Silicone-acrylic graft copolymer resin powder, method for producing same, resin composition, and cosmetic

Abstract

The present invention is a silicone-acrylic graft copolymer resin powder that includes a graft copolymer resin of (I) a polyorganosiloxane represented by general formula (1), and (II) an acrylic acid ester monomer and / or methacrylic acid ester monomer, and is characterized in that the mass ratio of (I) the polyorganosiloxane and (II) the acrylic acid ester monomer and / or methacrylic acid ester monomer when the total mass is 100 is (I) : (II) = 60-99 : 1-40, the octamethylcyclotetrasiloxane content in the powder is 1000 ppm or less, and the residual moisture content is 5% or less. Thereby, provided are a silicone-acrylic graft copolymer resin powder having a reduced octamethylcyclotetrasiloxane content, a method for producing the same, a resin composition, and cosmetic.

Description

Silicone acrylic graft copolymer resin powder, method for producing the same, and resin composition and cosmetic

[0001] This invention relates to silicone acrylic graft copolymer resin powder, a method for producing the same, and resin compositions and cosmetics.

[0002] Traditionally, powdered silicone acrylic graft copolymer resins have been used to impart lubricity and a pleasant tactile feel to substrates such as leather and resins, as well as cosmetics, and various studies have been conducted on them.

[0003] In recent years, there has been a growing demand for silicone-based products with reduced octamethylcyclotetrasiloxane content. Methods described in Patent Documents 1 and 2 are known to result in emulsions containing octamethylcyclotetrasiloxane at concentrations of 40,000 ppm or more, and methods to reduce this content are being investigated.

[0004] Patent Document 3 discloses a method for producing an organopolysiloxane emulsion composition that suppresses the by-product formation of octamethylcyclotetrasiloxane contained in organopolysiloxane, and in which the high-viscosity organopolysiloxane has a branched structure, small particle size, and good stability over time.

[0005] However, little research has been conducted on silicone powders with reduced octamethylcyclotetrasiloxane content, and no research has been conducted on acrylic graft copolymer resins with reduced octamethylcyclotetrasiloxane content. Nevertheless, there is a possibility that products with reduced octamethylcyclotetrasiloxane content will be required in the powder field and silicone-acrylic graft copolymer resins in the future, indicating room for improvement.

[0006] Japanese Patent Publication No. 56-038609, Japanese Patent Publication No. 63-286434, Japanese Patent Publication No. 2017-48342

[0007] The present invention has been made in view of the above circumstances, and aims to provide a silicone acrylic graft copolymer resin powder with reduced octamethylcyclotetrasiloxane, a method for producing the same, a resin composition, and a cosmetic.

[0008] To solve the above problems, the present invention provides a silicone acrylic graft copolymer resin powder comprising (I) a polyorganosiloxane represented by the following general formula (1), (In the formula, R １ These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms (however, R described below) ２ (Excluding the groups defined by and the phenyl group), R ２ R is an alkyl group having 1 to 6 carbon atoms, in which some of the hydrogen atoms bonded to the carbon atoms are substituted with a mercapto group, a vinyl group, an acryloxy group, or a methacryloxy group, independently of each other. ３ These are independently of each other, a phenyl group or the above R １ A group defined by and at least one R ３ is a phenyl group, X is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, a, b, c, and d are real numbers, and for the sum of a, b, c, and d, a is a number such that 0.11 ≤ a / (a+b+c+d) < 1, b is a number such that 0.00001 ≤ b / (a+b+c+d) ≤ 0.05, c is a number such that 0 ≤ c / (a+b+c+d) ≤ 0.6, and d is a number such that 0.000001 ≤ d / (a+b+c+d) ≤ 0.24. (II) A powder containing a graft copolymer resin of an acrylic acid ester monomer and / or a methacrylic acid ester monomer, wherein the mass ratio of the polyorganosiloxane of (I) and the acrylic acid ester monomer and / or methacrylic acid ester monomer of (II) when the total mass is 100 is (I):(II) = 60 to 99:1 to 40, and the content of octamethylcyclotetrasiloxane in the powder is 1000 ppm or less, and the residual moisture content is 5% or less.

[0009] If it is a silicone acrylic graft copolymer resin powder containing a graft copolymer resin obtained by graft polymerizing the above component (I) and the above component (II) at a specific blending ratio, octamethylcyclotetrasiloxane can be reduced, and a silicone acrylic graft copolymer resin powder that takes into account the regulation of residual organic pollutants can be provided.

[0010] Further, it is preferable that the molecular weight of the polyorganosiloxane of the above (I) is 5,000 to 500,000.

[0011] By having the polyorganosiloxane of the above (I) have the above molecular weight, good slipperiness peculiar to silicone can be imparted.

[0012] Further, it is preferable that the average particle diameter of the silicone acrylic graft copolymer resin powder of the present invention is 1 to 500 μm.

[0013] If it is within the range of the above average particle diameter, slidability can be imparted to the silicone acrylic graft copolymer resin powder of the present invention.

[0014] Further, the silicone acrylic graft copolymer resin powder can be made into a resin composition containing 0.1 to 20% by mass of a solid content with respect to the mass of the entire resin composition.

[0015] By including the silicone acrylic graft copolymer resin powder of the present invention within the range of the above solid content, excellent touch, water repellency, and slidability can be imparted to the above resin composition.

[0016] Further, the silicone acrylic graft copolymer resin powder can be made into a cosmetic containing 0.1 to 20% by mass of a solid content with respect to the mass of the entire cosmetic.

[0017] By including the silicone acrylic graft copolymer resin powder within the range of the above solid content, excellent touch, water repellency, and slidability can be imparted to the above cosmetic.

[0018] Furthermore, the present invention provides a method for producing a silicone-acrylic graft copolymer resin powder, comprising: adding an acrylic acid ester monomer and / or a methacrylic acid ester monomer of (II) to an emulsion containing the polyorganosiloxane of (I) and polymerizing the mixture to obtain a silicone-acrylic graft copolymer emulsion; and spray-drying the silicone-acrylic graft copolymer emulsion.

[0019] According to the method for producing a silicone-acrylic graft copolymer resin powder of the present invention, a silicone-acrylic graft copolymer resin powder with reduced octamethylcyclotetrasiloxane can be produced.

[0020] As described above, according to the silicone-acrylic graft copolymer resin powder and the production method thereof of the present invention, by reducing octamethylcyclotetrasiloxane, not only can consideration be given to the regulation of residual organic pollutants, but also the resin composition and cosmetics using the silicone-acrylic graft copolymer resin powder of the present invention can impart excellent touch, abrasion resistance, water repellency and slidability.

[0021] As described above, there has been a demand for the development of a silicone-acrylic graft copolymer resin powder with reduced octamethylcyclotetrasiloxane.

[0022] As a result of intensive studies to achieve the above object, the present inventors have found that a silicone-acrylic graft copolymer resin powder containing a graft copolymer obtained by graft-polymerizing a (meth)acrylic acid ester monomer to a specific polyorganosiloxane at a specific mixing ratio can reduce octamethylcyclotetrasiloxane, and that the resin composition and cosmetics using the silicone-acrylic graft copolymer resin powder of the present invention can impart excellent touch, abrasion resistance, water repellency, and slidability, thus completing the present invention.

[0023] That is, the present invention relates to a silicone-acrylic graft copolymer resin powder, comprising: (I) a polyorganosiloxane represented by the following general formula (1); (In the formula, R １ is, independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms (however, excluding the group defined by R ２ described later and the phenyl group), R ２ is, independently of each other, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which part of the hydrogen atoms bonded to the carbon atoms are substituted with a mercapto group, a vinyl group, an acryloxy group or a methacryloxy group, R ３ [[ID=S]] is, independently of each other, a phenyl group or the group defined by the above R １ , at least one R ３ is a phenyl group, X is, independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, a, b, c and d are real numbers, and with respect to the sum of a, b, c and d, a is a number such that 0.11 ≦ a / (a + b + c + d) < 1, b is a number such that 0.00001 ≦ b / (a + b + c + d) ≦ 0.05, c is a number such that 0 ≦ c / (a + b + c + d) ≦ 0.6, and d is a number such that 0.000001 ≦ d / (a + b + c + d) ≦ 〔〕). (II) A powder containing a graft copolymer resin with an acrylate monomer and / or a methacrylate monomer, When the total mass of the polyorganosiloxane of (I) and the acrylate monomer and / or methacrylate monomer of (II) is 100, the mass ratio is (I):(II) = 60 to 99:1 to 40, The silicone acrylate graft copolymer resin powder is characterized in that the content of octamethylcyclotetrasiloxane in the powder is 1000 ppm or less and the residual moisture content is 5% or less.

[0024] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0025] [Silicone Acrylate Graft Copolymer Resin Powder] The silicone acrylate graft copolymer resin powder of the present invention comprises (I) a polyorganosiloxane represented by the following general formula (1), and (In the formula, R １These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms (however, R described below) ２ (Excluding the groups defined by and the phenyl group), R ２ R is an alkyl group having 1 to 6 carbon atoms, in which some of the hydrogen atoms bonded to the carbon atoms are substituted with a mercapto group, a vinyl group, an acryloxy group, or a methacryloxy group, independently of each other. ３ These are independently of each other, a phenyl group or the above R １ A group defined by and at least one R ３ is a phenyl group, X is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, a, b, c, and d are real numbers, and for the sum of a, b, c, and d, a is a number such that 0.11 ≤ a / (a+b+c+d) < 1, b is a number such that 0.00001 ≤ b / (a+b+c+d) ≤ 0.05, c is a number such that 0 ≤ c / (a+b+c+d) ≤ 0.6, and d is a number such that 0.000001 ≤ d / (a+b+c+d) ≤ 0.24. (II) A powder containing a graft copolymer resin of an acrylic acid ester monomer and / or a methacrylic acid ester monomer, wherein the mass ratio of the polyorganosiloxane of (I) and the acrylic acid ester monomer and / or methacrylic acid ester monomer of (II) when the total mass is 100 is (I):(II) = 60 to 99:1 to 40, and the content of octamethylcyclotetrasiloxane in the powder is 1000 ppm or less, and the residual moisture content is 5% or less.

[0026] More specifically, the graft copolymerization of (I) a polyorganosiloxane represented by the general formula (1) above and (II) an acrylic acid ester monomer and / or a methacrylic acid ester monomer is preferably carried out by emulsion graft polymerization, and the silicone acrylic graft copolymer resin powder of the present invention can be obtained by drying the silicone acrylic graft copolymer emulsion obtained by the emulsion graft polymerization above.

[0027] The mixing ratio of component (I) and component (II) is such that the mass ratio when the total mass of the polyorganosiloxane (I) and the acrylic acid ester monomer and / or methacrylic acid ester monomer (II) is set to 100 is (I):(II) = 60 to 99:1 to 40, preferably with component (I) being 70 to 95 parts by mass and component (II) being 5 to 30 parts by mass.

[0028] [(I) Polyorganosiloxane] Component (I) of the present invention is a polyorganosiloxane represented by the following general formula (1). (In the formula, R １ These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms (however, R described below) ２ (Excluding the groups defined by and the phenyl group), R ２ R is an alkyl group having 1 to 6 carbon atoms, in which some of the hydrogen atoms bonded to the carbon atoms are substituted with a mercapto group, a vinyl group, an acryloxy group, or a methacryloxy group, independently of each other. ３ These are independently of each other, a phenyl group or the above R １ A group defined by and at least one R ３ (where is a phenyl group, X is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, a, b, c, and d are real numbers, and for the sum of a, b, c, and d, a is a number such that 0.11 ≤ a / (a+b+c+d) < 1, b is a number such that 0.00001 ≤ b / (a+b+c+d) ≤ 0.05, c is a number such that 0 ≤ c / (a+b+c+d) ≤ 0.6, and d is a number such that 0.000001 ≤ d / (a+b+c+d) ≤ 0.24.)

[0029] The above R １ These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, preferably monovalent hydrocarbon groups having 1 to 10 carbon atoms, more preferably monovalent hydrocarbon groups having 1 to 6 carbon atoms (however, R described below) ２(Excluding the groups defined as and the phenyl group). For example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, etc., cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, etc., aryl groups such as tolyl group, naphthyl group, etc., alkenylaryl groups such as vinylphenyl group, aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, etc., alkenylaralkyl groups such as vinylbenzyl group, vinylphenylpropyl group, etc., and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, carboxyl group, alkoxy group, alkenyloxy group, amino group, and alkyl or alkoxy groups. １ As such, an unsubstituted alkyl group having 1 to 6 carbon atoms is preferred, and a methyl group is more preferred.

[0030] The above R ２ These are, independently of each other, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which some of the hydrogen atoms bonded to the carbon atoms are substituted with a mercapto group, vinyl group, acryloxy group, or methacryloxy group. Examples of alkenyl groups having 2 to 6 carbon atoms include vinyl groups and allyl groups. The above R ２ Preferably, the alkyl group is a C1-C6 alkyl group having an acryloxy group or a methacryloxy group. The alkyl group is preferably a methyl group, an ethyl group, or a propyl group.

[0031] The above R ３ These are, independently of each other, a phenyl group or the above R １ A group defined by and at least one R ３ It is a phenyl group.

[0032] The above X is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. The above monovalent hydrocarbon group having 1 to 20 carbon atoms is preferably having 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. The above alkoxy group having 1 to 20 carbon atoms is preferably having 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The above R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. １ Examples of groups exemplified for this purpose include alkoxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and tetradecyloxy groups. Preferably, X is a hydroxyl group, methoxy, ethoxy, methyl, or butyl group.

[0033] The above a, b, c, and d are real numbers, and for the sum of a to d, a is a number such that 0.11 ≤ a / (a+b+c+d) < 1 (for example, it can be 0.999999 or less), preferably 0.59 ≤ a / (a+b+c+d) ≤ 0.99998. b is a number such that 0.00001 ≤ b / (a+b+c+d) ≤ 0.05 for the sum of a to d, preferably 0.00001 ≤ b / (a+b+c+d) ≤ 0.01. c is a number such that 0 ≤ c / (a+b+c+d) ≤ 0.6 for the sum of a to d, preferably 0 ≤ c / (a+b+c+d) ≤ 0.30. d is a number such that 0.000001 ≤ d / (a+b+c+d) ≤ 0.24 with respect to the total number of a to d, and preferably 0.00001 ≤ d / (a+b+c+d) ≤ 0.1. If b exceeds 5% (i.e., 0.05), the improvement in the tactile feel of the coating film will not be observed, and the antifouling properties will also decrease. If d exceeds 24.0% (i.e., 0.24), the weight-average molecular weight will decrease, and the improvement in tactile feel will not be observed. c is the number of siloxane units having a phenyl group. If c falls outside the above range, there is a risk of inferior transparency and heat resistance. If a falls outside the above range, there is a risk of not being able to obtain sufficient sliding properties.

[0034] The molecular weight (M) of the polyorganosiloxane (I) described above is preferably 5,000 to 500,000, more preferably 8,000 to 450,000, even more preferably 100,000 to 450,000, and most preferably 150,000 to 400,000. Having this molecular weight allows for the provision of the excellent lubricity characteristic of silicone.

[0035] Here, the molecular weight (M) of the polyorganosiloxane can be calculated from the specific viscosity ηsp (at 25°C) of a toluene solution of polyorganosiloxane at a concentration of 1 g / 100 ml. ηsp = (η / η0) - 1 (η0: viscosity of toluene, η: viscosity of the solution) ηsp = [η] + 0.3[η] ２ [η]=2.15×10 －４ M ０．６５

[0036] Specifically, 20 g of emulsion is mixed with 20 g of IPA (isopropyl alcohol), the emulsion is broken down, the IPA is discarded, and the remaining rubbery polyorganosiloxane is dried at 105°C for 3 hours. This is then prepared as a toluene solution of polyorganosiloxane at a concentration of 1 g / 100 ml, and its viscosity is measured at 25°C using an Ubbelohde viscometer. The molecular weight (M) can be determined by substituting the viscosity into the above formula (References: Nakamuta, Nichika, 77 858

[1956] , Doklady Akad. Nauk. U.S.S.R. 89 65

[1953] ).

[0037] As described above, it is preferable to emulsion graft polymerization of the above (I) polyorganosiloxane and the above (II) acrylic acid ester monomer and / or methacrylic acid ester monomer. Specifically, it is preferable to add (II) to an emulsion containing (I) and carry out emulsion graft polymerization.

[0038] Such emulsions containing (I) polyorganosiloxane may be obtained by emulsifying the corresponding polyorganosiloxane by a known method, or by emulsifying the monomer or macromer and carrying out a polymerization reaction in the emulsified particles.

[0039] When emulsifying using the corresponding polyorganosiloxane by a known method, it can be prepared, for example, by mixing the polyorganosiloxane, a surfactant, and water, and then emulsifying and dispersing it in accordance with conventional methods.

[0040] When emulsifying the above monomer or macromer and carrying out the polymerization reaction in the emulsified particles, it can be carried out by known emulsion polymerization methods. For example, organosiloxanes such as diorganocyclosiloxanes, α,ω-dihydroxydiorganosiloxane oligomers, and α,ω-dialkoxydiorganosiloxane oligomers, which may have substituents, and a silane coupling agent represented by the following general formula (2) are emulsified and dispersed in water using a surfactant, and then an acid catalyst is added as needed to carry out the polymerization reaction. ５ （４－ｅ－ｆ） R ６ ｆ Si ( OR ７ ) ｅ (2) (wherein, R ５ R represents a monovalent organic group having a polymerizable double bond, particularly an alkyl group having 1 to 6 carbon atoms substituted with an acryloxy group or a methacryloxy group. ６ R is an alkyl group having 1 to 4 carbon atoms. ７ (where e is an alkyl group having 1 to 4 carbon atoms, e is an integer between 2 and 3, and f is an integer between 0 and 1, so e + f = 2 to 3.)

[0041] The silane coupling agents mentioned above specifically include vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane; γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropyltriisopropoxysilane, and γ-(meth)acryloxypropyltriisopropoxysilane. Examples include acrylic silanes such as roxypropyltributoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxypropylmethyldiisopropoxysilane, and γ-(meth)acryloxypropylmethyldibutoxysilane; and mercaptosilanes such as γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropyltrimethoxysilane. Alternatively, oligomers obtained by condensation polymerization of these may be more preferable as they suppress the generation of alcohols. In this specification, (meth)acryloxy refers to acryloxy or methacryloxy. These silane coupling agents are preferably used in amounts of 0.01 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass, per 100 parts by mass of organosiloxane, which is a monomer or macromer. If the amount is 0.01 parts by mass or more, it will be transparent when used as a coating agent, and if the amount is 10 parts by mass or less, it will exhibit sufficient sliding properties.

[0042] By copolymerizing the above silane coupling agent, the effect of grafting the monomer of component (II) can be obtained.

[0043] As needed, any known polymerization catalyst may be used as the acid catalyst in the polymerization reaction. Examples include hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, ascorbic acid, alkyl sulfate, or their salts. If the surfactants listed below have catalytic activity, the above acid catalyst may not be necessary.

[0044] The amount of the above-mentioned acid catalyst used is preferably 0.01 to 10 parts by mass, and more preferably 0.2 to 2 parts by mass, per 100 parts by mass of polyorganosiloxane.

[0045] Furthermore, it is preferable that the surfactant used during polymerization contains at least an anionic surfactant. Examples of anionic surfactants include sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyl taurine salts, aliphatic soaps, alkyl phosphates, alkylnaphthalene sulfonic acid or its salts, among which alkylnaphthalene sulfonic acid or its salts are preferred. Specific examples include butylnaphthalene sulfonic acid, pentylnaphthalene sulfonic acid, decylnaphthalene sulfonic acid, dodecylnaphthalene sulfonic acid, tetradecylnaphthalene sulfonic acid, hexadecylnaphthalene sulfonic acid, isopropylnaphthalene sulfonic acid, bisisopropylnaphthalene acid, trisisopropylnaphthalene acid and its salts.

[0046] The amount of the above-mentioned anionic surfactant used can be 1 to 8 parts by mass, preferably 2 to 7 parts by mass, and more preferably 3 to 6 parts by mass, per 100 parts by mass of the polyorganosiloxane component.

[0047] The above-mentioned surfactants may include nonionic surfactants, which can be used individually or in combination of two or more. When using nonionic surfactants, the amount is preferably 0.1 to 8 parts by mass per 100 parts by mass of the polyorganosiloxane component.

[0048] Examples of the above-mentioned nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene propylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene fatty acid esters. Among these, nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene propylene alkyl ethers are preferred in terms of stability.

[0049] Specific examples of these include polyoxyethylene octyl ether, polyoxyethylene polyoxypropylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene oxypropylene decyl ether, polyoxyethylene polyoxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene polypropylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether. It is also possible to use reactive surfactants having functional groups. These surfactants can be used individually or in combination of two or more. The alkyl groups can be linear or branched.

[0050] The polymerization temperature is preferably 20°C or lower, the polymerization time is preferably 10 hours or more, and more preferably 15 hours or more.

[0051] The viscosity of the emulsion containing the polyorganosiloxane described above (I) with a solid content of 35-55% is preferably less than 1,000 mPa·s.

[0052] The content of octamethylcyclotetrasiloxane in the emulsion containing the above (I) polyorganosiloxane is preferably 3,000 ppm (by mass, the same applies hereinafter) or less, more preferably 1,000 ppm or less, and even more preferably 500 ppm or less. The lower limit is not particularly limited and may be 0 ppm.

[0053] The average particle size of the emulsion containing (I) polyorganosiloxane is preferably 1 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The particle size of the emulsion was measured using a laser diffraction / scattering particle size distribution analyzer LA-950 (manufactured by Horiba, Ltd.).

[0054] The following methods are examples of methods for reducing the average particle size of the emulsion containing the polyorganosiloxane described above (I). For example, when using a high-pressure homogenizer (an emulsifier that pressurizes the processing liquid to high pressure or ultra-high pressure and obtains shear force by passing it through a slit, or an emulsifier that atomizes by causing pressurized processing liquids to collide obliquely at ultra-high speed) to reduce the particle size of emulsion particles using high pressure, the amount of water used is preferably 1 to 10,000 parts by mass, more preferably 4 to 6,000 parts by mass, and even more preferably 6 to 4,000 parts by mass, per 100 parts by mass of the polyorganosiloxane component.

[0055] Furthermore, when using emulsifiers such as homodispers (emulsifiers that obtain shear force by rapidly rotating a circular disc with saw-toothed teeth on its outer circumference), homomixers (emulsifiers that generate shear force by rapidly rotating a rotor installed inside with a stator installed on the outer circumference), and colloid mills (emulsifiers that generate shear force by feeding each component into the gap between a rapidly rotating disc and a fixed disc to generate shear force), the amount of water used is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, and even more preferably 4 to 6 parts by mass, per 100 parts by mass of polyorganosiloxane component. Here, adding 10 parts by mass or less makes it easy to obtain the above emulsion with a particle size of 1 μm or less, and adding 1 part by mass or more makes it easier to obtain an O / W type emulsion, which is preferable.

[0056] [(II) Acrylic acid monomer and / or methacrylic acid monomer] The (II) acrylic acid monomer and / or methacrylic acid monomer (hereinafter sometimes referred to as the acrylic component) used in the present invention is not particularly limited as long as it is the above-mentioned acrylic component, but examples include those based on linear and branched esters having 1 to 20 carbon atoms and having functional groups such as amide groups, vinyl groups, carboxyl groups, and hydroxyl groups.

[0057] Examples of the acrylic components mentioned above include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. Only one of these, or two or more, may be copolymerized with (I) polyorganosiloxane. Preferably, it is methyl acrylate, ethyl acrylate, methyl methacrylate, or ethyl methacrylate. The acrylic acid ester and methacrylic acid ester preferably have a glass transition temperature (hereinafter sometimes referred to as Tg) of 120°C or less, and more preferably 110°C or less. The lower limit is preferably -50°C. The (II) component is adjusted so that the Tg of the resulting silicone acrylic graft copolymer resin is 0°C or higher, preferably 5°C or higher, and then graft copolymerized. By having the silicone acrylic graft copolymer resin have the above Tg, a resin with high antifouling performance can be obtained.

[0058] The calculation method for Tg is as follows: (Pa + Pb + Pc) / T = (Pa / Ta) + (Pb / Tb) + (Pc / Tc) In this formula, T represents the glass transition temperature (K) of the polymer particles, Pa, Pb, and Pc represent the mass %) content of monomers a, b, and c, respectively, and Ta, Tb, and Tc represent the homopolymer glass transition temperatures (K) of monomers a, b, and c, respectively. The glass transition temperature can be measured according to JIS K 7121.

[0059] [Method for producing silicone acrylic graft copolymer resin powder] The present invention provides a method for producing silicone acrylic graft copolymer resin powder, comprising the steps of: adding the acrylic acid ester monomer and / or methacrylic acid ester monomer described in (II) to an emulsion containing the polyorganosiloxane described in (I) above and polymerizing it to obtain a silicone acrylic graft copolymer emulsion; and spray-drying the silicone acrylic graft copolymer emulsion.

[0060] The method for preparing the emulsion containing the polyorganosiloxane described in (I) above is as described in the section [(I) Polyorganosiloxane] above, and it is preferable to emulsion graft polymerization of the polyorganosiloxane described in (I) above and the acrylic acid ester monomer and / or methacrylic acid ester monomer described in (II) above. Specifically, it is preferable to add (II) to the emulsion containing (I) and carry out emulsion graft polymerization.

[0061] The graft copolymerization of the above (I) polyorganosiloxane and the above (II) (meth)acrylic acid ester monomer can be carried out according to conventionally known methods, for example, using a radical initiator.

[0062] Radical initiators used here include persulfates such as potassium persulfate and ammonium persulfate, hydrogen persulfate solution, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, redox systems using reducing agents such as sodium acidic sulfite, rongalit, L-ascorbic acid, tartaric acid, sugars, and amines can also be used.

[0063] To improve stability, anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyl taurine salts, aliphatic soaps, and alkyl phosphates can be added. Nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can also be added.

[0064] Furthermore, a chain transfer agent can be added to adjust the molecular weight.

[0065] The obtained silicone acrylic graft copolymer resin emulsion is then subjected to drying after salting out, and spray drying, to obtain the silicone acrylic graft copolymer resin powder of the present invention. At this time, the residual moisture content must be 5% or less. If the residual moisture content exceeds 5%, there is a risk of air bubbles forming in the molded product.

[0066] Furthermore, the content of octamethylcyclotetrasiloxane in the silicone acrylic graft copolymer resin powder of the present invention is 1000 ppm or less, more preferably 500 ppm or less, and more preferably 300 ppm or less. The lower limit is not particularly limited and may be 0 ppm.

[0067] The particle size of the silicone acrylic graft copolymer resin powder of the present invention is preferably 1 to 500 μm, and more preferably 5 to 300 μm, based on the particle size measured in a methanol dispersion using a laser diffraction particle size analyzer. Within this range, the desired sliding properties are achieved.

[0068] [Resin Composition] The resin composition of the present invention preferably comprises: (A) the silicone acrylic graft copolymer resin powder described above: 0.1 to 20% by mass in terms of solid content; (B) thermoplastic resin other than the component in (A): 35 to 99.9% by mass, more preferably 80 to 99.9% by mass in terms of solid content.

[0069] Examples of the thermoplastic resins mentioned above include polyolefin resins (PP (polypropylene), PE (polyethylene)), polyester resins (PET), polyethylene resins (ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-(meth)acrylic acid copolymer), PVC (polyvinyl chloride), polyurethane, PC (polycarbonate), PS (polystyrene), AS, ABS, polyamide, PLA, and PHBH.

[0070] The amount of the silicone acrylic graft copolymer resin powder in the above resin composition is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass, in terms of solid content relative to the total mass of the resin composition. If the amount of the silicone acrylic graft copolymer resin powder is above the lower limit, a sliding effect will be exhibited. If it is below the upper limit, in the case of the resin composition, there will be no problems with the molded product, and the lubricity will be even better.

[0071] The powder (A) described above is mixed with the thermoplastic resin (B) in a dry blender (e.g., using a roll, kneader, Banba mixer, plastmill, extruder, etc.), and then molded into the desired shape by extrusion molding or injection molding. The thermoplastic resin may be pre-processed into pellets or powder form. The molding temperature should be above the melting temperature of the resin mixture, preferably at a set temperature of 150 to 250°C. For example, pellets are obtained from a strand die using a twin-screw extruder of Laboplastmill (manufactured by Toyo Seiki Seisakusho). Using these pellets, a 3cm x 3cm x 2mm injection molded piece is formed at a temperature of 150 to 250°C using a small 80tf injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd.). Similarly, a film of approximately 200μm is formed from a T-die using a twin-screw extruder of Laboplastmill.

[0072] In this case, transparency is required for the resin molded product, and it is preferable that the haze value of both the 2 mm thick resin molded product and the 200 μm thick resin molded product be 85% or less. If it is 85% or less, transparency can be perceived visually, and for example, the color and pattern of the base material can be clearly seen. The thickness of the molded product can be adjusted as appropriate, and for example, it can be molded to various thicknesses within the range of 10 μm to 10 mm.

[0073] Furthermore, the resin composition of the present invention may contain antioxidants, colorants, ultraviolet absorbers, light stabilizers, antistatic agents, plasticizers, flame retardants, other resins, etc., to the extent that they do not affect its performance.

[0074] The resin composition of the present invention is not particularly limited in its uses, but can be used as a material for stationery, toys, home appliances, car seats, furniture, clothing, shoes, bags, sanitary products, and outdoor tents.

[0075] [Cosmetic composition] The cosmetic composition of the present invention preferably contains 0.1 to 20% by mass of the silicone acrylic graft copolymer resin powder in terms of solid content relative to the total mass of the cosmetic composition, and more preferably 0.5 to 10% by mass. If the amount of the silicone acrylic graft copolymer resin powder is above the lower limit, a sliding effect is exhibited. If it is below the upper limit, good lubricity is achieved.

[0076] Furthermore, the cosmetic composition of the present invention may contain, in addition to the silicone acrylic graft copolymer resin powder of the present invention, oils, solvents, powders other than the silicone acrylic graft copolymer resin powder, etc.

[0077] Examples of the above-mentioned oils include hydrocarbons, silicone oils, triglycerides, ester oils, fats and oils, waxes, higher fatty acids having 12 to 20 carbon atoms, and higher alcohols having 8 to 20 carbon atoms. Low-boiling point silicone oils, low-boiling point isoparaffinic hydrocarbons, triglycerides, and ester oils are particularly preferred. For example, low-boiling point silicone oils include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tetradecamethylcyclohexasiloxane. Examples of ester oils include fatty acid esters having 6 to 20 carbon atoms or glycerin fatty acid esters.

[0078] The amount of oil in the above cosmetic composition varies depending on the dosage form of the cosmetic composition, and should be within a range suitable for the purpose of the present invention. Preferably, it is 0.1 to 95% by mass, more preferably 1 to 80% by mass, relative to the total amount of the powder and the silicone acrylic graft copolymer resin powder components of the present invention. If it is above the lower limit, the effects of the oil, such as lubricity and moisturizing properties, can be exhibited. If it is below the upper limit, there is no problem with storage stability.

[0079] Examples of the solvents mentioned above include intermediate and lower alcohols and aromatic alcohols, but lower alcohols having 1 to 4 carbon atoms, such as isopropyl alcohol, are preferred. The solvent content in the cosmetic composition of the present invention varies depending on the dosage form of the cosmetic composition, and may be within a range appropriate to the purpose of the present invention, but is preferably 0.1 to 80% by mass, and more preferably 1 to 50% by mass, relative to the total amount of the above powder and the silicone acrylic graft copolymer resin powder components of the present invention.

[0080] The above-mentioned powders are materials that can be used in ordinary (makeup) cosmetics and are not particularly limited. Typically, they have an average particle size of 0.1 to 50 μm and include, for example, colorants such as inorganic coloring pigments, inorganic white pigments, and organic pigments, pearl agents, extender pigments, and organic powders.

[0081] Examples of the above powders include titanium dioxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, red mica, biotite, lithium mica, silicic acid, anhydrous silicic acid, aluminum silicate, sodium silicate, sodium magnesium silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, tungstate metal salts, hydroxyapatite, vermiculite, hydylite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, etc.; examples of organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene Lens powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk powder, nylon powder, 1,2-nylon, 6-nylon, silicone powder, polymethylsilsesquioxane spherical powder, styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, vinyl resin, urea resin, phenolic resin, fluororesin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder, starch powder, lauroyl lysine, etc.; as surfactant metal salt powders, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc palmitate, zinc laurate, zinc cetyl phosphate, calcium cetyl phosphate, sodium zinc cetyl phosphate, etc.;As for colored pigments, inorganic red pigments such as red iron oxide, iron oxide, iron hydroxide, and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as yellow iron oxide and ochre; inorganic black pigments such as black iron oxide and carbon black; inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate; inorganic blue pigments such as Prussian blue and ultramarine; Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 2 Examples of pigments include lake-formed tar-based dyes such as No. 04, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, and Orange No. 207, as well as lake-formed natural pigments such as carminic acid, laccaic acid, calsamine, brazilin, and crocin; pearl pigments include titanium dioxide-coated mica, titanium mica, iron oxide-treated titanium mica, bismuth oxychloride, titanium dioxide-coated bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, and titanium dioxide-coated colored mica; and metal powder pigments include metal powders such as aluminum, gold, silver, copper, platinum, and stainless steel.

[0082] Furthermore, in addition to the above-mentioned components, the cosmetic composition of the present invention may also contain other ingredients commonly found in cosmetics, such as surfactants, oily components, polymer compounds, gelling agents, alkaline agents, polyhydric alcohols, pH adjusters, UV absorbers, antioxidants, preservatives, anti-inflammatory agents, skin beautifying ingredients, and fragrances, depending on the purpose of the present invention.

[0083] Examples of cosmetics of the present invention include makeup cosmetics such as foundation, face powder, eyeshadow, eyeliner, eyebrow products, blush, lipstick, and nail polish; basic cosmetics such as emulsion, cream, lotion, calamine lotion, sunscreen, suntan, aftershave lotion, preshave lotion, packs, acne treatment cosmetics, and essences; hair cosmetics such as shampoo, rinse, conditioner, hair color, hair tonic, styling agents, hair growth agents, and permanent wave agents; body powder, deodorant, hair removal agents, soap, body wash, bath additives, hand soap, and perfume. The silicone copolymer resin powder of the present invention is preferably used in powder cosmetics such as foundation, face powder, eyeshadow, and eyebrow products.

[0084] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, parts and % refer to parts by mass and mass%, respectively.

[0085] <(I) Production of polyorganosiloxane → (A) Production of silicone acrylic graft copolymer resin powder> [Example 1] Viscosity of 700 mm ２92.09 parts of dimethylpolysiloxane (A-1) (octamethylcyclotetrasiloxane content 50 ppm or less) having a silanol group at the end of the / s molecular chain and 0.09 parts of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltrimethoxysilane) were mixed, and 2.0 parts of Perex NBL (manufactured by Kao Corporation, 35% aqueous solution of alkylnaphthalene sulfonate sodium), 1.18 parts of Newcol 291-PG (manufactured by Nippon Emulsifier Co., Ltd., 70% propylene glycol solution of dialkyl succinate sulfonate sodium), and 1.51 parts of Emal 270J (manufactured by Kao Corporation, 70% aqueous solution of polyoxyethylene alkyl ether sulfate sodium) were dissolved in ion-exchanged water. The mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. To this emulsion, 2.6 parts of Neoperex GS-P (manufactured by Kao Corporation, alkylbenzene sulfonic acid), diluted with deionized water, were added, and emulsion polymerization was carried out at 10°C for 20 to 25 hours. Subsequently, 0.46 parts of sodium carbonate dissolved in deionized water were added to the obtained emulsion to neutralize it, and finally, 0.07 parts of the preservative ACTICIDE LA2011 (manufactured by So Japan Co., Ltd., aqueous solution of methylisothiazolinone, chloromethylisothiazolinone, and bronopol) were added to obtain an emulsion. In the obtained emulsion composition, in general formula (1), a = 99.866, b = 0.078, c = 0, d = 0.056, the solid content was 53.6%, the viscosity of the emulsion composition was 105 mPa·s, the average particle size was 0.28 μm, and the molecular weight (M) was 300,000.

[0086] 59.0 parts of the obtained emulsion were placed in a reaction vessel and diluted with 20.8 parts of deionized water. After adjusting the temperature to 30°C, 13.4 parts of methyl methacrylate were added dropwise over 3 to 5 hours using ferrous sulfate as an initiator, along with peroxide and activator, to carry out acrylic graft copolymerization by redox reaction. The obtained silicone acrylic graft copolymer emulsion had a solid content of 44.9% and an average particle size of 0.25 μm.

[0087] The obtained silicone acrylic graft copolymer emulsion was spray-dried to obtain a powder. The solid content, average particle size, D4 ​​(octamethylcyclotetrasiloxane) content, 2%, 10%, and 50% weight loss temperatures, and the static and dynamic friction coefficients of the coating film were measured for the obtained powder, and the results are shown in Table 1.

[0088] [Example 2] Viscosity of 700 mm ２ 92.09 parts of dimethylpolysiloxane (A-1) (octamethylcyclotetrasiloxane content 50 ppm or less) having a silanol group at the end of the / s molecular chain and 0.09 parts of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., same as above) were mixed, and 2.0 parts of Perex NBL (manufactured by Kao Corporation, same as above), 1.18 parts of Newcol 291-PG (manufactured by Nippon Emulsifier Co., Ltd., same as above), and 1.51 parts of Emal 270J (manufactured by Kao Corporation, same as above) were dissolved in deionized water. This mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. 2.6 parts of Neoperex GS-P (manufactured by Kao Corporation, same as above), diluted with deionized water, were added to this emulsion, and emulsion polymerization was carried out at 10°C for 20 to 25 hours. Subsequently, 0.46 parts of sodium carbonate dissolved in deionized water were added to the obtained emulsion to neutralize it, and finally, 0.07 parts of the preservative ACTICIDE LA2011 (manufactured by So Japan Co., Ltd., same as above) were added to obtain an emulsion. In the obtained emulsion composition, in general formula (1), a = 99.866, b = 0.078, c = 0, d = 0.056, the solid content was 53.6%, the viscosity of the emulsion was 105 mPa·s, the average particle size was 0.28 μm, and the molecular weight (M) was 300,000.

[0089] 59.0 parts of the obtained emulsion were placed in a reaction vessel and diluted with 13.2 parts of deionized water. After adjusting the temperature to 30°C, 7.9 parts of methyl methacrylate were added dropwise over 3 to 5 hours using ferrous sulfate as an initiator, along with peroxide and activator, to carry out acrylic graft copolymerization by redox reaction. The obtained silicone acrylic graft copolymer emulsion had a solid content of 44.5% and an average particle size of 0.24 μm.

[0090] The obtained silicone acrylic graft copolymer emulsion was spray-dried to obtain a powder. The solid content, average particle size, D4 ​​(octamethylcyclotetrasiloxane) content, 2%, 10%, and 50% weight loss temperatures, and the static and dynamic friction coefficients of the coating film were measured for the obtained powder, and the results are shown in Table 1.

[0091] [Example 3] Viscosity of 700 mm ２ 94.29 parts of dimethylpolysiloxane (A-1) (octamethylcyclotetrasiloxane content 50 ppm or less) having a silanol group at the end of the / s molecular chain and 0.09 parts of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., same as above) were mixed, and 1.02 parts of Perex NBL (manufactured by Kao Corporation, same as above), 0.6 parts of Newcol 291-PG (manufactured by Nippon Emulsifier Co., Ltd., same as above), and 0.77 parts of Emal 270J (manufactured by Kao Corporation, same as above) were dissolved in deionized water. This mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. 2.67 parts of Neoperex GS-P (manufactured by Kao Corporation, same as above), diluted with deionized water, were added to this emulsion, and emulsion polymerization was carried out at 10°C for 20 to 25 hours. Subsequently, 0.48 parts of sodium carbonate dissolved in deionized water were added to the obtained emulsion to neutralize it, and finally, 0.08 parts of the preservative ACTICIDE LA2011 (manufactured by So Japan Co., Ltd., same as above) were added to obtain an emulsion. In the obtained emulsion composition, in general formula (1), a = 99.868, b = 0.076, c = 0, d = 0.056, the solid content was 53.1%, the viscosity of the emulsion composition was 285 mPa·s, the average particle size was 0.68 μm, and the molecular weight (M) was 300,000.

[0092] 59.0 parts of the obtained emulsion were placed in a reaction vessel and diluted with 20.8 parts of deionized water. After adjusting the temperature to 30°C, 13.4 parts of methyl methacrylate were added dropwise over 3 to 5 hours using ferrous sulfate as an initiator, along with peroxide and activator, to carry out acrylic graft copolymerization by redox reaction. The obtained silicone acrylic graft copolymer emulsion had a solid content of 45.0% and an average particle size of 0.72 μm.

[0093] The obtained silicone acrylic graft copolymer emulsion was spray-dried to obtain a powder. The solid content, average particle size, D4 ​​content, and weight loss temperatures at 2%, 10%, and 50% were measured for the obtained powder, and the results are shown in Table 1.

[0094] [Example 4] Viscosity of 700 mm ２ 92.09 parts of dimethylpolysiloxane (A-1) (octamethylcyclotetrasiloxane content 50 ppm or less) having a silanol group at the end of the / s molecular chain and 0.09 parts of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., same as above) were mixed, and 2.0 parts of cinolin 100 (manufactured by Shin-Nippon Rika Co., Ltd., sodium alkyl sulfate), 1.18 parts of Newcol 291-PG (manufactured by Nippon Emulsifier Co., Ltd., same as above), and 1.51 parts of Emal 270J (manufactured by Kao Corporation, same as above) were dissolved in ion-exchanged water. This mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. 2.6 parts of Neoperex GS-P (manufactured by Kao Corporation, same as above), diluted with ion-exchanged water, were added to this emulsion, and emulsion polymerization was carried out at 10°C for 20 to 25 hours. Subsequently, 0.46 parts of sodium carbonate dissolved in deionized water were added to the obtained emulsion to neutralize it, and finally, 0.07 parts of the preservative ACTICIDE LA2011 (manufactured by So Japan Co., Ltd., same as above) were added to obtain an emulsion. In the obtained emulsion composition, in general formula (1), a = 99.866, b = 0.078, c = 0, d = 0.056, the solid content was 53.8%, the viscosity of the emulsion was 1,420 mPa·s, the average particle size was 0.32 μm, and the molecular weight (M) was 300,000.

[0095] 59.0 parts of the obtained emulsion were placed in a reaction vessel and diluted with 20.8 parts of deionized water. After adjusting the temperature to 30°C, 13.4 parts of methyl methacrylate were added dropwise over 3 to 5 hours using ferrous sulfate as an initiator, along with a peroxide and an activator, to carry out acrylic graft copolymerization by redox reaction. The obtained silicone acrylic graft copolymer emulsion had a solid content of 44.2% and an average particle size of 0.32 μm.

[0096] The obtained silicone acrylic graft copolymer emulsion was spray-dried to obtain a powder. The solid content, average particle size, D4 ​​content, and weight loss temperatures at 2%, 10%, and 50% were measured for the obtained powder, and the results are shown in Table 1.

[0097] [Example 5] Viscosity of 700 mm ２ 91.98 parts of dimethylpolysiloxane (A-1) (octamethylcyclotetrasiloxane content 50 ppm or less) having a silanol group at the end of the molecular chain of / s, 0.09 parts of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., same as above), and 0.12 parts of KF-96L-0.65cs (manufactured by Shin-Etsu Chemical Co., Ltd., hexamethyldisiloxane) were mixed, and 2.0 parts of Perex NBL (manufactured by Kao Corporation, same as above), 1.18 parts of Newcol 291-PG (manufactured by Nippon Emulsifier Co., Ltd., same as above), and 1.51 parts of Emal 270J (manufactured by Kao Corporation, same as above) were dissolved in ion-exchanged water. The mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. To this emulsion, 2.6 parts of Neoperex GS-P (manufactured by Kao Corporation) diluted with deionized water were added, and emulsion polymerization was carried out at 10°C for 20 to 25 hours. Then, 0.46 parts of sodium carbonate dissolved in deionized water were added to the obtained emulsion to neutralize it, and finally, 0.07 parts of the preservative ACTICIDE LA2011 (manufactured by So Japan Co., Ltd., same as above) were added to obtain an emulsion composition. In the general formula (1), the obtained emulsion composition had a = 99.797, b = 0.076, c = 0, and d = 0.127, with a solid content of 52.9%, an emulsion viscosity of 92 mPa·s, an average particle size of 0.22 μm, and a molecular weight (M) of 170,000.

[0098] 59.0 parts of the obtained emulsion were placed in a reaction vessel and diluted with 20.8 parts of deionized water. After adjusting the temperature to 30°C, 13.4 parts of methyl methacrylate were added dropwise over 3 to 5 hours using ferrous sulfate as an initiator, along with peroxide and activator, to carry out acrylic graft copolymerization by redox reaction. The obtained silicone acrylic graft copolymer emulsion had a solid content of 44.8% and an average particle size of 0.22 μm.

[0099] The obtained silicone acrylic graft copolymer emulsion was spray-dried to obtain a powder. The solid content, average particle size, D4 ​​content, and weight loss temperatures at 2%, 10%, and 50% were measured for the obtained powder, and the results are shown in Table 1.

[0100] [Example 6] Viscosity of 700 mm ２ 92.09 parts of dimethylpolysiloxane (A-1) (octamethylcyclotetrasiloxane content 50 ppm or less) having a silanol group at the end of the / s molecular chain and 0.09 parts of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., same as above) were mixed, and 2.0 parts of Perex NBL (manufactured by Kao Corporation, same as above), 1.18 parts of Newcol 291-PG (manufactured by Nippon Emulsifier Co., Ltd., same as above), and 1.51 parts of Emal 270J (manufactured by Kao Corporation, same as above) were dissolved in deionized water. This mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. 2.6 parts of Neoperex GS-P (manufactured by Kao Corporation, same as above), diluted with deionized water, were added to this emulsion, and emulsion polymerization was carried out at 10°C for 20 to 25 hours. Subsequently, 0.46 parts of sodium carbonate dissolved in deionized water were added to the obtained emulsion to neutralize it, and finally, 0.07 parts of the preservative ACTICIDE LA2011 (manufactured by So Japan Co., Ltd., same as above) were added to obtain an emulsion. In the obtained emulsion composition, in general formula (1), a = 99.866, b = 0.078, c = 0, d = 0.056, the solid content was 53.6%, the viscosity of the emulsion was 105 mPa·s, the average particle size was 0.28 μm, and the molecular weight (M) was 300,000.

[0101] 59.0 parts of the obtained emulsion were placed in a reaction vessel and diluted with 20.8 parts of deionized water. After adjusting the temperature to 30°C, 10.3 parts of methyl methacrylate and 3.1 parts of butyl acrylate were mixed and added dropwise over 3 to 5 hours using ferrous sulfate as an initiator, along with peroxide and activator, to carry out acrylic graft copolymerization by redox reaction. The obtained silicone acrylic graft copolymer emulsion had a solid content of 44.7% and an average particle size of 0.31 μm.

[0102] The obtained silicone acrylic graft copolymer emulsion was spray-dried to obtain a powder. The solid content, average particle size, D4 ​​content, and weight loss temperatures at 2%, 10%, and 50% were measured for the obtained powder, and the results are shown in Table 1.

[0103] [Comparative Example 1] Viscosity of 700 mm ２ 92.09 parts of dimethylpolysiloxane (A-1) (octamethylcyclotetrasiloxane content 50 ppm or less) having a silanol group at the end of the / s molecular chain and 0.09 parts of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., same as above) were mixed, and 2.0 parts of Perex NBL (manufactured by Kao Corporation, same as above), 1.18 parts of Newcol 291-PG (manufactured by Nippon Emulsifier Co., Ltd., same as above), and 1.51 parts of Emal 270J (manufactured by Kao Corporation, same as above) were dissolved in deionized water. This mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. 2.6 parts of Neoperex GS-P (manufactured by Kao Corporation, same as above), diluted with deionized water, were added to this emulsion, and emulsion polymerization was carried out at 10°C for 20 to 25 hours. Subsequently, 0.46 parts of sodium carbonate dissolved in deionized water were added to the obtained emulsion to neutralize it, and finally, 0.07 parts of the preservative ACTICIDE LA2011 (manufactured by So Japan Co., Ltd., same as above) were added to obtain an emulsion composition. In general formula (1), the obtained emulsion had a=99.866, b=0.078, c=0, and d=0.056, with a solid content of 53.6%, a viscosity of 105 mPa·s, an average particle size of 0.28 μm, and a molecular weight (M) of 300,000. This was spray-dried to obtain a powder.

[0104] We attempted to powderize the material by spray drying without performing acrylic graft copolymerization, but the solid material was oil and could not be powdered.

[0105] [Comparative Example 2] A mixture of 17.5 parts of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., same as above) and 0.007 parts of BHT (dibutylhydroxytoluene) was mixed with 5.61 parts of 0.1N hydrochloric acid water, and the mixture was stirred at 60°C for 3 hours to induce a hydrolysis and condensation reaction. After separating and removing the aqueous phase by liquid-liquid separatory, 14.03 parts of toluene and 6.0 parts of deionized water were added, and after washing with water to separate and remove residual hydrochloric acid and by-product methanol, the toluene was removed by reduced pressure distillation at 90°C to obtain the KBM-502 condensation reaction product. 0.08 parts of the obtained KBM-502 condensation reaction product and 97.29 parts of DMC (dimethylcyclosiloxane) were mixed, and 1.36 parts of NIKKOL SLS (manufactured by Nikko Chemicals Co., Ltd., sodium lauryl sulfate) was dissolved in deionized water. The mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. To this emulsion, 0.97 parts of Neoperex GS-P (manufactured by Kao Corporation, same as above), diluted with deionized water, were added, followed by emulsion polymerization at 55°C for 20 to 25 hours, and then emulsion polymerization again at 10 to 20°C for another 20 to 25 hours. Subsequently, 0.3 parts of sodium carbonate dissolved in deionized water were added to the resulting emulsion to neutralize it and obtain an emulsion composition. In the general formula (1), the obtained emulsion composition had a=99.884, b=0.060, c=0, and d=0.056, with a solid content of 45.0%, a viscosity of 80 mPa·s, an average particle size of 0.30 μm, and a molecular weight (M) of 250,000.

[0106] 59.0 parts of the obtained emulsion were placed in a reaction vessel and diluted with 71.8 parts of deionized water. After adjusting the temperature to 30°C, 7.9 parts of methyl methacrylate were added dropwise over 3 to 5 hours using ferrous sulfate as an initiator, along with peroxide and activator, to carry out acrylic graft copolymerization by redox reaction. The obtained silicone acrylic graft copolymer emulsion had a solid content of 45.0% and an average particle size of 0.33 μm.

[0107] The obtained silicone acrylic graft copolymer emulsion was spray-dried to obtain a powder. The solid content, average particle size, D4 ​​content, and weight loss temperatures at 2%, 10%, and 50% were measured for the obtained powder, and the results are shown in Table 2.

[0108] [Comparative Example 3] A mixture of 17.5 parts of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., same as above) and 0.007 parts of BHT (dibutylhydroxytoluene) was mixed with 5.61 parts of 0.1N hydrochloric acid water, and the mixture was stirred at 60°C for 3 hours to induce a hydrolysis and condensation reaction. After separating and removing the aqueous phase by liquid-liquid separatory, 14.03 parts of toluene and 6.0 parts of deionized water were added, and after washing with water to separate and remove residual hydrochloric acid and by-product methanol, the toluene was removed by reduced pressure distillation at 90°C to obtain the KBM-502 condensation reaction product. 0.08 parts of the obtained KBM-502 condensation reaction product and 97.29 parts of DMC (dimethylcyclosiloxane) were mixed, and 1.36 parts of NIKKOL SLS (manufactured by Nikko Chemicals Co., Ltd., sodium lauryl sulfate) was dissolved in deionized water. The mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. To this emulsion, 0.97 parts of Neoperex GS-P (manufactured by Kao Corporation, same as above), diluted with deionized water, were added, followed by emulsion polymerization at 55°C for 20 to 25 hours, and then emulsion polymerization again at 10 to 20°C for another 20 to 25 hours. Subsequently, 0.3 parts of sodium carbonate dissolved in deionized water were added to the resulting emulsion to neutralize it and obtain an emulsion composition. In the general formula (1), the obtained emulsion composition had a=99.884, b=0.060, c=0, and d=0.056, with a solid content of 45.0%, a viscosity of 80 mPa·s, an average particle size of 0.30 μm, and a molecular weight (M) of 250,000.

[0109] 69.2 parts of the obtained silicone emulsion were placed in a reaction vessel and diluted with 10.0 parts of deionized water. After adjusting the temperature to 30°C, 13.4 parts of methyl methacrylate were added dropwise over 3 to 5 hours using ferrous sulfate as an initiator, along with a peroxide and an activator, to carry out acrylic graft copolymerization by redox reaction. The obtained silicone acrylic graft copolymer emulsion had a solid content of 44.3% and an average particle size of 0.33 μm.

[0110] The obtained silicone acrylic graft copolymer emulsion was spray-dried to obtain a powder. The solid content, average particle size, D4 ​​content, 2%, 10%, and 50% weight loss temperatures, and the static and dynamic friction coefficients of the coating film were measured for the obtained powder, and the results are shown in Table 2.

[0111] [Comparative Example 4] 0.08 parts of the KBM-502 condensation reaction product described in Comparative Example 3 and 97.29 parts of DMC (dimethylcyclosiloxane) were mixed, and 1.36 parts of NIKKOL SLS (same as above) were dissolved in deionized water. This mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. 0.97 parts of Neoperex GS-P (same as above), diluted with deionized water, were added to this emulsion, and emulsion polymerization was carried out at 55°C for 20 to 25 hours, followed by further emulsion polymerization at 10 to 20°C for 20 to 25 hours. After that, 0.3 parts of sodium carbonate dissolved in deionized water were added to the obtained emulsion to neutralize it and obtain an emulsion composition. The resulting emulsion composition had the following properties in general formula (1): a = 99.884, b = 0.060, c = 0, d = 0.056, a solid content of 45.0%, a viscosity of 80 mPa·s, an average particle size of 0.30 μm, and a molecular weight (M) of 250,000.

[0112] 69.2 parts of the obtained emulsion were placed in a reaction vessel and diluted with 10.0 parts of deionized water. After adjusting the temperature to 30°C, 10.3 parts of methyl methacrylate and 3.1 parts of butyl acrylate were mixed and added dropwise over 3 to 5 hours using ferrous sulfate as an initiator, along with peroxide and activator, to carry out acrylic graft copolymerization by redox reaction. The obtained silicone acrylic graft copolymer emulsion had a solid content of 44.3% and an average particle size of 0.31 μm.

[0113] The obtained silicone acrylic graft copolymer emulsion was spray-dried to obtain a powder. The solid content, average particle size, D4 ​​content, and weight loss temperatures at 2%, 10%, and 50% were measured for the obtained powder, and the results are shown in Table 2.

[0114] The amounts of each component used in Examples 1 to 6 and Comparative Examples 1 to 4, as well as the measurement results described below, are shown in Tables 1 and 2, respectively.

[0115] <Method for measuring solid content> Approximately 1 g of the resin emulsion or powder (sample) from each example and comparative example was accurately weighed onto an aluminum foil dish, placed in a drying oven maintained at approximately 105°C, heated for 1 hour, then removed from the drying oven and allowed to cool in a desiccator. The weight of the dried sample was measured, and the evaporation residue was calculated using the following formula. R: Evaporation residue (%) W: Mass of aluminum foil dish containing sample before drying (g) L: Mass of aluminum foil dish (g) T: Mass of aluminum foil dish containing sample after drying (g) Dimensions of aluminum foil dish: 70φ × 12h (mm)

[0116] The residual moisture content of the silicone acrylic graft copolymer resin powder of the present invention may be calculated using the evaporation residue R of the powder and the following formula. The silicone acrylic graft copolymer resin powder of the present invention has a residual moisture content of 5% or less, preferably 2% or less. (Residual moisture content %) = 100 - R

[0117] <Octamethylcyclotetrasiloxane (D4) content> 0.1 g of the composition was extracted with 10 mL of acetone containing 20 ppm (by mass) of tetradecane as an internal standard (shaking for 3 hours). After standing overnight, the acetone layer was collected and the amount of octamethylcyclotetrasiloxane was quantified by gas chromatography analysis.

[0118] <Average Particle Diameter> This is the particle size (median diameter) at 50% of the cumulative value in the volume-based particle size distribution measured using the LA-950 laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd.).

[0119] <Viscosity Measurement> The viscosity of the emulsion was measured using a BM-type viscometer with a No. 2 rotor at 25°C and 6 rpm.

[0120] <2%, 10%, and 50% Weight Loss Temperatures> The weight change was measured by raising the temperature from room temperature to 600°C (heating rate 10°C / min) using a differential thermal and heat quantity simultaneous measurement device DTG-60 manufactured by Shimadzu Corporation. The temperatures at which the weight decreased by 2%, 5%, and 10%, respectively from the initial weight, are recorded.

[0121] <Measurement of Static and Dynamic Friction Coefficients of Coating Films> 2.7 g of Solvine CNL (manufactured by Nisshin Chemical Industry Co., Ltd.) and 0.3 g each of the powders prepared in Examples 1 and 2 and Comparative Example 3 were dissolved in 2.7 g of MEK (methyl ethyl ketone). The coating was applied using a bar coater No. 40, dried at 105°C for 5 minutes, and then a 200 g metal indenter was brought into contact perpendicularly with the coating film of each example using a HEIDON TYPE-38 (manufactured by Shinto Kagaku Co., Ltd.). The frictional force was measured when the indenter was moved at 3 cm / min, and the static and dynamic friction coefficients were calculated from the frictional force.

[0122] All raw materials used are listed in parts by mass. D4: Octamethylcyclotetrasiloxane MMA: Methyl methacrylate BA: Butyl acrylate

[0123] All raw materials used are listed in parts by mass. D4: Octamethylcyclotetrasiloxane MMA: Methyl methacrylate BA: Butyl acrylate

[0124] From the results in Tables 1 and 2 above, Examples 1 to 6 using the silicone acrylic graft copolymer resin powder of the present invention all had an octamethylcyclotetrasiloxane content of 1000 ppm or less and a residual moisture content of 5% or less.

[0125] On the other hand, in Comparative Example 1, where acrylic graft copolymerization of component (I) and component (II) was not performed, the solid content became oil and it was not possible to produce a powder. Furthermore, in Comparative Examples 2 to 4, which used DMC (dimethylcyclosiloxane) different from component (I) of the present invention, the residual moisture content was 5% or less in all cases, but the octamethylcyclotetrasiloxane content could not be reduced to 1000 ppm or less in any case.

[0126] Next, the silicone acrylic graft copolymer resin powder of the present invention was kneaded with ethylene-ethyl acrylate copolymer to obtain a resin product. <Molding Method> [Example 7, Comparative Examples 5, 6] Ethylene-ethyl acrylate copolymer (EEA resin, product name: NUC-6520, manufactured by ENEOS NUC Corporation), magnesium hydroxide (product name: Magseas S, manufactured by Kamishima Chemical Industry Co., Ltd.), and the resin powder obtained in Example 1 or Comparative Example 3 were kneaded in a kneader at approximately 170°C and 50 rpm in the amounts shown in Table 3 below, and molded into a plate shape of 127 × 13 × 3.1 mm thick by pressing, and test pieces were extracted by cutting. The static friction coefficient and dynamic friction coefficient of the obtained molded product were evaluated. The results are shown in Table 3. The density of the EEA resin used in Example 7 and Comparative Examples 5, 6 was 0.94 g / cm³ ３ The melt mass flow rate measured at 190°C and a load of 2.16 kg in accordance with JIS K7210-1:2014 was 1.6 g / 10 min, the ethyl acrylate content was 24% by mass, and the durometer hardness (D) was 85. The magnesium hydroxide used in Example 7 and Comparative Examples 5 and 6 was flame retardant magnesium hydroxide surface-treated with a silane coupling agent and had an average particle size of 1.0 μm.

[0127] The measurement methods used in Example 7 and Comparative Examples 5 and 6 are as follows: <Measurement of static and dynamic friction coefficients> Using HEIDON TYPE-38 (manufactured by Shinto Kagaku Co., Ltd.), a 200g metal indenter was brought into contact perpendicularly with the coating film of each example and moved at 3 cm / min. The frictional force was measured, and the static and dynamic friction coefficients were calculated from the frictional force.

[0128]

[0129] As shown in Table 3 above, Example 7 of the resin-formed product using the silicone acrylic graft copolymer resin powder of the present invention exhibited a higher sliding effect than Comparative Examples 5 and 6.

[0130] This specification includes the following embodiments: [1]: A silicone acrylic graft copolymer resin powder comprising (I) a polyorganosiloxane represented by the following general formula (1), (In the formula, R １These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms (however, R described below) ２ (Excluding the groups defined by and the phenyl group), R ２ R is an alkyl group having 1 to 6 carbon atoms, in which some of the hydrogen atoms bonded to the carbon atoms are substituted with a mercapto group, a vinyl group, an acryloxy group, or a methacryloxy group, independently of each other. ３ These are independently of each other, a phenyl group or the above R １ A group defined by and at least one R ３is a phenyl group, X is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, a, b, c, and d are real numbers, and for the sum of a, b, c, and d, a is a number such that 0.11 ≤ a / (a+b+c+d) < 1, b is a number such that 0.00001 ≤ b / (a+b+c+d) ≤ 0.05, c is a number such that 0 ≤ c / (a+b+c+d) ≤ 0.6, and d is a number such that 0.000001 ≤ d / (a+b+c+d) ≤ 0.24. (II) A powder comprising a graft copolymer resin of an acrylic acid ester monomer and / or a methacrylic acid ester monomer, wherein the mass ratio when the total mass of the polyorganosiloxane of (I) and the acrylic acid ester monomer and / or methacrylic acid ester monomer of (II) is 100 is (I):(II) = 60 to 99:1 to 40, and the content of octamethylcyclotetrasiloxane in the powder is 1000 ppm or less, and the residual moisture content is 5% or less. [2]: The silicone acrylic graft copolymer resin powder according to [1], wherein the molecular weight of the polyorganosiloxane of (I) is 5,000 to 500,000. [3]: The silicone acrylic graft copolymer resin powder according to [1] or [2], wherein the average particle size is 1 to 500 μm. [4]: A resin composition characterized by containing 0.1 to 20% by mass, in terms of solid content, of the silicone acrylic graft copolymer resin powder described in any one of [1] to [3]. [5]: A cosmetic characterized by containing 0.1 to 20% by mass, in terms of solid content, of the silicone acrylic graft copolymer resin powder described in any one of [1] to [3].[6]: A method for producing a silicone acrylic graft copolymer resin powder according to any one of [1] to [3], comprising the steps of: adding the acrylic acid ester monomer and / or methacrylic acid ester monomer of (II) to an emulsion containing the polyorganosiloxane of (I) and polymerizing it to obtain a silicone acrylic graft copolymer emulsion; and spray-drying the silicone acrylic graft copolymer emulsion.

[0131] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. A silicone acrylic graft copolymer resin powder comprising (I) a polyorganosiloxane represented by the following general formula (1), (In the formula, R １ These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms (however, R described below) ２ (Excluding the groups defined by and the phenyl group), R ２ R is an alkyl group having 1 to 6 carbon atoms, which is independently of each other, and consists of an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which some of the hydrogen atoms bonded to the carbon atoms are substituted with a mercapto group, a vinyl group, an acryloxy group, or a methacryloxy group. ３ These are independently of each other, a phenyl group or the above R １ A group defined by and at least one R ３ is a phenyl group, X is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, a, b, c, and d are real numbers, and for the sum of a, b, c, and d, a is a number such that 0.11 ≤ a / (a+b+c+d) < 1, b is a number such that 0.00001 ≤ b / (a+b+c+d) ≤ 0.05, c is a number such that 0 ≤ c / (a+b+c+d) ≤ 0.6, and d is a number such that 0.000001 ≤ d / (a+b+c+d) ≤ 0.

24. (II) A powder containing a graft copolymer resin of either an acrylic acid ester monomer or a methacrylic acid ester monomer, or both thereof, wherein the mass ratio of the polyorganosiloxane of (I) and either or both of the acrylic acid ester monomer and methacrylic acid ester monomer of (II) is 100, and the content of octamethylcyclotetrasiloxane in the powder is 1000 ppm or less, and the residual moisture content is 5% or less.

2. The silicone acrylic graft copolymer resin powder according to claim 1, characterized in that the molecular weight of the polyorganosiloxane in (I) is 5,000 to 500,000.

3. The silicone acrylic graft copolymer resin powder according to claim 1, characterized in that the average particle size is 1 to 500 μm.

4. A resin composition characterized by containing 0.1 to 20% by mass, in terms of solid content, of the silicone acrylic graft copolymer resin powder described in any one of claims 1 to 3, relative to the total mass of the resin composition.

5. A cosmetic composition characterized by containing 0.1 to 20% by mass, in terms of solid content, of the silicone acrylic graft copolymer resin powder described in any one of claims 1 to 3, relative to the total mass of the cosmetic composition.

6. A method for producing a silicone acrylic graft copolymer resin powder according to any one of claims 1 to 3, comprising the steps of: adding either or both of the acrylic acid ester monomer and the methacrylic acid ester monomer of (II) to an emulsion containing the polyorganosiloxane of (I) and polymerizing them to obtain a silicone acrylic graft copolymer emulsion; and spray-drying the silicone acrylic graft copolymer emulsion.

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