene resin or (meth) acrylic-styrene resin is preferable.
• the amount of the polymer particles contained in the resin molded product is in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the transparent resin. It can be preferably in the range of 0.1 to 5 parts by mass.
• the resin molded product may contain additives such as an ultraviolet absorber, an antioxidant, a heat stabilizer, a light stabilizer, and a fluorescent whitening agent, if necessary.
• the thickness and shape of the resin molded product can be appropriately selected depending on the intended use.
• the resin molded product can be obtained by melt-kneading the transparent resin and the polymer particles with a single-screw extruder, a twin-screw extruder or the like. Further, the resin composition obtained by melt-kneading may be molded into a plate shape via a T die and a roll unit to obtain a resin molded product. Further, the resin composition obtained by melt-kneading may be pelletized, and the pellet may be molded by injection molding, press molding or the like to obtain a resin molded product.
• the resin molded product containing the polymer particles of the present invention is excellent in the dispersion uniformity of the polymer particles, and exhibits optical characteristics such as uniform light diffusivity and antiglare property without unevenness.
• 0.1 g of polymer particles were placed in 10 ml of a 0.1 mass% nonionic surfactant aqueous solution in a touch mixer (manufactured by Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31") and an ultrasonic cleaner ("TOUCHMIXER MT-31").
• a dispersion obtained by dispersing using "ULTRASONIC CLEANER VS-150" manufactured by Vervocrea Co., Ltd. is used.
• the beaker is gently stirred so that no bubbles enter, and the measurement is completed when 100,000 polymer particles are measured.
• the volume average particle size of the polymer particles is an arithmetic mean in the volume-based particle size distribution of 100,000 particles.
• Coefficient of variation of particle size (CV value) The coefficient of variation (CV value) of the particle size of the polymer particles is calculated by the following formula.
• Coefficient of variation (CV value) of particle size of polymer particles (standard deviation of particle size distribution based on volume of polymer particles ⁇ volume average particle size of polymer particles) ⁇ 100
• volume average particle size of seed particles The volume average particle size of the seed particles used in the production of the polymer particles is measured using a laser diffraction / scattering type particle size distribution measuring device (“LS 13 320” manufactured by Beckman Coulter, Inc.) and a universal liquid sample module.
• LS 13 320 manufactured by Beckman Coulter, Inc.
• a sample for measurement 0.1 g of a slurry containing seed particles was put into 10 ml of a 0.1 mass% nonionic surfactant aqueous solution with a touch mixer (manufactured by Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31") and ultrasonic cleaning.
• a dispersion obtained by dispersing using a vessel (“ULTRASONIC CLEANER VS-150” manufactured by Vervocreer Co., Ltd.) is used.
• the measurement was performed in a state where the seed particles were dispersed by performing pump circulation in the universal liquid sample module and in a state where the ultrasonic unit (ULM ULTRASONIC MODULE) was activated, and the volume average particle size (volume average particle size) of the seed particles ( Calculate the arithmetic mean diameter in the volume-based particle size distribution).
• the measurement conditions are shown below.
• the content of the surfactant in the polymer particles is measured by extracting the polymer particles with a solvent and using a liquid chromatograph mass spectrometer (LC / MS / MS apparatus).
• LC / MS / MS apparatus As the LC / MS / MS apparatus, "UHPLC ACCELA” manufactured by Thermo Fisher Scientific and “Linear Ion Trap LC / MSn LXQ” manufactured by Thermo Fisher Scientific were used.
• Examples 1 to 17 and Comparative Examples 1 to 10 were used as surfactants.
• POSPS Plysurf AL (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) ⁇ Polyoxyethylene styrenated phenyl ether phosphoric acid ester
• POELE Prysurf A210G (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) ⁇ Polyoxyethylene lauryl ether phosphoric acid ester
• Approximately 0.10 g of polymer particles as a sample are precisely weighed in a centrifuge tube, and 5 ml of methyl alcohol as an extract is poured with a whole pipette to mix the polymer particles and the extract well. After ultrasonic extraction at room temperature for 15 minutes, centrifugation is performed at a rotation speed of 3500 rpm for 15 minutes, and the supernatant obtained by this is used as a test solution.
• the surfactant concentration in this test solution is measured using an LC / MS / MS device. Then, the concentration of the surfactant in the measured test solution ( ⁇ g / ml), the mass of the polymer particles used as the sample (sample mass (g)), and the amount of the extract (extract amount (ml)). Therefore, the content ( ⁇ g / g) of the surfactant in the polymer particles is determined by the following formula. The amount of the extract is 5 ml.
• Surfactant content ( ⁇ g / g) ⁇ Concentration of surfactant in test solution ( ⁇ g / ml) x amount of extract (ml) ⁇ ⁇ sample mass (g)
• the surfactant concentration is calculated from the calibration curve prepared in advance from the peak area value on the obtained chromatogram using an LC / MS / MS apparatus.
• a calibration line is prepared for each of the surfactants, and the surfactant concentration is calculated from the prepared calibration lines, and each of the calculated ones.
• the total surfactant concentration of the surfactant is defined as the "surfactant concentration in the test solution ( ⁇ g / ml)" in the above formula, and the content of the surfactant in the polymer particles is determined.
• the method of creating the calibration curve is as follows.
• ⁇ Calibration curve of surfactant having polyoxyethylene chain> For example, in the case of polyoxyethylene nonylphenyl ether phosphoric acid, after preparing an intermediate standard solution (methyl alcohol solution) of about 1000 ppm of polyoxyethylene nonylphenyl ether phosphate, it is further diluted stepwise with methyl alcohol to 0.1 ppm. , 0.5 ppm, 1.0 ppm, 2.0 ppm, 10.0 ppm, and a standard solution for preparing a calibration line is prepared.
• methyl alcohol solution methyl alcohol solution
• ⁇ Calibration curve of surfactant without polyoxyethylene chain For example, in the case of di (2-ethylhexyl) sulfosuccinic acid, an intermediate standard solution (methyl alcohol solution) of about 1000 ppm of di (2-ethylhexyl) sulfosuccinate is prepared, and then diluted stepwise with methyl alcohol to 0.1 ppm. , 0.2 ppm, 0.5 ppm, 1.0 ppm, 2.0 ppm for preparing standard solutions for preparing calibration lines.
• methyl alcohol solution methyl alcohol solution
• the specific surface area of the polymer particles was measured by the BET method (nitrogen adsorption method) described in ISO 9277 1st edition JIS Z 8830: 2001.
• BET method nitrogen adsorption method
• For the target polymer particles use an automatic specific surface area / pore distribution measuring device (manufactured by Shimadzu Corporation, "Tristar 3000") to measure the BET nitrogen adsorption isotherm, and use the BET multipoint method from the amount of nitrogen adsorption.
• the specific surface area was calculated.
• nitrogen was used as the adsorbent, and the constant volume method was used under the condition of the adsorbate cross-sectional area of 0.162 nm 2.
• nitrogen purging was performed for 20 minutes while heating the container containing the polymer particles at 65 ° C., allowing the container to cool at room temperature, and then heating the container at 65 ° C. This was performed by vacuum degassing until the pressure in the container became 0.05 mmHg or less.
• a centrifuge tube having an inner diameter of 24 mm for example, a centrifuge tube having an inner volume of 50 ml and an inner diameter of 24 mm (manufactured by Thermo Fisher Scientific Co., Ltd., product name "Nargen (registered trademark) 3119-0050").
• a centrifuge tube having an inner diameter of 24 mm for example, a centrifuge tube having an inner volume of 50 ml and an inner diameter of 24 mm (manufactured by Thermo Fisher Scientific Co., Ltd., product name "Nargen (registered trademark) 3119-0050").
• the rotor is set in the Speed refrigerated centrifuge (model number "CR22GII", manufactured by Hitachi Koki Co., Ltd.), and the K factor 6943 (when the angle rotor is used, the rotation speed is 4800 rpm) using the high-speed cooling centrifuge. (Sometimes the K factor is 6943), and after centrifugation under the condition of a rotation time of 30 minutes, the supernatant is collected.
• Quantification of by-products The quantification of the content of by-products contained in 5.0 g of the recovered supernatant was determined as follows. 5.0 g of the supernatant is weighed in a sample bottle having a mass of 10 ml and placed in a vacuum oven at a temperature of 60 ° C. for 5 hours to evaporate the water content. Weigh the evaporatively dried residue, i.e. the mass (g) of the sample bottle containing the non-volatile components.
• the supernatant is determined by the following formula.
• the concentration (mass%) of the non-volatile component (corresponding to the by-product (emulsified polymerization product)) in the liquid was calculated.
• the gel fraction of the polymer particles indicates the degree of cross-linking of the polymer particles, and is measured by the following method. 1.0 g of polymer particles as a sample and 0.03 g of boiling stone were precisely weighed and put into a 200 ml eggplant flask, and 100 ml of toluene was further poured, and then a cooling tube was attached to the eggplant flask to make 130. Immerse the eggplant flask in an oil bath kept at ° C and reflux for 24 hours. After refluxing, the contents (dissolved solution) in the eggplant flask were weighed by attaching ADVANTEC glass fiber filters "GB-140 ( ⁇ 37 mm)" and "GA-200 ( ⁇ 37 mm)".
• Filtration is performed using a Büchner funnel type filter 3G (glass particle pore diameter 20 to 30 ⁇ m, capacity 30 mL), and solid content is recovered in the Büchner funnel type filter 3G. Then, the solid content recovered in the Büchner funnel type filter 3G is dried together with the Büchner funnel type filter 3G in a vacuum oven at 130 ° C. for 1 hour, and then dried at a gauge pressure of 0.06 MPa for 2 hours to toluene. Remove and cool to room temperature. After cooling, the total mass of the Büchner funnel type filter 3G, the glass fiber filter, and the solid content is measured with the solid content contained in the Büchner funnel type filter 3G.
• a Büchner funnel type filter 3G glass particle pore diameter 20 to 30 ⁇ m, capacity 30 mL
• a resin composition was prepared using the polymer particles obtained in Examples 1 to 17 and Comparative Examples 1 to 10. The resin composition was applied to one side of a transparent polyester film so as to have a dry coating film of X ⁇ m to prepare an optical film. An optical film cut into a 6 cm x 6 cm square is used as a test piece, and each of the four end portions and the center portion (five locations in total) on the top, bottom, left, and right of the surface coated with the resin composition for coating the test piece. Haze is measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., "NDH-4000") according to JIS K 7136. Then, using the maximum value, the minimum value, and the average value of the haze (%) at the five measured points, the haze difference (%) is calculated by the following formula, and the haze difference (%) is evaluated as follows. Evaluated by criteria.
• [Production example of seed particles] [Production example 1 of seed particles] In a separable flask equipped with a stirrer, a thermometer and a reflux condenser, 1300 g of water as an aqueous medium, 70 g of methyl methacrylate as a (meth) acrylic acid ester-based monomer, and n-octyl as a molecular weight adjuster. 0.70 g of mercaptan was charged, and the inside of the separable flask was replaced with nitrogen while stirring the contents of the separable flask, and the internal temperature of the separable flask was raised to 70 ° C.
• an aqueous solution prepared by dissolving 0.35 g of potassium persulfate as a polymerization initiator in 50 g of water was added to the contents in the separable flask, and then polymerization was carried out for 5 hours. It was reacted. Then, 256 g of methyl methacrylate and 2.56 g of n-octyl mercaptan as a molecular weight adjuster were newly charged, put into the polymerization reaction solution, and then the inside of the separable flask was replaced with nitrogen again to change the internal temperature of the separable flask. Was heated to 70 ° C.
• an aqueous solution prepared by dissolving 1.28 g of potassium persulfate as a polymerization initiator in 50 g of water was added to the contents of the separable flask, and then the polymerization reaction was carried out for 12 hours. I let you.
• the reaction solution after the polymerization was filtered through a wire mesh of 400 mesh (opening 32 ⁇ m) to prepare a slurry containing 20% by mass of seed particles (referred to as seed particles (1)) made of polymethyl methacrylate as a solid content.
• seed particles (1) contained in this slurry were spherical particles having a volume average particle diameter of 0.54 ⁇ m.
• an aqueous solution prepared by dissolving 2.0 g of potassium persulfate as a polymerization initiator in 60 g of water was added to the contents in the reactor, and then the polymerization reaction was carried out for 12 hours. rice field.
• the reaction solution after the polymerization was filtered through a wire mesh of 400 mesh (opening 32 ⁇ m) to prepare a slurry containing 20% by mass of seed particles made of polymethyl methacrylate (hereinafter referred to as seed particles (2)) as solid content. ..
• seed particles (2) contained in this slurry were spherical particles having a volume average particle diameter of 1.02 ⁇ m.
• an aqueous solution prepared by dissolving 5.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in 60 g of water was added to the reactor. After being added to the contents, it was polymerized for 12 hours. Then, the internal temperature of the reactor was raised to 70 ° C., and the reaction was carried out for 1 hour and 30 minutes.
• the reaction solution after the polymerization was filtered through a wire mesh of 400 mesh (opening 32 ⁇ m) to prepare a slurry containing 20% by mass of seed particles made of polymethyl methacrylate (hereinafter referred to as seed particles (3)) as solid content. ..
• the seed particles (3) contained in this slurry were spherical particles having a volume average particle diameter of 2.30 ⁇ m.
• Example 1 [Production of Polymer Particles: Example 1]
• MMA methyl methacrylate
• St styrene
• EGDMA ethylene glycol methacrylate
• 2,4-dimethylvaleronitrile polymerization initiator 9.7 g are dissolved.
• a body mixture was prepared. Solubility of di (2-ethylhexyl) sodium sulfosuccinate (manufactured by Nichiyu Co., Ltd., product name "Lapisol (registered trademark) A-80", solubility in water at a liquid temperature of 25 ° C.
• sodium polyoxyethylene nonylphenyl ether phosphate manufactured by Toho Chemical Co., Ltd., product name "Phosphanol (registered trademark) LO-529"; anionic surfactant having a polyoxyalkylene chain
• 2250 g of an aqueous solution in which 15 g was dissolved was added as a minute, and then the polymerization reaction was carried out by stirring at 75 ° C. for 4 hours and then at 100 ° C. for 1.5 hours to obtain a slurry of polymer particles.
• Example 2 As an anionic surfactant (other surfactant) having no polyoxyalkylene chain, 10 g of sodium alkenyl succinate was used as a pure content. In the drying step, the degree of vacuum was ⁇ 0.100 MPa and the stirring share coefficient was 2441. Except for the above, the target polymer particles were obtained in the same manner as in Example 1.
• Example 3 The solid-liquid separation step was carried out until 79% of the charged water was recovered as a filtrate. In the drying step, the degree of vacuum was set to ⁇ 0.05 MPa and the stirring share coefficient was set to 1983. Except for the above, the target polymer particles were obtained in the same manner as in Example 1.
• Example 4 The monomer composition was methyl methacrylate (MMA) 300 g, styrene (St) 200 g, ethylene glycol methacrylate (EGDMA) 300 g, and polyethylene glycol-propylene glycol-monomethacrylate 45 g.
• MMA methyl methacrylate
• St styrene
• EGDMA ethylene glycol methacrylate
• an anionic surfactant having a polyoxyalkylene chain 15 g of polyoxyethylene styrenated phenyl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Plysurf AL") was used as a pure content.
• the solid-liquid separation step was carried out until 79% of the charged water was recovered as a filtrate.
• the operation of the washing step was repeated 3 times.
• Example 5 The monomer composition was methyl methacrylate (MMA) 300 g, styrene (St) 200 g, ethylene glycol methacrylate (EGDMA) 300 g, and polyethylene glycol-propylene glycol-monomethacrylate 45 g.
• MMA methyl methacrylate
• St styrene
• EGDMA ethylene glycol methacrylate
• an anionic surfactant having a polyoxyalkylene chain 15 g of polyoxyethylene lauryl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Plysurf A210G") was used as a pure content. Except for the above, the target polymer particles were obtained in the same manner as in Example 1.
• the monomer composition was methyl methacrylate (MMA) 300 g, styrene (St) 200 g, ethylene glycol methacrylate (EGDMA) 300 g, and polyethylene glycol-propylene glycol-monomethacrylate 45 g.
• MMA methyl methacrylate
• St styrene
• EGDMA ethylene glycol methacrylate
• polyethylene glycol-propylene glycol-monomethacrylate 45 g As an anionic surfactant (other surfactant) having no polyoxyalkylene chain, 25 g of sodium di (2-ethylhexyl) sulfosuccinate was used as a pure content.
• an anionic surfactant having a polyoxyalkylene chain 15 g of polyoxyethylene alkyl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Prysurf A208F") was used as a pure content.
• the filtration rate was set to 0.200 [kg / min ⁇ m 2 ].
• the target polymer particles were obtained in the same manner as in Example 1.
• Example 7 The monomer composition was 900 g of styrene (St) and 108 g of divinylbenzene (DVB).
• St styrene
• DVD divinylbenzene
• an anionic surfactant having a polyoxyalkylene chain 15 g of polyoxyethylene styrenated phenyl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Plysurf AL”) was used as a pure content. Except for the above, the target polymer particles were obtained in the same manner as in Example 1.
• Example 8 As an anionic surfactant having a polyoxyalkylene chain, 35 g of polyoxyethylene styrenated phenyl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Plysurf AL”) was used as a pure content. In the solid-liquid separation step, the liquid removal rate was set to 0.070 [kg / min ⁇ m 2 ], and 80% of the charged water was recovered as a filtrate. In the washing step, the filtration rate was set to 0.200 [kg / min ⁇ m 2 ]. Except for the above, the target polymer particles were obtained in the same manner as in Example 1.
• Example 9 In the solid-liquid separation step, the liquid removal rate was set to 0.030 [kg / min ⁇ m 2 ], and the process was carried out until 83% of the charged water was recovered as a filtrate. In the washing step, the filtration rate was set to 0.035 [kg / min ⁇ m 2 ]. In the drying step, the degree of vacuum was ⁇ 0.100 MPa and the stirring share coefficient was 2056. Except for the above, the target polymer particles were obtained in the same manner as in Example 1.
• Example 10 The slurry of the seed particles was used as the slurry of the seed particles (2) obtained in Production Example 2 of the seed particles, and the amount used was 6.3 g as the solid content (seed particles).
• the monomer composition was 560 g of methyl methacrylate (MMA) and 300 g of ethylene glycol methacrylate (EGDMA).
• MMA methyl methacrylate
• EGDMA ethylene glycol methacrylate
• an anionic surfactant (other surfactant) having no polyoxyalkylene chain 5 g of sodium di (2-ethylhexyl) sulfosuccinate was used as a pure content.
• the washing step the filtration rate was set to 0.085 [kg / min ⁇ m 2 ].
• the degree of vacuum was ⁇ 0.060 MPa and the stirring share coefficient was 2030. Except for the above, the target polymer particles were obtained in the same manner as in Example 1.
• Example 11 The slurry of the seed particles (1) was used as the slurry of the seed particles (3) obtained in Production Example 3 of the seed particles, and the amount used was 4.7 g as the solid content (seed particles).
• the monomer composition was 560 g of methyl methacrylate (MMA) and 300 g of ethylene glycol methacrylate (EGDMA).
• MMA methyl methacrylate
• EGDMA ethylene glycol methacrylate
• an anionic surfactant having a polyoxyalkylene chain 20 g of polyoxyethylene styrenated phenyl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Plysurf AL”) was used as a pure content.
• the degree of vacuum was ⁇ 0.060 MPa
• the drying time was 9 hours
• stirring share coefficient was 2579. Except for the above, the target polymer particles were obtained in the same manner as in Example 10.
• Example 12 As an anionic surfactant (other surfactant) having no polyoxyalkylene chain, 15 g of sodium lauryl sulfate was used as a pure content. In the drying step, the stirring share coefficient was set to 2545. Except for the above, the target polymer particles were obtained in the same manner as in Example 11.
• Example 13 As an anionic surfactant (other surfactant) having no polyoxyalkylene chain, 15 g of sodium lauryl sulfate was used as a pure content. As an anionic surfactant having a polyoxyalkylene chain, 13 g of polyoxyethylene lauryl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Plysurf A210G”) was used as a pure content. In the drying step, the stirring share coefficient was set to 2709. Except for the above, the target polymer particles were obtained in the same manner as in Example 11.
• Example 14 As an anionic surfactant having a polyoxyalkylene chain, 15 g of glyceryl polyoxyethylene caprylate was used as a pure content. In the drying step, the stirring share coefficient was set to 2673. Except for the above, the target polymer particles were obtained in the same manner as in Example 11.
• Example 15 As an anionic surfactant having a polyoxyalkylene chain, 13 g of polyoxyethylene styrenated phenyl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Plysurf AL”) was used as a pure content. In the solid-liquid separation step, the deliquescent rate was set to 0.065 [kg / min ⁇ m 2 ], and 80% of the charged water was recovered as a filtrate. In the washing step, the filtration rate was set to 0.150 [kg / min ⁇ m 2 ]. Except for the above, the target polymer particles were obtained in the same manner as in Example 1.
• Example 16 As an anionic surfactant having a polyoxyalkylene chain, 35 g of polyoxyethylene styrenated phenyl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Plysurf AL”) was used as a pure content. In the solid-liquid separation step, the liquid removal rate was set to 0.070 [kg / min ⁇ m 2 ], and 80% of the charged water was recovered as a filtrate. In the washing step, water at 60 ° C., which was twice the amount of the polymer particles, was supplied as a washing liquid and immersed for 0.5 hours. In the drying step, the stirring share coefficient was set to 2376. Except for the above, the target polymer particles were obtained in the same manner as in Example 1.
• Example 17 As an anionic surfactant having a polyoxyalkylene chain, 35 g of polyoxyethylene styrenated phenyl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Plysurf AL”) was used as a pure content. In the solid-liquid separation step, the deliquescent rate was set to 0.055 [kg / min ⁇ m 2 ], and 80% of the charged water was recovered as a filtrate.
• Plysurf AL polyoxyethylene styrenated phenyl ether phosphoric acid ester
• the washing step water at 60 ° C., which was twice the amount of the polymer particles, was supplied as a washing liquid and immersed for 0.5 hours to set the filtration rate to 0.085 [kg / min ⁇ m 2 ].
• the degree of vacuum was set to ⁇ 0.055 MPa and the stirring share coefficient was set to 2344.
• the target polymer particles were obtained in the same manner as in Example 1.
• Example 2 To the composition of Example 1, 45 g of polyethylene glycol-propylene glycol-monomethacrylate, which is a hydrophilic monomer, was added. In the solid-liquid separation step, the deliquescent rate was set to 0.100 [kg / min ⁇ m 2 ], and 80% of the charged water was recovered as a filtrate. In the washing step, the filtration rate was set to 0.300 [kg / min ⁇ m 2 ]. In the drying step, the stirring share coefficient was set to 2553. Other than that, the target polymer particles were obtained in the same manner as in Comparative Example 1.
• the monomer composition was methyl methacrylate (MMA) 300 g, styrene (St) 200 g, ethylene glycol methacrylate (EGDMA) 300 g, and polyethylene glycol-propylene glycol-monomethacrylate 45 g.
• MMA methyl methacrylate
• St styrene
• EGDMA ethylene glycol methacrylate
• polyethylene glycol-propylene glycol-monomethacrylate 45 g As an anionic surfactant (other surfactant) having no polyoxyalkylene chain, 35 g of di (2-ethylhexyl) sodium sulfosuccinate was used as a pure content.
• an anionic surfactant having a polyoxyalkylene chain 15 g of polyoxyethylene styrenated phenyl ether phosphoric acid ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "Plysurf AL") was used as a pure content. Except for the above, the target polymer particles were obtained in the same manner as in Example 1.
• Example 1 to 17 and Comparative Examples 1 to 10 the volume average particle diameter, CV value, gel fraction, specific surface area of the obtained polymer particles, the type and SP value of each surfactant, and the unit of the polymer particles.
• Tables 2 to 4 show the amount of each surfactant per surface area, the amount of non-volatile components per unit surface area of the polymer particles, the viscosity measurement result, the dispersibility, the time until uniform dispersion, and the optical characteristics.
• DSS Lapizol A-80 (manufactured by NOF CORPORATION) ⁇ Di (2-ethylhexyl) sodium sulfosuccinate ii: ASK: Sodium alkenyl succinate iii: RSN: Sodium Lauryl Sulfate iv: PAI: Isopropyl palmitate v: TOS: Sorbitan trioleate

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