JP5844889B2 - POLYMER PARTICLE, PROCESS FOR PRODUCING THE SAME, AND USE THEREOF - Google Patents

Description

  The present invention relates to polymer particles and a method for producing the same. More specifically, the present invention relates to polymer particles having a surface porous structure and a method for producing the same. Further, the present invention provides a use of the polymer particles, specifically, an external preparation such as cosmetics containing the polymer particles, a paint containing the polymer particles, and a light diffusing resin containing the polymer particles. It also relates to a composition.

  The polymer particles having an average particle diameter of 0.01 to 100 μm include, for example, paints, additives for ink pressure-sensitive adhesives, adhesives, artificial marbles, fillers for paper processing agents, cosmetics, etc. It is used for applications such as chromatography column packing materials, toner additives used for electrostatic image development, anti-blocking agents for films, and light diffusing agents. Among them, polymer particles having a porous structure on the surface are used for the purpose of their adsorption characteristics, sustained release, improvement in tactile sensation, adjustment of viscosity, improvement in light diffusibility, and the like.

  For example, in Patent Documents 1 and 2, as a technique for obtaining polymer particles having a porous structure, when polymer particles are formed from a mixture containing an unsaturated monomer and a linear polymer compound, polymerization is performed. As the process progresses, the compatibility between the polymer produced by the polymerization of the unsaturated monomer and the linear polymer compound gradually decreases, and a mechanism for partially forming a phase separation state in the polymer particles The technology used is disclosed. The polymer particles obtained by the techniques disclosed in Patent Documents 1 and 2 are particles having a porous structure having a large number of pores both inside and on the surface of the polymer particles. , Give the cosmetics a unique feel derived from the porous structure.

JP-A-10-60011 JP 2003-81738 A

  As described above, polymer particles having a porous structure, in particular, polymer particles having a surface porous structure having a plurality of pores on the surface, have various characteristics derived from the porous structure. Development of a polymer particle having a new surface porous structure that can have unique characteristics that have never existed or that has superior characteristics as compared to conventional techniques has been underway.

  The present invention has been made in view of the above situation, and aims to provide a polymer particle having a novel surface porous structure having a plurality of pores on the surface, and a method for producing the polymer particle. To do.

  Another object of the present invention is to provide an external preparation, a paint, and a resin composition containing polymer particles having a novel surface porous structure having a plurality of pores on the surface.

The polymer particles according to the present invention include a vinyl polymer derived from a monomer mixture containing 100 parts by weight of a monofunctional vinyl monomer and 5 to 100 parts by weight of a polyfunctional vinyl monomer, and C3 to C20. 1 to 15.4 parts by weight of a non-crosslinked polymer having a weight average molecular weight of 50,000 to 200,000 derived from a monomer containing 50% by weight or more of an alkyl (meth) acrylate having a branched alkyl group of It has a surface porous structure having a plurality of pores of ˜2 μm on the surface, has a specific surface area of 0.1-5.0 m ² / g, and a volume average particle size of 1-200 μm. In the present specification, “(meth) acryl” means “methacryl” or “acryl”.

Alternatively, the polymer particle according to the present invention is a polymer particle having a surface porous structure having a plurality of pores on its surface, and includes a vinyl polymer and a non-crosslinked polymer, and the non-crosslinked polymer And the vinyl polymer phase-separated, and the polymer particles have a sea-island structure in which the phase composed of the non-crosslinked polymer is dispersed in the phase composed of the vinyl polymer and exists on the surface The plurality of holes have a center diameter of 0.1 to 2 μm, a specific surface area of 0.1 to 5.0 m ² / g, and a volume average particle diameter of 1 to 200 μm.

Moreover, the manufacturing method of the polymer particle which concerns on this invention is a C3-C20 monomer mixture containing 100 weight part of monofunctional vinyl monomers, and 5-100 weight parts of polyfunctional vinyl monomers. An aqueous medium in the presence of 1 to 15.4 parts by weight of a non-crosslinked polymer having a weight average molecular weight of 50,000 to 200,000 derived from a monomer containing 50% by weight or more of an alkyl (meth) acrylate having a branched alkyl group and a polymerization initiator It has a surface porous structure having a plurality of pores with a central diameter of 0.1 to 2 μm on its surface by suspension polymerization in the inside, a specific surface area of 0.1 to 5.0 m ² / g, and a volume average particle Polymer particles having a diameter of 1 to 200 μm are obtained.

  Moreover, the external preparation which concerns on this invention is characterized by including the polymer particle which concerns on above-described this invention.

  Moreover, the coating material which concerns on this invention is characterized by including the polymer particle which concerns on above-described this invention.

  The light diffusing resin composition according to the present invention includes the above-described polymer particles according to the present invention and a transparent base resin.

  ADVANTAGE OF THE INVENTION According to this invention, the polymer particle of the novel surface porous structure which has a some hole on the surface, and its manufacturing method can be provided. Furthermore, an external preparation, a coating material, and a light diffusing resin composition containing novel polymer particles having a plurality of pores on the surface can be provided.

FIG. 1 is a scanning electron microscope (SEM) image of polymer particles according to Example 1 of the present invention. FIG. 2 is a transmission electron microscope (TEM) image of the polymer particles according to Example 1 of the present invention. FIG. 3 is a transmission electron microscope (TEM) image of particles obtained by extracting a non-crosslinked polymer from the polymer particles according to Example 1 of the present invention. FIG. 4 is a scanning electron microscope (SEM) image of the polymer particles according to Example 2 of the present invention. FIG. 5 is a scanning electron microscope (SEM) image of polymer particles according to Example 3 of the present invention. FIG. 6 is a scanning electron microscope (SEM) image of polymer particles according to Example 4 of the present invention. FIG. 7 is a scanning electron microscope (SEM) image of polymer particles according to Example 6 of the present invention. FIG. 8 is a scanning electron microscope (SEM) image of polymer particles according to Example 7 of the present invention. FIG. 9 is a scanning electron microscope (SEM) image of polymer particles according to Comparative Example 6.

[Polymer particles of the present invention and production method thereof]
The polymer particle of the present invention is a particle having a surface porous structure having a plurality of pores having a central diameter of 0.1 to 2 μm on the surface. This polymer particle of the present invention comprises a vinyl polymer and a non-crosslinked polymer, has a specific surface area of 0.1 to 5.0 m ² / g, and has a volume average particle diameter of 1 to 200 μm. Have.

  Specifically, the polymer particles of the present invention have a plurality of pores on the surface, and the surface porous structure in which the center diameter of these pores is 0.1 to 2 μm, preferably 0.5 to 1.5 μm. Is provided. When the pore center diameter is outside the range of 0.1 to 2 μm, the effect of having a porous structure on the surface of the polymer particles (for example, the viscosity characteristics of the paint when the polymer particles are blended with the paint) Dispersion characteristics when polymer particles are blended with products such as paints and cosmetics, and light of products when polymer particles are blended with products such as paints, cosmetics, and light diffusing films (light diffusing resin compositions) There is a possibility that the diffusibility and the tactile sensation when polymer particles are blended into cosmetics and the like cannot be obtained. In the present specification, the center diameter of the pore means a mode diameter (mode) of pore distribution measured by a mercury intrusion method, for example, a center diameter measuring method described later in the section of the examples. And

The specific surface area of the polymer particles is 0.1 to 5.0 m ² / g, preferably 1.0 to 5.0 m ² / g. If the specific surface area is less than 0.1 m ² / g, the effect of having a porous structure on the surface of the polymer particles may not be exhibited. Here, the specific surface area refers to the surface area per unit weight, and in the present invention means the specific surface area obtained by the BET method (N ₂ ). The method for measuring the specific surface area by the BET method (N ₂ ) will be described in the Examples section.

  The volume average particle diameter of the polymer particles of the present invention is 1 to 200 μm. Depending on the use of the polymer particles, 1 to 150 μm is preferable, and 2 to 100 μm is more preferable.

  The polymer particles of the present invention have a plurality of pores on the surface, the viscosity characteristics of the paint when the polymer particles are blended with the paint, and the polymer particles when blended with products such as paints and cosmetics. Dispersion characteristics, light diffusibility of products when polymer particles are blended with products such as paints, cosmetics, and light diffusing films (light diffusing resin compositions), touch when polymer particles are blended with cosmetics, etc. Is excellent. In particular, the polymer particles having a surface porous structure according to the present invention mainly have a large number of pores on the surface and no pores inside (or a small number of pores inside). From the conventional porous structure polymer particles having a large number of pores both on the surface and inside, the viscosity characteristics of the paint when the polymer particles are blended into the paint, the polymer particles as paint, cosmetics, etc. Excellent dispersion characteristics when blended with products.

  The polymer particles of the present invention have a sea-island structure in which a non-crosslinked polymer and a vinyl polymer are phase-separated and a phase composed of the non-crosslinked polymer is dispersed in a phase composed of the vinyl polymer. It is preferable to have inside the particles. Specifically, the interior of the polymer particles of the present invention is composed of a phase composed of a non-crosslinked polymer and a phase composed of a vinyl polymer, and the internal structure of the polymer particles is It is preferable to have a sea-island structure in which a phase (dispersed phase) composed of a non-crosslinked polymer is dispersed in the form of particles in a phase composed of a polymer (continuous phase). Since the inside of such polymer particles is in a state in which materials having different optical refractive indexes (that is, non-crosslinked polymer and vinyl polymer) are mixed, this polymer particle can be used in paints, cosmetics, light diffusing properties. When blended in a product such as a film (light diffusing resin composition), a light diffusivity specific to the product can be expressed. Here, the length of the phase composed of the non-crosslinked polymer is preferably 50 to 3000 nm, and more preferably in the range of 50 to 1000 nm. If the length of the phase composed of the non-crosslinked polymer is not within the range of 50 to 3000 nm, the dispersion of the phase composed of the non-crosslinked polymer in the phase composed of the vinyl polymer is not sufficient, and the photorefractive index There is a possibility that the effect of improving the light diffusibility due to the mixture of different materials (that is, non-crosslinked polymer and vinyl polymer) is not sufficiently exhibited.

  As described above, the polymer particles of the present invention contain a vinyl polymer that is a polymer of a vinyl monomer. The vinyl monomer is a compound having at least one alkenyl group (broadly defined vinyl group). The vinyl monomer includes a monofunctional vinyl monomer that is a compound having one alkenyl group (vinyl group) and a polyfunctional vinyl that is a compound having two or more alkenyl groups (vinyl group). There are system monomers. The polymer particles of the present invention are polymers derived from a monomer mixture containing a monofunctional vinyl monomer and a polyfunctional vinyl monomer, that is, a monofunctional vinyl monomer and a polyfunctional vinyl monomer. It is preferable that a crosslinked polymer which is a copolymer with a monomer is included as a vinyl polymer. Thereby, solvent resistance can be provided to polymer particles.

  Examples of the monofunctional vinyl monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p- t-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene, Styrene such as p-chlorostyrene and 3,4-dichlorostyrene and derivatives thereof; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; methyl acrylate, ethyl acrylate, propyl acrylate, n-acrylate Butyl, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-acrylate Tylhexyl, stearyl acrylate, lauryl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacryl N-octyl acid, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, etc. α-methylene aliphatic monocarboxylic acid esters; acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, 2-hydroxyethylene acrylate Le, acrylic acid 2-hydroxypropyl, 2-hydroxyethyl methacrylate, acrylic acid or methacrylic acid derivatives such as 2-hydroxypropyl methacrylate.

  In some cases, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and the like can be used as the monofunctional vinyl monomer. Further, two or more of these may be used in combination. In addition, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl compounds such as N-vinylpyrrolidone; vinyl naphthalene salts and the like can be used as a monofunctional vinyl monomer in combination of one or more kinds within a range not impeding the effects of the present invention.

  Among the monofunctional vinyl monomers described above, (meth) acrylic acid esters are preferable. When the monofunctional vinyl monomer is (meth) acrylic acid ester, the viscosity characteristics of the paint when polymer particles are blended with paint, and the dispersion characteristics when polymer particles are blended with products such as paint and cosmetics Furthermore, when the polymer particles are blended with products such as paints, cosmetics, and light diffusing films (light diffusing resin compositions), the light diffusibility of the products, the tactile sensation when the polymer particles are blended with cosmetics, etc. Can be good.

  Examples of the polyfunctional vinyl monomer include ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinylbenzene, polyfunctional isocyanurate and the like. By using these monomers, crosslinked polymer particles can be obtained.

  In the crosslinked polymer as a vinyl polymer, the ratio of the number of structural units derived from monofunctional vinyl monomers to the number of structural units derived from polyfunctional vinyl monomers is converted to weight. The structural unit derived from the polyfunctional vinyl monomer is preferably in the range of 5 to 100 parts by weight with respect to 100 parts by weight of the structural unit derived from the monofunctional vinyl monomer. More preferably, it is in the range of 10 to 70 parts by weight. When the structural unit derived from the polyfunctional vinyl monomer is 5 parts by weight or more with respect to 100 parts by weight of the structural unit derived from the monofunctional vinyl monomer, the polymer particles have sufficient solvent resistance. Can be granted. On the other hand, when the structural unit derived from the polyfunctional vinyl monomer is 100 parts by weight or less with respect to 100 parts by weight of the structural unit derived from the monofunctional vinyl monomer, a desired surface porous structure is obtained. be able to. The amount of the polymer derived from the monomer contained in the polymer particle (polymer derived from a monomer mixture containing a monofunctional vinyl monomer and a polyfunctional vinyl monomer) The amount of the monomer (monofunctional vinyl monomer and polyfunctional vinyl monomer) added during the production of is substantially equal.

  The polymer particles of the present invention contain a non-crosslinked polymer as described above. In the polymer particles of the present invention, the non-crosslinked polymer has a non-crosslinked polymer (for example, C3 to C20 (3 to 20 carbon atoms) branched alkyl group that is incompatible with the vinyl polymer (crosslinked polymer). It is preferably an alkyl (meth) acrylate homopolymer or copolymer). Such a non-crosslinked polymer that is incompatible with the vinyl polymer (crosslinked polymer) can form a porous structure on the surface of the polymer particles, and is composed of the vinyl polymer inside the polymer particles. A sea-island structure in which the phase composed of the non-crosslinked polymer is dispersed in the phase can be formed.

  The polymer particles according to the present invention are obtained by suspension polymerization of a monomer mixture containing a monofunctional vinyl monomer and a polyfunctional vinyl monomer in an aqueous medium in the presence of a non-crosslinked polymer. By doing so, it can be manufactured.

  Moreover, the surface of the polymer particles of the present invention may be treated with an oil agent, a silicone compound, or a fluorine compound. Thus, when the surface of the polymer particles is treated with an oil agent, a silicone compound, or a fluorine compound, the water repellency of the polymer particles can be improved.

  Examples of oils include hydrocarbon oils such as liquid paraffin, squalane, petrolatum, paraffin wax; lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin Higher fatty acids such as fatty acids and synthetic fatty acids; ester oils such as glyceryl trioctanoate, propylene glycol dicaprate, cetyl 2-ethylhexanoate and isocetyl stearate; waxes such as beeswax, whale wax, lanolin, carnauba wax and candelilla wax; Fats and oils such as linseed oil, cottonseed oil, castor oil, egg yolk oil and coconut oil; metal soaps such as zinc stearate and zinc laurate; higher alcohols such as cetyl alcohol, stearyl alcohol and oleyl alcohol.

  The method of treating the surface of the polymer particles with the oil agent is not particularly limited. For example, a dry method in which the oil agent is coated on the surface of the polymer particles by adding the oil agent to the polymer particles and stirring with a mixer or the like; Is dissolved in a suitable solvent such as ethanol, propanol, ethyl acetate, hexane, etc., and the particles are added thereto and mixed and stirred. Then, the solvent is removed under reduced pressure or removed by heating to coat the surface of the polymer particles with an oil agent. A wet method or the like can be used.

  Examples of the silicone compound include dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, acrylic-silicone graft polymer, and organosilicone resin partially crosslinked organopolysiloxane polymer.

  The method for treating the surface of the polymer particles with the silicone compound is not particularly limited, and for example, the dry method or the wet method described above can be used. In addition, if necessary, a baking treatment may be performed, or in the case of a reactive silicone compound, a reaction catalyst or the like may be added as appropriate.

  Examples of the fluorine compound include perfluoroalkyl group-containing esters, perfluoroalkylsilanes, perfluoropolyethers, polymers having a perfluoro group, and the like.

  A method of treating the surface of the polymer particles with a fluorine compound is not particularly limited, and for example, the dry method or the wet method described above can be used. In addition, if necessary, a baking treatment may be performed, or in the case of a reactive silicone compound, a reaction catalyst or the like may be added as appropriate.

  The polymer particles of the present invention described above include, for example, paint additives (matting agents, coating film softening agents, design imparting agents, etc.), ink additives (matting agents, adhesives, etc.), Main component or additive of adhesive, additive for artificial marble (low shrinkage agent, etc.), filler for paper processing agent, filler for cosmetics (filler for improving slipperiness), etc. Raw materials for external preparations, column fillers for chromatography, additives for toners used for electrostatic image development, anti-blocking agents for films, light diffusers (lighting covers, light diffusion sheets, light diffusion films, etc.) It can be suitably used for applications such as a light diffusing agent.

[Preferred form of polymer particles and production method thereof]
The polymer particles of the present invention include a polymer (vinyl polymer) derived from a monomer mixture containing 100 parts by weight of a monofunctional vinyl monomer and 5 to 100 parts by weight of a polyfunctional vinyl monomer. , A non-crosslinked polymer having a weight average molecular weight of 50,000 to 200,000 derived from a monomer containing 50% by weight or more of an alkyl (meth) acrylate having a branched alkyl group of C3 to C20 (C3 to C20) A form containing parts by weight is particularly preferred.

  The polymer particles of this form can be produced by using a monomer mixture containing a monofunctional vinyl monomer and a polyfunctional vinyl monomer and a non-crosslinked polymer without using an organic solvent. Therefore, the adverse effect due to the presence of the organic solvent in the polymer particles can be reduced. In addition, by including an alkyl (meth) acrylate having a C3-20 branched alkyl group as a non-crosslinked polymer, the viscosity characteristics of the paint when the polymer particles are blended with the paint, the polymer particles can be used in paints, cosmetics, etc. Dispersion characteristics when blended with products, polymer particles into paints, cosmetics, light diffusing films (light diffusing resin compositions), etc., products light diffusibility, polymer particles into cosmetics, etc. Excellent tactile sensation when blended.

  In the monomer mixture forming the vinyl polymer contained in the polymer particles of this embodiment, the ratio of the weight of the monofunctional vinyl monomer to the weight of the polyfunctional vinyl monomer is as described above. The polyfunctional vinyl monomer is in the range of 5 to 100 parts by weight with respect to 100 parts by weight of the monofunctional vinyl monomer. In the vinyl polymer (crosslinked polymer) obtained by polymerizing such a monomer mixture, the number of structural units derived from the monofunctional vinyl monomer and the polyfunctional vinyl monomer The ratio to the number of structural units is approximately equal to the ratio of the weight of the monofunctional vinyl monomer in the monomer mixture to the weight of the polyfunctional vinyl monomer.

  Moreover, in the polymer particle of this form, content of a non-crosslinked polymer is 1-15.4 weight part with respect to 100 weight part of monofunctional vinylic monomers as above-mentioned. The polymer particles whose non-crosslinked polymer content is outside the range of 1 part by weight to 15.4 parts by weight with respect to 100 parts by weight of the monofunctional vinyl monomer may not have a porous structure on the surface. There is.

  In this embodiment, the non-crosslinked polymer is obtained by polymerizing a monomer containing 50% by weight or more, preferably 70 to 90% by weight of an alkyl (meth) acrylate having a C3 to C20 branched alkyl group. . In other words, the number of structural units derived from an alkyl (meth) acrylate having a C3-C20 branched alkyl group contained in the non-crosslinked polymer is the total structure constituting the non-crosslinked polymer in terms of weight. It is 50% by weight or more of the unit, preferably 70 to 90% by weight. Here, as for carbon number of a branched alkyl group, it is more preferable that it is 4-18. Examples of the alkyl (meth) acrylate having a C3 to C20 branched alkyl group include isobutyl methacrylate, isobutyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isostearyl acrylate, methacrylic acid. Examples include acid isostearyl.

  If the said monomer which forms a non-crosslinked polymer is less than 50 weight%, it may contain polymeric components other than the alkyl (meth) acrylate which has a branched alkyl group. Examples of such a polymerizable component include acrylic acid or methacrylic acid derivatives having a linear alkyl group, such as methyl methacrylate, butyl methacrylate, and butyl acrylate.

  In this embodiment, the weight average molecular weight of the non-crosslinked polymer is 50,000 to 200,000, preferably 75,000 to 150,000. If the weight average molecular weight is less than 50000, a porous structure may not be formed on the surface of the polymer particles. On the other hand, if it exceeds 200,000, the pore diameter on the surface of the polymer particles becomes too large, and the effect of having a porous structure on the surface of the polymer particles (for example, the viscosity characteristics of the paint when the polymer particles are blended with the paint) Dispersion characteristics when polymer particles are blended with products such as paints and cosmetics, and light of products when polymer particles are blended with products such as paints, cosmetics, and light diffusing films (light diffusing resin compositions) There is a possibility that the diffusibility and the tactile sensation when the polymer particles are blended into cosmetics or the like cannot be obtained.

  In this embodiment, since the non-crosslinked polymer has the above-described configuration, the above-described monomer is subjected to a known polymerization method such as suspension polymerization in an aqueous medium in the presence of a suspension stabilizer, a polymerization initiator, or the like. It may be produced by polymerization. The aqueous medium, suspension stabilizer, polymerization initiator, and the like used in the production are not particularly limited, and known materials similar to those used in the production of polymer particles described later may be used. Further, the obtained non-crosslinked polymer may be in the form of particles. In the production of non-crosslinked polymers, organic solvents (for example, hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; dioxane and ethylene) It is preferable to obtain the non-crosslinked polymer by polymerizing the above-mentioned monomer without using an ether solvent such as glycol diethyl ether). Polymer particles obtained by polymerizing the above-described monomers without using an organic solvent to obtain a non-crosslinked polymer, and using the non-crosslinked polymer to produce polymer particles described below. Mainly has a large number of pores on the particle surface, and the vinyl polymer and the non-crosslinked polymer are phase-separated, and the phase composed of the non-crosslinked polymer is dispersed in the phase composed of the vinyl polymer. It has a sea-island structure inside the particles and is excellent in light diffusibility. On the other hand, polymer particles produced using a non-crosslinked polymer produced using an organic solvent are compared to polymer particles produced using a non-crosslinked polymer produced without using the organic solvent described above. In addition to the particle surface, the number of pores in the interior of the particle and the size of the phase composed of the non-crosslinked polymer dispersed inside the particle is too small, resulting in poor light diffusibility.

  The polymer particles having the above-described form have a C3-C20 branched alkyl group in a monomer mixture containing 100 parts by weight of a monofunctional vinyl monomer and 5 to 100 parts by weight of a polyfunctional vinyl monomer. Suspended in an aqueous medium in the presence of 1 to 15.4 parts by weight of a non-crosslinked polymer having a weight average molecular weight of 50,000 to 200,000 derived from a monomer containing 50% by weight or more of alkyl (meth) acrylate and a polymerization initiator Manufactured by polymerization.

  As the aqueous medium, water is preferred.

  Examples of the polymerization initiator include oil-soluble peroxide polymerization initiators and azo polymerization initiators that are usually used in aqueous suspension polymerization.

  Peroxide polymerization initiators include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochloroperoxybenzoic acid, orthomethoxybenzoic peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide. Examples thereof include oxide, t-butyl hydroperoxide, t-butyl peroxyneodecanoate, and diisopropylbenzene hydroperoxide.

  As the azo polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis2,3-dimethylbutyronitrile 2,2′-azobis (2-methylbutyronitrile), 2,2 ′-(azobis2,3,3-trimethylbutyronitrile), 2,2′-azobis (2-isopropylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), (2-carbamoylazo) isobutyronitrile, 4,4 ′ -Azobis (4-cyanovaleric acid), dimethyl-2,2'-azobisisobutyrate and the like.

  Among the above polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2 ′-(azobis 2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide and the like are polymerization initiators. It is preferable from the viewpoint of decomposition rate and the like.

  The amount of the polymerization initiator used is preferably in the range of 0.01 to 10 parts by weight and in the range of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the monomer mixture. Is more preferable. By setting the amount of the polymerization initiator used to 0.01 parts by weight or more with respect to 100 parts by weight of the monomer mixture, the polymerization can be started more reliably. On the other hand, by setting the amount of the polymerization initiator used to 10 parts by weight or less with respect to 100 parts by weight of the monomer mixture, an effect commensurate with the amount of polymerization initiator used can be obtained, and an effect commensurate with the cost can be obtained. Can be obtained.

  Moreover, you may add a suspension stabilizer (dispersion stabilizer) to an aqueous medium as needed. Examples of the suspension stabilizer include phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate and zinc pyrophosphate; calcium carbonate Metal hydroxides such as magnesium carbonate, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; poorly water-soluble inorganic compounds such as calcium metasilicate, calcium sulfate, barium sulfate, colloidal silica; polyvinyl alcohol, methylcellulose, hydroxypropylmethylcellulose And water-soluble polymers such as polyvinylpyrrolidone. Among these, tricalcium phosphate, magnesium pyrophosphate and calcium pyrophosphate obtained by the metathesis generation method, and colloidal silica are preferable because polymer particles can be stably obtained. In addition, the suspension stabilizer may be selected appropriately and the amount used may be appropriately adjusted in consideration of the desired particle diameter of the polymer particles and the dispersion stability of the monomer mixture during suspension polymerization. .

  Furthermore, a surfactant may be added to the aqueous medium, and a suspension stabilizer and a surfactant can be used in combination. As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant can be used.

  Examples of the anionic surfactant include sodium oleate; fatty acid soap such as castor oil potash soap; alkyl sulfate ester salt such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonate such as sodium dodecylbenzenesulfonate; alkylnaphthalene Sulfonates; alkane sulfonates; dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate; alkenyl succinates (dipotassium salts); alkyl phosphate esters; naphthalene sulfonate formalin condensates; polyoxyethylene alkylphenyl ether sulfates Salt, polyoxyethylene alkyl ether sulfate such as sodium polyoxyethylene lauryl ether sulfate; polyoxyethylene alkyl sulfate ester salt, etc.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxy Examples include ethylene-oxypropylene block polymers.

  Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate; quaternary ammonium salts such as lauryltrimethylammonium chloride.

  Examples of zwitterionic surfactants include lauryl dimethylamine oxide, phosphate ester surfactants, and phosphite ester surfactants.

  The said surfactant may be used independently and may be used in combination of 2 or more type. The surfactant may be selected as appropriate and the amount used may be adjusted appropriately in consideration of the desired particle diameter of the polymer particles and the dispersion stability of the monomer mixture during suspension polymerization.

  In addition, in order to suppress the generation of emulsion particles in water (polymer particles having a particle diameter of less than 1 μm produced by secondary emulsion polymerization) in the polymerization step in which the suspension polymerization is performed, nitrites, sulfurous acid Water-soluble polymerization inhibitors such as salts, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citric acid and polyphenols may be added to the aqueous medium.

  In the method for producing polymer particles of this embodiment, the non-crosslinked polymer is usually mixed (dissolved) with respect to the monomer mixture, and further, a polymerization initiator and the like are mixed as necessary to prepare a mixture, The prepared mixture is dispersed in an aqueous medium containing a suspension stabilizer and / or a surfactant as necessary, and an aqueous suspension polymerization is performed.

  As a dispersion method for dispersing a mixture obtained by mixing a non-crosslinked polymer or the like with a monomer mixture in an aqueous medium, for example, a mixture (a non-crosslinked polymer or the like is mixed with a monomer mixture). The mixture is directly added and dispersed in the aqueous medium as droplets by the stirring force of a propeller blade or the like; the high shear composed of the rotor and the stator is directly added to the aqueous medium A method of dispersing the mixture in an aqueous medium using a homomixer which is a disperser utilizing force; adding the mixture directly into the aqueous medium, and then dispersing the mixture in the aqueous medium using an ultrasonic disperser or the like Various methods such as a dispersion method can be mentioned. Among these, the mixture is directly added to an aqueous medium, and the mixture is used by using a high-pressure disperser such as a microfluidizer or a nanomizer, and using the collision between the droplets of the mixture or the collision of the mixture against the machine wall. It is preferable to disperse the mixture as droplets in an aqueous medium; by dispersing the mixture in an aqueous medium through an MPG (microporous glass) porous film, etc., because the particle diameter can be made more uniform.

  The suspension polymerization is then initiated by heating the aqueous medium (aqueous suspension) in which the mixture is dispersed as droplets. It is preferable to stir the aqueous suspension during the polymerization reaction. The stirring may be performed to such an extent that the mixture can be prevented from floating as droplets and the polymer particles generated by the polymerization can be prevented from settling.

  The polymerization temperature is preferably about 30 to 120 ° C, more preferably about 40 to 80 ° C. The time for maintaining this polymerization temperature is preferably about 0.1 to 20 hours. The polymerization may be performed in an inert gas atmosphere that is inert to the reactants (mixture, etc.) in the polymerization reaction system, such as a nitrogen atmosphere.

  If the boiling point of the monomer mixture and non-crosslinked polymer is near or below the polymerization temperature, use a pressure-resistant polymerization facility such as an autoclave so that the monomer mixture and non-crosslinked polymer do not volatilize. Thus, it is preferable to carry out the suspension polymerization under sealing or under pressure.

  After the polymerization is completed, the obtained polymer particles are separated as a hydrous cake by a method such as suction filtration, centrifugal dehydration, centrifugal separation, pressure dehydration, and the obtained hydrous cake is washed with water and dried. The desired polymer particles can be obtained.

  According to the production method of this embodiment, polymer particles having a surface porous structure mainly having a plurality of pores on the surface can be obtained. In the polymer particles obtained by the production method of this embodiment, the vinyl polymer and the non-crosslinked polymer are phase-separated, and the phase composed of the non-crosslinked polymer is dispersed in the phase composed of the vinyl polymer. It has a sea-island structure (phase-separated structure of non-crosslinked polymer and vinyl polymer) inside the polymer particles. The reason why the sea-island structure is formed inside the polymer particles is considered to be that the compatibility between the resulting vinyl polymer and the non-crosslinked polymer decreases as the polymerization of the monomer mixture proceeds. It is done. Furthermore, since no organic solvent is present in the polymerization reaction system, phase separation between the vinyl polymer and the non-crosslinked polymer is further promoted, and thereby, the inside of the polymer particle is composed of a vinyl polymer. It is considered that the formation of a sea-island structure in which a phase composed of a non-crosslinked polymer is dispersed is promoted. The reason for forming a plurality of pores on the surface of the polymer particles is that the phase separation between the vinyl polymer and the non-crosslinked polymer is caused inside the particles as the polymerization of the monomer mixture proceeds. It is considered that this is because a change occurs in the stable state on the particle surface.

  The polymer particle of this embodiment has a sea-island structure in which the non-crosslinked polymer and the vinyl polymer are phase-separated and the phase made of the non-crosslinked polymer is dispersed in the phase made of the vinyl polymer. Therefore, compared with conventional polymer particles having a porous surface structure, it has an unprecedented characteristic that is superior in characteristics when blended with paints and cosmetics. Specifically, since the inside of the polymer particles of the present embodiment is in a state where materials having different optical refractive indexes (that is, non-crosslinked polymer and vinyl polymer) are mixed, the polymer particles of the present embodiment are When blended in products such as paints, cosmetics, and light diffusing films (light diffusing resin compositions), the light diffusivity specific to the product can be expressed.

  Further, according to the manufacturing method of the present embodiment, it is possible to form the surface porous structure with the non-crosslinked polymer without using the organic solvent for forming the surface porous structure, so that the removal of the organic solvent No process is required. Therefore, it is possible to reduce the number of manufacturing steps and reduce the manufacturing cost.

[External preparation]
The polymer particles of the present invention can be used as a raw material for external preparations. The external preparation of the present invention contains the polymer particles of the present invention. Although content of the polymer particle in an external preparation can be suitably set according to the kind of external preparation, it exists in the range of 1-80 weight%, and it is more preferable that it exists in the range of 5-70 weight%. When the content of the polymer particles with respect to the total amount of the external preparation is less than 1% by weight, a clear effect due to the inclusion of the polymer particles may not be recognized. On the other hand, if the content of the polymer particles exceeds 80% by weight, a remarkable effect commensurate with the increase in the content may not be recognized, which is not preferable in terms of production cost.

  Examples of external preparations include cosmetics (cosmetics) and external medicines.

  The cosmetic is not particularly limited as long as it has an effect due to the inclusion of the polymer particles. For example, liquid systems such as pre-shave lotion, body lotion, lotion, cream, emulsion, body shampoo, antiperspirant, etc. Cosmetics for soap, scrubs, facial cleansers, etc .; packs; shave creams; funny products; foundations; lipsticks; lip balms; blushers; eyebrows cosmetics; nail polish cosmetics; Aromatic cosmetics; toothpaste; bath preparation; sunscreen product; suntan product; body powder, baby powder and other body cosmetics.

  The topical pharmaceutical is not particularly limited as long as it is applied to the skin, and examples thereof include pharmaceutical creams, ointments, pharmaceutical emulsions, and pharmaceutical lotions.

  Moreover, the main agent or additive generally used can be mix | blended with these external preparations according to the objective in the range which does not impair the effect of this invention. Examples of such main agents or additives include water, lower alcohols (alcohols having 5 or less carbon atoms), oils and fats, hydrocarbons (such as petroleum jelly and liquid paraffin), and higher fatty acids (such as stearic acid having 12 carbon atoms). Fatty acids), higher alcohols (alcohols having 6 or more carbon atoms such as cetyl alcohol), sterols, fatty acid esters (octyldodecyl myristate, oleate, etc.), metal soaps, moisturizers, surfactants (polyethylene glycol, etc.) , Polymer compounds, clay minerals (components having several functions such as extender pigments and adsorbents; talc, mica, etc.), coloring materials (red iron oxide, yellow iron oxide, black iron oxide, etc.), perfume , Antiseptic / disinfectant, antioxidant, UV absorber, acrylic resin particles (poly (meth) acrylic acid ester particles), silicon System particles, resin particles such as polystyrene particles, organic-inorganic composite particles, pH modifiers (triethanolamine), a special formulation additives, pharmaceutical active ingredients, and the like.

〔paint〕
The polymer particles of the present invention can be contained in a paint as a coating film softening agent or a paint matting agent. The coating material of the present invention contains the polymer particles of the present invention. The coating material of this invention contains at least one of binder resin and a solvent as needed. As the binder resin, a resin soluble in an organic solvent or water, or an emulsion-type aqueous resin that can be dispersed in water can be used. Examples of such binder resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins. These binder resins can be appropriately selected depending on the adhesion of the paint to the substrate to be coated, the environment in which it is used, and the like.

  The amount of the binder resin and polymer particles added varies depending on the film thickness of the coating film to be formed, the volume average particle diameter of the polymer particles, and the coating method. The addition amount of the binder resin is preferably in the range of 5 to 50% by weight with respect to the total of the binder resin (solid content when an emulsion type aqueous resin is used) and the polymer particles. It is more preferably within the range of ˜50% by weight, and further preferably within the range of 20 to 40% by weight.

  The addition amount of the polymer particles is preferably in the range of 5 to 50% by weight with respect to the total of the binder resin (solid content when using an emulsion type aqueous resin) and the polymer particles, The content is more preferably in the range of 10 to 50% by weight, and further preferably in the range of 20 to 40% by weight. When the content of the polymer particles is less than 5% by weight, the matte effect may not be sufficiently obtained. When the content of the polymer particles exceeds 50% by weight, the dispersion of the polymer particles may be poor because the viscosity of the coating becomes too high. Therefore, the appearance defect of the coating film may occur, such as micro cracks occurring in the coating film obtained, or roughness on the surface of the coating film obtained.

  Although it does not specifically limit as a solvent which comprises the said coating material, It is preferable to use the solvent which can melt | dissolve or disperse | distribute binder resin. For example, when the paint is an oil paint, as the solvent, hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; dioxane and ethylene And ether solvents such as glycol diethyl ether and ethylene glycol monobutyl ether. When the paint is an aqueous paint, water, alcohols, etc. can be used as the solvent. These solvents may be used alone or in combination of two or more. The content of the solvent in the coating is usually in the range of 20 to 60% by weight with respect to the total amount of the coating.

  The paint includes known coating surface modifiers, fluidity modifiers, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, colored pigments, metal pigments, mica powder pigments, dyes, etc., as necessary. It may be.

  The formation method of the coating film using a coating material is not specifically limited, Any well-known method can be used. Examples of the method for forming the coating film include methods such as spray coating, roll coating, and brush coating. The paint may be diluted by adding a diluent to adjust the viscosity as necessary. Diluents include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and ethylene glycol diethyl ether; water An alcohol solvent or the like. These diluents may be used alone or in combination of two or more.

[Light diffusing resin composition]
By dispersing the polymer particles of the present invention in a transparent base resin (transparent resin) as a light diffusing agent, it can be used as a light diffusing resin composition. Specifically, since the polymer particles of the present invention have a plurality of pores on the surface and an uneven structure on the surface, light is irregularly reflected compared to particles having a smooth surface. easy. For this reason, the polymer particle of this invention can exhibit a high light-diffusion effect with a small addition in a light diffusable resin composition.

  Therefore, the light diffusing resin composition of the present invention contains the polymer particles of the present invention and a transparent base resin. The light diffusing resin composition can be used as a raw material for a light diffusing member (light diffusing body) such as a lighting cover, a light diffusing sheet or the like.

  The light diffusing resin composition diffuses light on the surface of the polymer particles. Therefore, the refractive index of the transparent base resin and the refractive index of the polymer particles may be the same or different. When the refractive index of the transparent base resin and the refractive index of the polymer particles are different, light is diffused on the surface of the polymer particles, and light is also emitted at the interface between the transparent base resin and the polymer particles. Is diffused, so that a higher light diffusion effect can be obtained. In order to make the refractive index of the transparent base resin different from the refractive index of the polymer particles, a thermoplastic resin different from the polymer particles may be used as the transparent base resin.

  Examples of the thermoplastic resin used as the transparent base resin include acrylic resin, alkyl (meth) acrylate-styrene copolymer, polycarbonate, polyester, polyethylene, polypropylene, and polystyrene. Among these thermoplastic resins, acrylic resin, alkyl (meth) acrylate-styrene copolymer, polycarbonate, polyester, and polystyrene are preferable when excellent transparency is required for the transparent base resin. These thermoplastic resins can be used alone or in combination of two or more.

  The addition ratio of the polymer particles to the transparent base resin is preferably in the range of 0.01 to 40 parts by weight, and in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the transparent base resin. More preferably, it is within. When the polymer particles are less than 0.01 parts by weight, it may be difficult to impart light diffusibility to the light diffusing member. When the amount of polymer particles is more than 40 parts by weight, the light diffusing member can be given light diffusibility, but the light diffusing member may have low light transmittance.

  The method for producing the light diffusing resin composition is not particularly limited, and can be produced by mixing the polymer particles and the transparent base resin by a conventionally known method such as a mechanical pulverization and mixing method. In the mechanical pulverization and mixing method, for example, the polymer particles and the transparent base resin are mixed and stirred using a device such as a Henschel mixer, a V-type mixer, a turbula mixer, a hybridizer, or a rocking mixer, and light is mixed. A diffusible resin composition can be produced.

  A light diffusing sheet can be produced by molding the light diffusing resin composition. In this case, for example, a light diffusing agent and a transparent base resin are mixed with a mixer, and a pellet made of a light diffusing resin composition is obtained by kneading with a melt kneader such as an extruder. A light diffusing sheet having an arbitrary shape can be obtained by extrusion molding or injection molding after melting the pellet.

  The light diffusion sheet can be used as, for example, a light diffusion sheet of a liquid crystal display device. The configuration of the liquid crystal display device is not particularly limited as long as it includes a light diffusion sheet. For example, the liquid crystal display device includes at least a liquid crystal display panel having a display surface and a back surface, a light guide plate disposed on the back surface side of the liquid crystal display panel, and a light source that makes light incident on the side surface of the light guide plate. In addition, the liquid crystal display device includes a light diffusion sheet on a surface of the light guide plate facing the liquid crystal display panel, and a reflection sheet on the surface opposite to the surface of the light guide plate facing the liquid crystal display panel. This arrangement of light sources is generally referred to as an edge light type backlight arrangement. Furthermore, as the arrangement of the light source, there is a direct type backlight arrangement in addition to the edge light type backlight arrangement. Specifically, this arrangement is an arrangement in which a light source is arranged on the back side of the liquid crystal display panel and at least a light diffusion sheet arranged between the liquid crystal display panel and the light source.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this. First, measurement methods and calculation methods in Examples and Comparative Examples will be described.

[Measurement method of volume average particle diameter]
The volume average particle diameter of the polymer particles was calculated by filling the electrolyte solution into pores having a pore diameter of 20 to 400 μm and determining the volume from the change in conductivity of the electrolyte solution when the particles pass through the electrolyte solution. Specifically, the volume average particle size of the polymer particles is measured by using a Coulter type precision particle size distribution measuring device “Multisizer III” (manufactured by Beckman Coulter, Inc.). Arithmetic mean diameter). In measurement, according to “Reference MANUAL FOR THE COULTER MULTISIZER” (1987) published by Coulter Electronics Limited, multisizer III is calibrated and measured using an aperture suitable for the particle diameter of the particles to be measured.

  Specifically, 0.1 g of polymer particles are dispersed in 10 ml of a 0.1 wt% nonionic surfactant solution using a touch mixer and ultrasonic waves to obtain a dispersion. In a beaker filled with the measurement electrolyte “ISOTON (registered trademark) II” (manufactured by Beckman Coulter, Inc.) provided in the “Multisizer III” main body, the dispersion is dropped with a dropper while gently stirring. Adjust the concentration meter reading on the Multisizer III screen to around 10%. Next, the aperture size (diameter), current (aperture current), gain (gain), and polarity (polarity of the inner electrode) are set on the “Multisizer III” main body according to REFERENCE MANUAL FOR THE COULTER MULTISIZER (198) issued by Coulter Electronics Limited. Enter and measure the volume-based particle size distribution in manual (manual mode). During the measurement, the beaker is stirred gently to the extent that bubbles do not enter, and the measurement ends when the particle size distribution of 100,000 particles is measured. The volume average particle diameter is an average value of the measured particle diameters of 100,000 particles, and means an arithmetic average diameter in a volume-based particle size distribution.

[Measurement method of center diameter of pores in surface porous structure]
The center diameter (center pore diameter) of the pores of the polymer particles having a surface porous structure is measured using a pore distribution measuring device “Autopore 9520 type” manufactured by Shimadzu Corporation. This pore distribution measuring apparatus is an apparatus using a mercury intrusion method. In the mercury intrusion method, using the fact that the surface tension of mercury is large, a pressure for intruding mercury into the pores of polymer particles is applied, and the fine pressure is calculated from the applied pressure and the amount of mercury intruded into the pores. Measure the pore distribution. Specifically, 0.1 to 0.5 g of a sample (polymer particles) is taken in a 5 ml cell, and the pore distribution measuring device is used under the condition of an initial pressure of about 6 kPa (corresponding to a pore diameter of about 230 μm). Measure the pore distribution of the sample. The mode value (mode diameter) in the pore distribution was defined as the center diameter (mode mode diameter).

  When polymer particles having pores are measured by this method, the gap between the polymer particles as well as the pores of the polymer particles may be measured as a peak of the pore distribution. For this reason, two pore peaks may be seen in the measured pore distribution. In such a case, the larger pore peak is usually due to the gap between the polymer particles, and is a pore peak of about 1/2 to 1/4 of the volume average particle diameter of the polymer particles to be measured. appear. For this reason, when two pore peaks exist in the measured pore distribution, the pore distribution larger than the pore value at the minimum point between the two pore peaks is ignored and the pore distribution is recalculated. The mode value (mode diameter) in the recalculated pore distribution was defined as the center diameter (mode diameter).

[Method for measuring specific surface area]
The specific surface area of the polymer particles is measured by the BET method (nitrogen adsorption method) described in JIS R1626. For the target polymer particles, the BET nitrogen adsorption isotherm was measured using AS-6 manufactured by Cantachrome Co., and from the three points of nitrogen adsorption amounts of P / Po = 0.1, 0.2 and 0.3. The specific surface area is calculated using the BET multipoint method. The measurement of the nitrogen adsorption isotherm was performed by using the constant dissolution method under the condition of the adsorbate cross section of 0.162 nm ² using nitrogen as the adsorbate.

[Method for measuring weight average molecular weight of non-crosslinked polymer]
The weight average molecular weight of the non-crosslinked polymer is measured using gel permeation chromatography (GPC). The weight average molecular weight (Mw) to be measured is a polystyrene (PS) conversion weight average molecular weight. The measuring method is as follows. First, 50 mg of a sample (non-crosslinked polymer) is dissolved in 10 ml of tetrahydrofuran (THF). The resulting solution is filtered using a 0.45 μm non-aqueous chromatographic disk. The obtained filtrate is analyzed by GPC, and the weight average molecular weight in terms of PS is measured. The GPC measurement conditions are as follows.

GPC apparatus: trade name “Gel Permeation Chromatograph HLC-8020” manufactured by Tosoh Corporation
Column: Trade name “TSKgel GMH-XL-L” (diameter 7.8 mm × length 30 cm) manufactured by Tosoh Corporation Column temperature: 40 ° C.
Carrier gas (effluent): Tetrahydrofuran (THF)
Carrier gas flow rate (flow rate): 1 ml / min Injection / pump temperature (flow temperature): 35 ° C
Detection: RI (differential refractive index detector)
Injection volume: 100 μl
Standard polystyrene for calibration curve to calculate PS-converted weight average molecular weight: trade name “shodex (registered trademark)” (weight average molecular weight: 1030000) manufactured by Showa Denko KK, and standard polystyrene for calibration curve manufactured by Tosoh Corporation (Weight average molecular weight: 5480000, 3840000, 355000, 102000, 37900, 9100, 2630, 870)
[Production Example 1 of Non-crosslinked Polymer]
In a 5 L autoclave as a polymerization vessel, 2200 g of water, 28 g of metathesis magnesium pyrophosphate as a suspension stabilizer, and 0.8 g of sodium dodecyl sulfate as a surfactant are mixed to contain a suspension stabilizer. The obtained dispersion medium was obtained in the form of an aqueous solution.

  On the other hand, 1300 g of isobutyl methacrylate as an alkyl (meth) acrylate having a branched alkyl group (86.7% by weight based on the total weight of isobutyl methacrylate and methyl methacrylate as a polymerizable component) and other polymerizable components 200 g of methyl methacrylate (13.3 wt% with respect to the total weight of isobutyl methacrylate and methyl methacrylate as polymerizable components), 5 g of n-dodecyl mercaptan as a molecular weight regulator, and as a polymerization initiator A monomer mixture was prepared by uniformly mixing 6 g of benzoyl peroxide.

  This monomer mixture is added to the dispersion medium in the polymerization vessel and about 10 at a stirring speed of 3,000 rpm using a high-speed emulsification / dispersing machine “TK homomixer Mark 2.5 type” (manufactured by PRIMIX Corporation). The mixture was stirred for a minute to finely disperse the monomer mixture in the dispersion medium.

  Thereafter, the dispersion medium to which the monomer mixture was added was subjected to a polymerization reaction at 75 ° C. and a stirring speed of 300 rpm for 4 hours, and then allowed to undergo a polymerization reaction at 100 ° C. and a stirring speed of 350 rpm for 1 hour.

  Next, the reaction solution in the polymerization vessel was cooled to room temperature while stirring, and then 40 ml of 20 wt% hydrochloric acid was added to decompose the suspension stabilizer (magnesium pyrophosphate). Subsequently, the reaction liquid was subjected to suction filtration. The filtration residue was washed with ion-exchanged water, drained, and then dried overnight in a 50 ° C. oven to obtain the desired non-crosslinked polymer. The weight average molecular weight of the obtained non-crosslinked polymer was 103,000 as measured by the measurement method described above. The obtained non-crosslinked polymer was a particle. When the volume average particle size was measured by the method for measuring the volume average particle size of the polymer particles described above, the volume average particle size was 31.2 μm. It was. Let the non-crosslinked polymer obtained by this method be a non-crosslinked polymer (1).

[Production Example 2 of Non-crosslinked Polymer]
In a 5 L autoclave as a polymerization vessel, 2200 g of water, 45 g of metathesis magnesium pyrophosphate as a suspension stabilizer and 0.8 g of sodium dodecyl sulfate as a surfactant are mixed, and a suspension stabilizer is contained. The obtained dispersion medium was obtained in the form of an aqueous solution.

  On the other hand, 1050 g of isostearyl methacrylate as an alkyl (meth) acrylate having a branched alkyl group (70% by weight based on the total weight of isostearyl methacrylate and methyl methacrylate as a polymerizable component) and other polymerizable components As a polymerization initiator, 450 g of methyl methacrylate (30% by weight with respect to the total weight of isostearyl methacrylate and methyl methacrylate as a polymerizable component), 5 g of n-dodecyl mercaptan as a molecular weight regulator, and excess as a polymerization initiator. A monomer mixture was prepared by uniformly mixing 6 g of benzoyl oxide.

  This monomer mixture is added to the dispersion medium in the polymerization vessel and about 10 at a stirring speed of 3,000 rpm using a high-speed emulsification / dispersing machine “TK homomixer Mark 2.5 type” (manufactured by PRIMIX Corporation). The mixture was finely dispersed in the dispersion medium.

  Thereafter, the dispersion medium to which the monomer mixture was added was subjected to a polymerization reaction at 75 ° C. and a stirring speed of 300 rpm for 4 hours, and then allowed to undergo a polymerization reaction at 100 ° C. and a stirring speed of 350 rpm for 1 hour.

  Next, the reaction solution in the polymerization vessel was cooled to room temperature with stirring, and then 60 ml of 20 wt% hydrochloric acid was added to decompose the suspension stabilizer (magnesium pyrophosphate). Subsequently, the reaction liquid was subjected to suction filtration. The filtration residue was washed with ion-exchanged water, drained, and then dried overnight in a 50 ° C. oven to obtain the desired non-crosslinked polymer. The weight average molecular weight of the obtained non-crosslinked polymer was 86,000 as measured by the measurement method described above. The obtained non-crosslinked polymer was a particle. When the volume average particle size was measured by the method for measuring the volume average particle size of the polymer particles described above, the volume average particle size was 34.9 μm. It was. Let the non-crosslinked polymer obtained by this method be a non-crosslinked polymer (2).

[Production Example 3 of Non-crosslinked Polymer]
In a 5 L autoclave as a polymerization vessel, 2200 g of water, 28 g of metathesis magnesium pyrophosphate as a suspension stabilizer, and 0.8 g of sodium dodecyl sulfate as a surfactant are mixed to contain a suspension stabilizer. The obtained dispersion medium was obtained in the form of an aqueous solution.

  On the other hand, 1500 g of methyl methacrylate as a polymerizable component, 5 g of n-dodecyl mercaptan as a molecular weight regulator, and 6 g of benzoyl peroxide as a polymerization initiator were uniformly mixed to prepare a monomer mixture.

  This monomer mixture is added to the dispersion medium in the polymerization vessel and about 10 at a stirring speed of 3,000 rpm using a high-speed emulsification / dispersing machine “TK homomixer Mark 2.5 type” (manufactured by PRIMIX Corporation). The mixture was stirred for a minute to finely disperse the monomer mixture in the dispersion medium.

  Thereafter, the dispersion medium to which the monomer mixture was added was subjected to a polymerization reaction at 75 ° C. and a stirring speed of 300 rpm for 4 hours, and then allowed to undergo a polymerization reaction at 100 ° C. and a stirring speed of 350 rpm for 1 hour.

  Next, the reaction solution in the polymerization vessel was cooled to room temperature while stirring, and then 40 ml of 20 wt% hydrochloric acid was added to decompose the suspension stabilizer (magnesium pyrophosphate). Subsequently, the reaction liquid was subjected to suction filtration. The filtration residue was washed with ion-exchanged water, drained, and then dried overnight in a 50 ° C. oven to obtain the desired non-crosslinked polymer. The weight average molecular weight of the obtained non-crosslinked polymer was 120,000 as measured by the measurement method described above. The obtained non-crosslinked polymer was a particle. When the volume average particle size was measured by the method for measuring the volume average particle size of the polymer particles described above, the volume average particle size was 27.6 μm. It was. Let the non-crosslinked polymer obtained by this method be a non-crosslinked polymer (3).

[Production Example 4 of Non-crosslinked Polymer]
In a 5 L autoclave as a polymerization vessel, 2200 g of water, 28 g of metathesis magnesium pyrophosphate as a suspension stabilizer, and 0.8 g of sodium dodecyl sulfate as a surfactant are mixed to contain a suspension stabilizer. The obtained dispersion medium was obtained in the form of an aqueous solution.

  On the other hand, 1500 g of isobutyl methacrylate as an alkyl (meth) acrylate having a branched alkyl group (100% by weight based on the total weight of the polymerizable component), 5 g of n-dodecyl mercaptan as a molecular weight regulator, and as a polymerization initiator A monomer mixture was prepared by uniformly mixing 6 g of benzoyl peroxide.

  This monomer mixture is added to the dispersion medium in the polymerization vessel and about 10 at a stirring speed of 3,000 rpm using a high-speed emulsification / dispersing machine “TK homomixer Mark 2.5 type” (manufactured by PRIMIX Corporation). The mixture was stirred for a minute to finely disperse the monomer mixture in the dispersion medium.

  Thereafter, the dispersion medium to which the monomer mixture was added was subjected to a polymerization reaction at 75 ° C. at a stirring speed of 220 rpm for 4 hours, and then at 100 ° C. at a stirring speed of 280 rpm for 1 hour.

  Next, the reaction solution in the polymerization vessel was cooled to room temperature while stirring, and then 40 ml of 20 wt% hydrochloric acid was added to decompose the suspension stabilizer (magnesium pyrophosphate). Subsequently, the reaction liquid was subjected to suction filtration. The filtration residue was washed with ion-exchanged water, drained, and then dried overnight in a 50 ° C. oven to obtain the desired non-crosslinked polymer. The weight average molecular weight of the obtained non-crosslinked polymer was 107,000 as measured by the measurement method described above. The obtained non-crosslinked polymer was a particle. When the volume average particle size was measured by the method for measuring the volume average particle size of the polymer particles described above, the volume average particle size was 27.0 μm. It was. Let the non-crosslinked polymer obtained by this method be a non-crosslinked polymer (4).

[Production Example 5 of Non-crosslinked Polymer]
In a 500 ml flask, 200 g of water, 3 g of metathesis magnesium pyrophosphate as a suspension stabilizer, and 0.1 g of sodium dodecyl sulfate as a surfactant are mixed, and a dispersion medium containing the suspension stabilizer is mixed. Obtained in the form of an aqueous solution.

  On the other hand, 80 g of t-butyl methacrylate as an alkyl (meth) acrylate having a branched alkyl group (100 wt% with respect to the total weight of the polymerizable component) was added to 2,2′-azobisisobutyrate as a polymerization initiator. A monomer mixture was prepared by dissolving 0.8 g of nitrile.

  After the dispersion medium in the flask was heated to 80 ° C., the monomer mixture was added dropwise over 2 hours. Subsequently, a solution prepared by dissolving 0.22 g of 2,2′-azobisisobutyronitrile in 1.5 g of water was dropped 5 times every 20 minutes in the dispersion medium in which the monomer mixture was dropped. Thereafter, the dispersion medium in which the monomer mixture was dropped was stirred at 80 ° C. for 100 minutes to cause a polymerization reaction.

  Next, the reaction solution in the flask was cooled to room temperature with stirring, and 10 ml of 20 wt% hydrochloric acid was added to decompose the suspension stabilizer (magnesium pyrophosphate). Subsequently, the reaction liquid was subjected to suction filtration. The filtration residue was washed with ion-exchanged water, drained, and then dried overnight in a 50 ° C. oven to obtain the desired non-crosslinked polymer. When the weight average molecular weight of the obtained non-crosslinked polymer was measured by the measurement method described above, it was 100,000. The obtained non-crosslinked polymer was a particle. When the volume average particle size was measured by the method for measuring the volume average particle size of the polymer particles described above, the volume average particle size was 38.1 μm. It was. Let the non-crosslinked polymer obtained by this method be a non-crosslinked polymer (5).

[Production Example 6 of non-crosslinked polymer]
2,2′-azobisisobutyronitrile as a polymerization initiator was added to 200 g of t-butyl methacrylate (100% by weight based on the total weight of the polymerizable component) as an alkyl (meth) acrylate having a branched alkyl group. 2 g was dissolved to prepare a monomer mixture.

  200 g of toluene was put into a 500 ml flask and heated to 100 ° C., and then the monomer mixture was added dropwise over 2 hours. Next, a solution prepared by dissolving 0.22 g of 2,2′-azobisisobutyronitrile in 1.5 g of toluene was dropped 5 times every 20 minutes in toluene to which the monomer mixture was dropped. Thereafter, the toluene in which the monomer mixture was dropped was stirred at 100 ° C. for 100 minutes to cause a polymerization reaction, thereby obtaining a non-crosslinked polymer containing toluene. Let the non-crosslinked polymer obtained by this method be a non-crosslinked polymer (6).

[Example 1: Production of polymer particles]
In a 5 L autoclave as a polymerization vessel, 2300 g of water, 83 g of metathesis magnesium pyrophosphate as a suspension stabilizer, and 4.0 g of sodium dodecyl sulfate as a surfactant are mixed, and a suspension stabilizer is contained. The obtained dispersion medium was obtained in the form of an aqueous solution.

  On the other hand, 910 g of butyl acrylate as a monofunctional vinyl monomer and 390 g of ethylene glycol dimethacrylate as a polyfunctional vinyl monomer (based on 100 parts by weight of butyl acrylate as a monofunctional vinyl monomer) 42.9 parts by weight) and 39 g of the non-crosslinked polymer (1) obtained in Production Example 1 of the non-crosslinked polymer (4 parts per 100 parts by weight of butyl acrylate as a monofunctional vinyl monomer) .3 parts by weight), 5.2 g of 2,2′-azobis2,4-dimethylvaleronitrile as a polymerization initiator) and 2.6 g of benzoyl peroxide are uniformly mixed to prepare a monomer mixture. did.

  This monomer mixture is added to the dispersion medium in the polymerization vessel, and the dispersion medium to which the monomer mixture is added is subjected to a polymerization reaction at 50 ° C. and a stirring speed of 320 rpm for 2 hours, and then at 90 ° C. and a stirring speed of 475 rpm. The polymerization reaction was allowed to take for 5 hours.

  Next, the reaction solution in the polymerization vessel was cooled to room temperature with stirring, and 115 ml of 20 wt% hydrochloric acid was added to decompose the suspension stabilizer (magnesium pyrophosphate). Subsequently, the reaction liquid was subjected to suction filtration. The filtration residue was washed with ion-exchanged water, drained, and then dried overnight in a 50 ° C. oven to obtain the desired polymer particles.

The volume average particle diameter of the obtained polymer particles was 41.5 μm as measured by the measurement method described above. The specific surface area of the obtained polymer particles was 1.83 m ² / g as measured by the measurement method described above.

  Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image of FIG. 1 was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, cut into a thin film section, stained with ruthenium tetroxide, and then the cross section was imaged with a transmission electron microscope (TEM), and the TEM image in FIG. Got. From the SEM image shown in FIG. 1 and the TEM image shown in FIG. 2, it was confirmed that a porous structure was formed on the surface of the polymer particles. In the porous structure formed on the surface of the polymer particles, the pores were present irregularly on the entire surface of the polymer particles. In addition, from the TEM image shown in FIG. 2, the number of pores inside the polymer particles is very small compared to the number of pores on the surface of the polymer particles, and the inside of the polymer particles of Example 1 It was observed that almost no pores were formed. The center diameter of the plurality of holes formed on the surface of the polymer particles was 1.1 μm as measured by the measurement method described above.

  Furthermore, by extracting a non-crosslinked polymer from the obtained polymer particles, and imaging the cross section of the polymer particles after extraction with a transmission electron microscope (TEM), the presence or absence of the sea island structure in the polymer particles, that is, Then, it was confirmed whether or not the phase composed of the non-crosslinked polymer was present in the phase composed of the vinyl polymer inside the polymer particles. Specifically, 0.1 g of the obtained polymer particles were precisely weighed into a 50 ml centrifuge tube. Next, after adding about 30 ml of ethyl acetate to the centrifuge tube, the mixture was stirred for 1 hour with a magnetic stirrer and allowed to stand for 24 hours to extract the non-crosslinked polymer from the polymer particles. The centrifuge tube was centrifuged at 3300 rpm for 30 minutes and filtered, and then the precipitate (particles) was dried at about 70 ° C. After drying, the particles were embedded in an epoxy resin, cut into thin film sections, and the cross section was imaged with a transmission electron microscope (TEM) to obtain the TEM image of FIG. From the TEM image shown in FIG. 3, there are a plurality of pores that were not confirmed in the TEM image of the polymer particles before extraction of the non-crosslinked polymer shown in FIG. 2 inside the particles after extraction of the non-crosslinked polymer. It was confirmed. Therefore, it was confirmed that the phase composed of the non-crosslinked polymer was present in a dispersed state in the phase composed of the vinyl polymer inside the polymer particles of Example 1. That is, the polymer particles of Example 1 have a sea-island structure in which a non-crosslinked polymer and a vinyl polymer are phase-separated, and a phase composed of the non-crosslinked polymer is dispersed in a phase composed of the vinyl polymer. It was confirmed that the polymer particles had inside the polymer particles.

  Further, when the maximum value of the length of the phase composed of the non-crosslinked polymer existing inside the obtained polymer particles was measured based on the long diameter of the pores inside the particles confirmed in the TEM image shown in FIG. 760 nm.

[Example 2: Production of polymer particles]
In a 5 L autoclave as a polymerization vessel, 2300 g of water, 42 g of metathesis magnesium pyrophosphate as a suspension stabilizer, and 0.3 g of sodium dodecyl sulfate as a surfactant are mixed to contain a suspension stabilizer. The obtained dispersion medium was obtained in the form of an aqueous solution.

  Next, the monomer mixture obtained in the same manner as in Example 1 was added to the dispersion medium in the polymerization vessel, and the dispersion medium to which the monomer mixture was added was added to the high-speed emulsification / dispersing machine “TK homomixer Mark 2”. .5 type "(manufactured by PRIMIX Co., Ltd.) was processed at a stirring speed of 5000 rpm for 5 minutes to obtain an emulsion.

  This emulsion was subjected to a polymerization reaction at 50 ° C. and a stirring speed of 300 rpm over 2 hours, and then subjected to a polymerization reaction at 90 ° C. and a stirring speed of 450 rpm over 1.5 hours.

  The reaction solution in the polymerization vessel was cooled to room temperature while stirring, and then 65 ml of 20 wt% hydrochloric acid was added to decompose the suspension stabilizer (magnesium pyrophosphate). Subsequently, the reaction liquid was subjected to suction filtration. The filtration residue was washed with ion-exchanged water, drained, and then dried overnight in a 50 ° C. oven to obtain the desired polymer particles.

The volume average particle diameter of the obtained polymer particles was 18.1 μm as measured by the measurement method described above. The specific surface area of the obtained polymer particles was 2.46 m ² / g as measured by the measurement method described above.

  Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image of FIG. 4 was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the SEM image and TEM image shown in FIG. 4, it was confirmed that a porous structure was formed on the surface of the polymer particles. In the porous structure formed on the surface of the polymer particles, the pores were present irregularly on the entire surface of the polymer particles. Further, from the TEM image, the number of pores inside the polymer particles is very small compared to the number of pores on the surface of the polymer particles, and almost no pores are formed inside the polymer particles of Example 2. It was recognized that it was not. The center diameter of the plurality of holes formed on the surface of the polymer particles was 0.7 μm as measured by the measurement method described above.

  Further, in the same manner as in Example 1, a non-crosslinked polymer was extracted from the obtained polymer particles, and a cross section of the extracted polymer particles was imaged with a transmission electron microscope (TEM). It was confirmed that a plurality of pores that were not confirmed in the TEM image of the polymer particles before extraction of the non-crosslinked polymer were present inside the particles after extraction of. Therefore, the polymer particles of Example 2 have a sea-island structure in which the non-crosslinked polymer and the vinyl polymer are phase-separated, and the phase made of the non-crosslinked polymer is dispersed in the phase made of the vinyl polymer. It was confirmed that the polymer particles had inside the polymer particles. In addition, the maximum value of the length of the phase composed of the non-crosslinked polymer present inside the obtained polymer particles is based on the long diameter of the pores inside the particles confirmed in the TEM image after extraction of the non-crosslinked polymer. And measured to be 530 nm.

[Example 3: Production of polymer particles]
1170 g of methyl methacrylate as a monofunctional vinyl monomer and 130 g of ethylene glycol dimethacrylate as a polyfunctional vinyl monomer (11 parts per 100 parts by weight of methyl methacrylate as a monofunctional vinyl monomer) .1 part by weight) and 39 g of the non-crosslinked polymer (1) obtained in Production Example 1 of the non-crosslinked polymer (based on 100 parts by weight of methyl methacrylate as a monofunctional vinyl monomer) Parts by weight), a monomer mixture obtained by uniformly mixing 5.2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 2.6 g of benzoyl peroxide. Except for, polymer particles were obtained in the same manner as in Example 2.

The volume average particle diameter of the obtained polymer particles was 28.2 μm as measured by the measurement method described above. The specific surface area of the obtained polymer particles was 2.25 m ² / g as measured by the measurement method described above.

  Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image of FIG. 5 was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the SEM image and TEM image shown in FIG. 5, it was confirmed that a porous structure was formed on the surface of the polymer particles. In the porous structure formed on the surface of the polymer particles, the pores were present irregularly on the entire surface of the polymer particles. Further, from the TEM image, the number of pores inside the polymer particles is very small compared to the number of pores on the surface of the polymer particles, and almost no pores are formed inside the polymer particles of Example 3. It was recognized that it was not. The center diameter of the plurality of holes formed on the surface of the polymer particles was 0.8 μm as measured by the measurement method described above.

  Further, in the same manner as in Example 1, a non-crosslinked polymer was extracted from the obtained polymer particles, and a cross section of the extracted polymer particles was imaged with a transmission electron microscope (TEM). It was confirmed that a plurality of pores that were not confirmed in the TEM image of the polymer particles before extraction of the non-crosslinked polymer were present inside the particles after extraction of. Therefore, the polymer particles of Example 3 have a sea-island structure in which the non-crosslinked polymer and the vinyl polymer are phase-separated, and the phase made of the non-crosslinked polymer is dispersed in the phase made of the vinyl polymer. It was confirmed that the polymer particles had inside the polymer particles. In addition, the maximum value of the length of the phase composed of the non-crosslinked polymer present inside the obtained polymer particles is based on the long diameter of the pores inside the particles confirmed in the TEM image after extraction of the non-crosslinked polymer. It was 500 nm when measured.

[Example 4: Production of polymer particles]
In a 5 L autoclave as a polymerization vessel, 2600 g of water, 66 g of metathesis magnesium pyrophosphate as a suspension stabilizer and 0.8 g of sodium dodecyl sulfate as a surfactant are mixed, and a suspension stabilizer is contained. The obtained dispersion medium was obtained in the form of an aqueous solution.

  On the other hand, 910 g of butyl acrylate as a monofunctional vinyl monomer and 390 g of ethylene glycol dimethacrylate as a polyfunctional vinyl monomer (based on 100 parts by weight of butyl acrylate as a monofunctional vinyl monomer) 42.9 parts by weight) and 39 g of the non-crosslinked polymer (2) obtained in Production Example 2 of the non-crosslinked polymer (4 parts per 100 parts by weight of butyl acrylate as a monofunctional vinyl monomer) .3 parts by weight), 5.2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and 2.6 g of benzoyl peroxide are uniformly mixed to obtain a monomer mixture. Was prepared.

  This monomer mixture is added to the dispersion medium in the polymerization vessel, and the dispersion medium to which the monomer mixture is added is converted into a high-speed emulsification / dispersing machine “TK homomixer Mark 2.5 type” (manufactured by Primics Co., Ltd.). Was used for 15 minutes at a stirring speed of 7000 rpm to obtain an emulsion.

  This emulsion was subjected to a polymerization reaction at 50 ° C. and a stirring speed of 300 rpm over 2 hours, and then subjected to a polymerization reaction at 90 ° C. and a stirring speed of 450 rpm over 1.5 hours.

  The reaction solution in the polymerization vessel was cooled to room temperature while stirring, and 90 ml of 20 wt% hydrochloric acid was added to decompose the suspension stabilizer (magnesium pyrophosphate). Subsequently, the reaction liquid was subjected to suction filtration. The filtration residue was washed with ion-exchanged water, drained, and then dried overnight in a 50 ° C. oven to obtain the desired polymer particles.

The volume average particle diameter of the obtained polymer particles was 11.9 μm as measured by the measurement method described above. The specific surface area of the obtained polymer particles was 3.95 m ² / g as measured by the measurement method described above.

  Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image of FIG. 6 was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the SEM image and TEM image shown in FIG. 6, it was confirmed that a porous structure was formed on the surface of the polymer particles. In the porous structure formed on the surface of the polymer particles, the pores were present irregularly on the entire surface of the polymer particles. Further, from the TEM image, the number of pores inside the polymer particles is very small compared to the number of pores on the surface of the polymer particles, and almost no pores are formed inside the polymer particles of Example 4. It was recognized that it was not. Further, the center diameter of the plurality of holes formed on the surface of the polymer particles was 0.9 μm as measured by the measurement method described above.

  Further, in the same manner as in Example 1, a non-crosslinked polymer was extracted from the obtained polymer particles, and a cross section of the extracted polymer particles was imaged with a transmission electron microscope (TEM). It was confirmed that a plurality of pores that were not confirmed in the TEM image of the polymer particles before extraction of the non-crosslinked polymer were present inside the particles after extraction of. Therefore, the polymer particles of Example 4 have a sea-island structure in which the non-crosslinked polymer and the vinyl polymer are phase-separated, and the phase made of the non-crosslinked polymer is dispersed in the phase made of the vinyl polymer. It was confirmed that the polymer particles had inside the polymer particles.

[Example 5: Production of polymer particles]
140 g of non-crosslinked polymer (1) obtained in Production Example 1 of non-crosslinked polymer (15.4 parts by weight with respect to 100 parts by weight of butyl acrylate as a monofunctional vinyl monomer) Except for the points described above, polymer particles were obtained in the same manner as in Example 1.

The volume average particle diameter of the obtained polymer particles was 39.7 μm as measured by the measurement method described above. The specific surface area of the obtained polymer particles was 1.22 m ² / g as measured by the measurement method described above.

  Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the SEM image and the TEM image, it was confirmed that a porous structure was formed on the surface of the polymer particles. In the porous structure formed on the surface of the polymer particles, the pores were present irregularly on the entire surface of the polymer particles. Further, from the TEM image, the number of pores inside the polymer particles is very small compared to the number of pores on the surface of the polymer particles, and almost no pores are formed inside the polymer particles of Example 5. It was recognized that it was not. The center diameter of the plurality of holes formed on the surface of the polymer particles was 1.4 μm as measured by the measurement method described above.

  Further, in the same manner as in Example 1, a non-crosslinked polymer was extracted from the obtained polymer particles, and a cross section of the extracted polymer particles was imaged with a transmission electron microscope (TEM). It was confirmed that a plurality of pores that were not confirmed in the TEM image of the polymer particles before extraction of the non-crosslinked polymer were present inside the particles after extraction of. Therefore, the polymer particles of Example 5 have a sea-island structure in which the non-crosslinked polymer and the vinyl polymer are phase-separated, and the phase composed of the non-crosslinked polymer is dispersed in the phase composed of the vinyl polymer. It was confirmed that the polymer particles had inside the polymer particles.

[Example 6: Production of polymer particles]
In a 5 L autoclave as a polymerization vessel, 2300 g of water, 83 g of metathesis magnesium pyrophosphate as a suspension stabilizer and 0.8 g of sodium dodecyl sulfate as a surfactant are mixed, and a suspension stabilizer is contained. The obtained dispersion medium was obtained in the form of an aqueous solution.

  On the other hand, 910 g of butyl acrylate as a monofunctional vinyl monomer and 390 g of ethylene glycol dimethacrylate as a polyfunctional vinyl monomer (based on 100 parts by weight of butyl acrylate as a monofunctional vinyl monomer) 42.9 parts by weight) and 39 g of the non-crosslinked polymer (4) obtained in Production Example 4 of the non-crosslinked polymer (4 parts per 100 parts by weight of butyl acrylate as a monofunctional vinyl monomer) .3 parts by weight), 2.6 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and 1.3 g of benzoyl peroxide are uniformly mixed to obtain a monomer mixture. Was prepared.

  This monomer mixture is added to the dispersion medium in the polymerization vessel, and the dispersion medium to which the monomer mixture is added is allowed to undergo a polymerization reaction at 50 ° C. and a stirring speed of 150 rpm for 3 hours, and then at 90 ° C. and a stirring speed of 200 rpm. The polymerization reaction was allowed to take for 5 hours.

  Next, the reaction solution in the polymerization vessel was cooled to room temperature with stirring, and 115 ml of 20 wt% hydrochloric acid was added to decompose the suspension stabilizer (magnesium pyrophosphate). Subsequently, the reaction liquid was subjected to suction filtration. The filtration residue was washed with ion-exchanged water, drained, and then dried overnight in a 50 ° C. oven to obtain the desired polymer particles.

The volume average particle diameter of the obtained polymer particles was 28.0 μm as measured by the measurement method described above. The specific surface area of the obtained polymer particles was 1.21 m ² / g as measured by the measurement method described above.

  Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image of FIG. 7 was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the SEM image and TEM image shown in FIG. 7, it was confirmed that a porous structure was formed on the surface of the polymer particles. In the porous structure formed on the surface of the polymer particles, the pores were present irregularly on the entire surface of the polymer particles. Further, from the TEM image, the number of pores inside the polymer particles is very small compared to the number of pores on the surface of the polymer particles, and almost no pores are formed inside the polymer particles of Example 6. It was recognized that it was not. The center diameter of the plurality of holes formed on the surface of the polymer particles was 0.6 μm as measured by the measurement method described above.

  Further, in the same manner as in Example 1, a non-crosslinked polymer was extracted from the obtained polymer particles, and a cross section of the extracted polymer particles was imaged with a transmission electron microscope (TEM). It was confirmed that a plurality of pores that were not confirmed in the TEM image of the polymer particles before extraction of the non-crosslinked polymer were present inside the particles after extraction of. Therefore, the polymer particles of Example 6 have a sea-island structure in which the non-crosslinked polymer and the vinyl polymer are phase-separated and the phase composed of the non-crosslinked polymer is dispersed in the phase composed of the vinyl polymer. It was confirmed that the polymer particles had inside the polymer particles. In addition, the maximum value of the length of the phase composed of the non-crosslinked polymer present inside the obtained polymer particles is based on the long diameter of the pores inside the particles confirmed in the TEM image after extraction of the non-crosslinked polymer. It was 960 nm when measured.

[Example 7: Production of polymer particles]
In a 500 ml flask, 5 g of hydroxypropylmethylcellulose (Metroze (registered trademark) 65SH-50 manufactured by Shin-Etsu Chemical Co., Ltd.) as a suspension stabilizer was dissolved in 195 g of water, and a dispersion medium containing the suspension stabilizer Was obtained in the form of an aqueous solution.

  On the other hand, 36 g of methyl methacrylate as a monofunctional vinyl monomer and 24 g of trimethylolpropane trimethacrylate as a polyfunctional vinyl monomer (based on 100 parts by weight of methyl methacrylate as a monofunctional vinyl monomer) 66.7 parts by weight) and 3 g of the non-crosslinked polymer (5) obtained in Production Example 5 of the non-crosslinked polymer (8.3% with respect to methyl methacrylate as the monofunctional vinyl monomer) Parts by weight) and 0.8 g of t-butylperoxyneodecanoate as a polymerization initiator were uniformly mixed and dissolved to prepare a monomer mixture.

  This monomer mixture was gradually added dropwise to the dispersion medium in the flask. The dispersion medium in which the monomer mixture was dropped was stirred for 15 minutes, and then subjected to a polymerization reaction at 50 ° C. for 30 minutes and then at 63 ° C. for 4 hours.

  Next, the reaction solution in the flask was cooled to room temperature with stirring, and then the reaction solution was suction filtered. The residue of filtration was washed with ion-exchanged water and drained, and then dried in an oven at 80 ° C. for 2 hours to obtain the intended polymer particles.

The volume average particle diameter of the obtained polymer particles was 18.1 μm as measured by the measurement method described above. The specific surface area of the obtained polymer particles was 2.74 m ² / g as measured by the measurement method described above.

  Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image of FIG. 8 was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the SEM image and TEM image shown in FIG. 8, it was confirmed that a porous structure was formed on the surface of the polymer particles. In the porous structure formed on the surface of the polymer particles, the pores were present irregularly on the entire surface of the polymer particles. Further, from the TEM image, the number of pores inside the polymer particles is very small compared to the number of pores on the surface of the polymer particles, and almost no pores are formed inside the polymer particles of Example 7. It was recognized that it was not. The center diameter of the plurality of holes formed on the surface of the polymer particles was 1.20 μm as measured by the measurement method described above.

  Further, in the same manner as in Example 1, a non-crosslinked polymer was extracted from the obtained polymer particles, and a cross section of the extracted polymer particles was imaged with a transmission electron microscope (TEM). It was confirmed that a plurality of pores that were not confirmed in the TEM image of the polymer particles before extraction of the non-crosslinked polymer were present inside the particles after extraction of. Therefore, the polymer particles of Example 7 have a sea-island structure in which the non-crosslinked polymer and the vinyl polymer are phase-separated, and the phase composed of the non-crosslinked polymer is dispersed in the phase composed of the vinyl polymer. It was confirmed that the polymer particles had inside the polymer particles. In addition, the maximum value of the length of the phase composed of the non-crosslinked polymer present inside the obtained polymer particles is based on the long diameter of the pores inside the particles confirmed in the TEM image after extraction of the non-crosslinked polymer. To be 2760 nm.

[Comparative Example 1: Production of polymer particles]
Polymer particles were obtained in the same manner as in Example 3 except that the non-crosslinked polymer (1) obtained in Production Example 1 of the non-crosslinked polymer was not used.

  The volume average particle diameter of the obtained polymer particles was 29.6 μm as measured by the measurement method described above. Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the TEM image and SEM image, a porous structure could not be confirmed on the surface of the polymer particles.

[Comparative Example 2: Production of polymer particles]
Polymer particles were obtained in the same manner as in Example 1 except that the non-crosslinked polymer (1) obtained in Production Example 1 of the non-crosslinked polymer was not used.

  The volume average particle diameter of the obtained polymer particles was 52.0 μm as measured by the measurement method described above. Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the TEM image and SEM image, a porous structure could not be confirmed on the surface of the polymer particles.

[Comparative Example 3: Production of polymer particles]
5 g of non-crosslinked polymer (1) obtained in Production Example 1 of non-crosslinked polymer (0.5 parts by weight with respect to 100 parts by weight of butyl acrylate as a monofunctional vinyl monomer) Except for the above, polymer particles were obtained in the same manner as in Example 1.

  The volume average particle diameter of the obtained polymer particles was 41.8 μm as measured by the measurement method described above. Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the TEM image and SEM image, a porous structure could not be confirmed on the surface of the polymer particles.

  Further, in the same manner as in Example 1, a non-crosslinked polymer was extracted from the obtained polymer particles, and the cross section of the polymer particles after extraction was imaged with a transmission electron microscope (TEM). The presence of pores could not be confirmed inside the particles after extraction. Therefore, in the polymer particles of Comparative Example 3, the non-crosslinked polymer and the vinyl polymer were phase-separated, and the phase composed of the non-crosslinked polymer was dispersed in the phase composed of the vinyl polymer. It is thought that the sea-island structure is not formed.

[Comparative Example 4: Production of polymer particles]
550 g of non-crosslinked polymer (1) obtained in Production Example 1 of non-crosslinked polymer (60.4 parts by weight with respect to 100 parts by weight of butyl acrylate as a monofunctional vinyl monomer) The same operation as in Example 1 was performed except that the polymerization stability was poor and particles could not be obtained.

[Comparative Example 5: Production of polymer particles]
Instead of the non-crosslinked polymer (1) obtained in Production Example 1 of the non-crosslinked polymer, 39 g (monofunctional vinyl-based single polymer) of the non-crosslinked polymer (3) obtained in Production Example 3 of the non-crosslinked polymer was used. Polymer particles were obtained in the same manner as in Example 1, except that 4.3 parts by weight was used with respect to 100 parts by weight of butyl acrylate as a monomer.

  The volume average particle diameter of the obtained polymer particles was 41.2 μm as measured by the measurement method described above. Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the TEM image and SEM image, a porous structure could not be confirmed on the surface of the polymer particles.

  Further, in the same manner as in Example 1, a non-crosslinked polymer was extracted from the obtained polymer particles, and the cross section of the polymer particles after extraction was imaged with a transmission electron microscope (TEM). The presence of pores could not be confirmed inside the particles after extraction. Therefore, in the polymer particles of Comparative Example 5, the non-crosslinked polymer and the vinyl polymer were phase-separated, and the phase composed of the non-crosslinked polymer was dispersed in the phase composed of the vinyl polymer. It is thought that the sea-island structure is not formed.

[Comparative Example 6: Production of polymer particles]
Instead of 3 g of the non-crosslinked polymer (5) obtained in Production Example 5 of the non-crosslinked polymer, 6 g of pure non-crosslinked polymer (6) containing toluene obtained in Production Example 6 of the non-crosslinked polymer The polymer particles were obtained in the same manner as in Example 7 except that 8.3 parts by weight in terms of pure part was used with respect to methyl methacrylate as the monofunctional vinyl monomer. Obtained.

The volume average particle diameter of the obtained polymer particles was 22.3 μm as measured by the measurement method described above. The specific surface area of the obtained polymer particles was 3.79 m ² / g as measured by the measurement method described above.

  Moreover, the obtained polymer particle was imaged with the scanning electron microscope (SEM), and the SEM image of FIG. 9 was obtained. Further, the obtained polymer particles were embedded in an epoxy resin, then cut into thin film sections, stained with ruthenium tetroxide, and the cross section was imaged with a transmission electron microscope (TEM) to obtain a TEM image. . From the SEM image and TEM image shown in FIG. 9, it was confirmed that a porous structure was formed on the surface of the polymer particles. Further, from the TEM image, it was confirmed that a large number of holes were formed inside the polymer particles. Further, the center diameter of the plurality of holes formed on the surface of the polymer particles was 0.04 μm as measured by the measurement method described above.

  Further, in the same manner as in Example 1, a non-crosslinked polymer was extracted from the obtained polymer particles, and the cross section of the polymer particles after extraction was imaged with a transmission electron microscope (TEM). The presence of pores could not be confirmed inside the particles after extraction. Therefore, in the polymer particles of Comparative Example 6, the non-crosslinked polymer and the vinyl polymer were phase-separated, and the phase composed of the non-crosslinked polymer was dispersed in the phase composed of the vinyl polymer. It is thought that the sea-island structure is not formed.

  In Tables 1 and 2 below, the amounts of raw materials used in the production of the polymer particles of Examples 1 to 7 and Comparative Examples 1 to 6, and the characteristics of the obtained polymer particles (volume average particle diameter, specific surface area, The presence or absence of a surface porous structure, the center diameter, the presence or absence of a sea-island structure, and the maximum value of the length of a phase composed of a non-crosslinked polymer). The “presence / absence of the sea-island structure” described in Tables 1 and 2 specifically means that the vinyl polymer and the non-crosslinked polymer are phase-separated, and the non-cross-linked polymer is contained in the phase composed of the vinyl polymer. It means presence or absence of formation of a sea-island structure in which a phase composed of a crosslinked polymer is dispersed. Moreover, in Table 2, the usage-amount of the non-crosslinked polymer (6) of the comparative example 6 is shown by the quantity (amount remove | excluding toluene) converted into a pure part.

  From the results of Examples 1 to 7 and Comparative Examples 1 to 6 shown in Tables 1 and 2, a predetermined non-crosslinked polymer, a monofunctional vinyl monomer, and a polyfunctional vinyl monomer are used at a predetermined ratio. The obtained polymer particles of the present invention (polymer particles obtained in Examples 1 to 7) were obtained by phase-separating the non-crosslinked polymer and the vinyl polymer into the phase composed of the vinyl polymer. It has a sea-island structure in which a phase composed of a non-crosslinked polymer is dispersed, and a surface porous structure having a plurality of pores with a center diameter of 0.1 to 2 μm on the surface of the polymer particles. I was able to confirm.

[Example 8: Production example of cosmetic]
10 parts by weight of polymer particles obtained in Example 1, 40 parts by weight of talc as clay minerals, 23 parts by weight of mica as clay minerals, 1 part by weight of red iron oxide as a coloring material raw material, 1 part by weight of yellow iron oxide as a color material material and 0.1 part by weight of black iron oxide as a color material material were mixed with a Henschel mixer. Thereafter, 5 parts by weight of petrolatum as a hydrocarbon, 2 parts by weight of octyldodecyl myristate as a fatty acid ester, an appropriate amount of preservative, and an appropriate amount of perfume were supplied to a Henschel mixer and mixed uniformly. The obtained mixture was pulverized and passed through a sieve, and then compression molded to obtain a powder foundation.

[Comparative Example 7: Production Example of Comparative Cosmetics]
A powder foundation was obtained by the same formulation and operation as in Example 8, except that the polymer particles obtained in Comparative Example 2 were used instead of the polymer particles obtained in Example 1.

  The cosmetics (powder foundation) obtained in Example 8 and Comparative Example 7 were subjected to sensory evaluation (sensory test) by 10 panelists (participants in sensory evaluation). Three evaluation items were selected as evaluation items in this sensory evaluation: moist feeling, soft feeling, and elongation. Each of the three evaluation items of the cosmetics obtained in Example 8 and Comparative Example 7 was subjected to a five-step sensory evaluation based on the following criteria.

1 ... bad 2 ... somewhat bad 3 ... normal 4 ... somewhat good 5 ... good Table 3 shows the results of this sensory evaluation. In addition, the numerical value in a table | surface is an average value of the evaluation result of 10 persons.

  From the results in Table 3 above, it was confirmed that the cosmetics containing the polymer particles according to the present invention had excellent moist feeling, soft feeling, and elongation, and had excellent properties.

[Example 9: Production example of paint]
1 part by weight of the polymer particles obtained in Example 1, a commercially available aqueous resin binder liquid (“Vainal (registered trademark) MD-1200” manufactured by Toyobo Co., Ltd., water-dispersed high molecular weight copolymerized polyester resin, solid content 34 parts by weight) and 20 parts by weight were mixed for 10 minutes using a stirring deaerator and deaerated for 1 minute to obtain a paint (coating composition).

  The obtained coating material was applied to an ABS (acrylonitrile-butadiene-styrene copolymer resin) plate having a thickness of 2 mm using a coating apparatus on which a doctor blade having a clearance of 75 μm was set, and then dried to obtain a coating film.

[Comparative Example 8: Production Example of Comparative Paint]
A paint (coating composition) was obtained in the same manner as in Example 9, except that the polymer particles obtained in Comparative Example 2 were used in place of the polymer particles obtained in Example 1.

  In accordance with the method described in JIS Z8741, the gloss at 60 ° of the coating films of Example 9 and Comparative Example 8 was measured using a gloss checker (gloss meter) (IG-331) manufactured by Horiba, Ltd. It was measured. Table 4 shows the evaluation results (gloss and matte properties) of the coating films of Example 9 and Comparative Example 8.

    From the results of Table 4 above, the coating film obtained from the coating material containing the polymer particles according to the present invention has a lower gloss value than the coating film of the comparative example, and the polymer particles (Examples) of the present invention have a small amount. It has been found that a high matting effect can be obtained with the addition of.

[Example 10: Production example of light diffusing resin composition]
In an oven, 1 part by weight of the polymer particles obtained in Example 1 and 100 parts by weight of a polymethyl methacrylate resin (“SUMIPEX (registered trademark) EXA” manufactured by Sumitomo Chemical Co., Ltd.) as a transparent base resin are placed in an oven. It was dried at 90 ° C. for 3 hours. These dried products were put into an extruder, melt-kneaded at 250 ° C. in the extruder, and then pelletized. The obtained pellets were molded by an injection molding machine (cylinder temperature 270 ° C., residence time 15 minutes) to obtain a light diffusing resin composition having a thickness of 2 mm × 50 mm × 100 mm.

[Comparative Example 9: Production Example of Comparative Light Diffusing Resin Composition]
A light diffusing resin composition was obtained in the same manner as in Example 10 except that the polymer particles obtained in Comparative Example 2 were used in place of the polymer particles obtained in Example 1.

  The haze (haze) and total light transmittance of the light diffusing resin compositions obtained in Example 10 and Comparative Example 9 were measured using a haze meter “NDH-2000” manufactured by Nippon Denshoku Industries Co., Ltd. . The total light transmittance was measured according to JIS K 7361-1, and the haze was measured according to JIS K 7136. Table 5 shows the evaluation results (haze and total light transmittance) of the light diffusing resin compositions of Example 10 and Comparative Example 9. In addition, the total light transmittance and haze shown in Table 5 are average values of the measurement values of five measurement samples (measurement sample number n = 5).

  From the results of Table 5, since the polymer particles of the present invention have a plurality of pores on the entire particle surface, the haze of the light diffusing resin composition can be increased by adding a small amount. The light diffusing resin composition containing the polymer particles is useful for effectively erasing the lamp image when used as a diffusion plate for a liquid crystal display device, a molded article for a lighting cover, or the like. I understood that.

[Example 11: Example of surface treatment of polymer particles, and Example of production of cosmetics containing surface-treated polymer particles]
100 parts by weight of the polymer particles obtained in Example 1 were put into a mixer, and stirred at room temperature (about 25 ° C.), methylhydrogenpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone compound. Shin-Etsu Silicone (registered trademark) KF99 ") and a mixture of 7 parts by weight of ethanol as a solvent were gradually added to the polymer particles, and then the temperature in the mixer was raised to 60 ° C. The ethanol was evaporated. Next, the temperature in the mixer was set to 130 ° C., and the polymer particles were heated for 3 hours to obtain polymer particles whose surface was treated with a silicone compound.

  Next, 10 parts by weight of polymer particles whose surface is treated with this silicone compound, 40 parts by weight of talc as clay minerals, 23 parts by weight of mica as clay minerals, and red iron oxide 1 as a color material raw material 1 Part by weight, 1 part by weight of yellow iron oxide as a color material material, and 0.1 part by weight of black iron oxide as a color material material were mixed with a Henschel mixer. Thereafter, 5 parts by weight of petrolatum as a hydrocarbon, 2 parts by weight of octyldodecyl myristate as a fatty acid ester, an appropriate amount of preservative, and an appropriate amount of perfume were supplied to a Henschel mixer and mixed uniformly. The obtained mixture was pulverized and passed through a sieve, and then compression molded to obtain a powder foundation.

[Comparative Example 10: Production Example of Comparative Cosmetics]
A powder foundation was obtained by the same formulation and operation as in Example 11 except that the polymer particles obtained in Comparative Example 2 were used in place of the polymer particles obtained in Example 1.

  For the cosmetics (powder foundation) obtained in Example 11 and Comparative Example 10, sensory evaluation (sensory test) was performed by 10 panelists (participants in sensory evaluation). Three evaluation items were selected as evaluation items in this sensory evaluation: moist feeling, soft feeling, and elongation. Each of the three evaluation items of the cosmetics obtained in Example 11 and Comparative Example 10 was subjected to a five-step sensory evaluation based on the following criteria.

1 ... bad 2 ... slightly bad 3 ... normal 4 ... slightly good 5 ... good Table 6 shows the results of this sensory evaluation. In addition, the numerical value in a table | surface is an average value of the evaluation result of 10 persons.

  From the results of Table 6 above, it was found that the cosmetic containing the polymer particles according to the present invention has excellent moist feeling, soft feeling, and elongation, and has excellent properties. Moreover, the difference of the tactile sensation (moist feeling, soft feeling, and elongation) between the cosmetic according to Example 11 and the cosmetic according to Comparative Example 10 is related to the cosmetic according to Example 8 and Comparative Example 7 described above. It was large compared to the difference in feel (moist feeling, soft feeling, and elongation) with the cosmetic. This is because the surface of the polymer particles is treated with a silicone compound so that the polymer particles have high water repellency, and when the polymer particles are blended into cosmetics, a smoother tactile sensation is imparted to the cosmetics. It is thought that it was because of.

  The present invention can be implemented in various other forms without departing from the spirit or main features thereof. For this reason, the above-described embodiment is merely an example in all respects and should not be interpreted in a limited manner. The scope of the present invention is indicated by the claims, and is not restricted by the text of the specification. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.

  This application claims priority based on Japanese Patent Application No. 2012-102388 filed in Japan on April 27, 2012. By this reference, the entire contents thereof are incorporated into the present application.

  The polymer particles of the present invention include, for example, paint additives (matting agents, coating film softening agents, design imparting agents, etc.), ink additives (matting agents, pressure-sensitive adhesives, etc.), and adhesives. Topical agents or additives, additives for artificial marble (low shrinkage agents, etc.), fillers for paper treatment agents, fillers for cosmetics (fillers for improving slipperiness), etc. Raw materials, column fillers for chromatography, toner additives used for electrostatic charge image development, anti-blocking agents for films, light diffusers (lighting covers, light diffusion sheets, light diffusion films, etc.) It can be used for applications such as a light diffusing agent.

  Further, the external preparation of the present invention can be used as cosmetics, external pharmaceuticals, etc., the paint of the present invention can be used as oil paints, aqueous paints, etc., the light diffusing resin composition of the present invention, It can be used as a raw material for a light diffusing member such as an illumination cover, a light diffusing sheet, or a light diffusing film (a raw material used for forming the light diffusing member).

Claims (10)

A vinyl polymer derived from a monomer mixture containing 100 parts by weight of a monofunctional vinyl monomer and 5 to 100 parts by weight of a polyfunctional vinyl monomer, and an alkyl having a branched alkyl group of C3 to C20 (meta And 1 to 15.4 parts by weight of a non-crosslinked polymer having a weight average molecular weight of 50,000 to 200,000 derived from a monomer containing 50% by weight or more of an acrylate, and a plurality of pores having a center diameter of 0.1 to 2 μm on the surface A polymer particle comprising a surface porous structure having a specific surface area of 0.1 to 5.0 m ² / g and a volume average particle diameter of 1 to 200 μm. The polymer particles according to claim 1,
The polymer particles have a sea-island structure in which the non-crosslinked polymer and the vinyl polymer are phase-separated and the phase composed of the non-crosslinked polymer is dispersed in the phase composed of the vinyl polymer. Polymer particles characterized by Polymer particles having a surface porous structure having a plurality of pores on the surface,
A vinyl polymer and a non-crosslinked polymer,
The polymer particles have a sea-island structure in which the non-crosslinked polymer and the vinyl polymer are phase-separated and the phase composed of the non-crosslinked polymer is dispersed in the phase composed of the vinyl polymer. ,
The center diameter of the plurality of holes present on the surface is 0.1 to 2 μm, the specific surface area is 0.1 to 5.0 m ² / g, and the volume average particle diameter is 1 to 200 μm. Coalesced particles. The polymer particles according to claim 2 or 3,
Polymer particles, wherein the phase length of the non-crosslinked polymer is 50 to 3000 nm. The polymer particle according to any one of claims 1 to 4,
Polymer particles, wherein the surface is treated with an oil agent, a silicone compound, or a fluorine compound. A monomer mixture containing 100 parts by weight of a monofunctional vinyl monomer and 5 to 100 parts by weight of a polyfunctional vinyl monomer, and 50% by weight of alkyl (meth) acrylate having a C3-C20 branched alkyl group By carrying out suspension polymerization in an aqueous medium in the presence of 1 to 15.4 parts by weight of a non-crosslinked polymer having a weight average molecular weight of 50,000 to 200,000 derived from the above-mentioned monomers and a polymerization initiator, a center diameter of 0.1 Obtaining polymer particles having a surface porous structure having a plurality of pores of ˜2 μm on the surface, a specific surface area of 0.1 to 5.0 m ² / g, and a volume average particle diameter of 1 to 200 μm. A method for producing polymer particles, which is characterized. It is a manufacturing method of the polymer particle according to claim 6,
A sea-island structure in which the vinyl polymer derived from the monomer mixture and the non-crosslinked polymer are phase-separated and the phase composed of the non-crosslinked polymer is dispersed in the phase composed of the vinyl polymer. A method for producing polymer particles, comprising: obtaining the polymer particles in a container.   An external preparation comprising the polymer particles according to any one of claims 1 to 5.   A paint comprising the polymer particles according to claim 1.   A light-diffusing resin composition comprising the polymer particles according to claim 1 and a transparent base resin.