Silicone acrylic graft copolymer resin emulsion, method for producing same, and coating composition

Abstract

The present invention is a silicone acrylic graft copolymer resin emulsion, said silicone acrylic graft copolymer resin emulsion being characterized by comprising a graft copolymer resin of (I) a polyorganosiloxane represented by general formula (1), and (II) an acrylic acid ester monomer and / or a methacrylic acid ester monomer, wherein: when the total mass of the polyorganosiloxane (I) and the acrylic acid ester monomer and / or methacrylic acid ester monomer (II) is represented as 100, the mass ratio (I):(II) therebetween is 60-99:1-40; the content of octamethylcyclotetrasiloxane in the emulsion is not more than 3,000 ppm; and the average particle size is not more than 1 μm. Thus, provided are: a silicone acrylic graft copolymer resin emulsion in which octamethylcyclotetrasiloxane is reduced; a method for producing the same; and a coating composition.

Description

Silicone acrylic graft copolymer resin emulsion, method for producing the same, and coating composition

[0001] This invention relates to a silicone acrylic graft copolymer resin emulsion, a method for producing the same, and a coating composition.

[0002] Silicone acrylic graft copolymer resin emulsions have traditionally been used to impart sliding properties to substrates such as leather and resin, and various studies have been conducted on them.

[0003] In recent years, there has been a growing demand for silicone emulsions with reduced octamethylcyclotetrasiloxane content. Methods described in Patent Documents 1 and 2 have shown that the resulting emulsions contain over 40,000 ppm of octamethylcyclotetrasiloxane, 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] Until now, no silicone acrylic graft copolymer resin emulsions with reduced octamethylcyclotetrasiloxane content had been considered. However, there is a possibility that products with reduced octamethylcyclotetrasiloxane content may be required in the future, so there was 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 emulsion with reduced octamethylcyclotetrasiloxane, a method for producing the same, and a coating composition that, when applied to a substrate and dried, imparts excellent tactile properties, water repellency, and sliding properties to the surface of the substrate.

[0008] To solve the above problems, the present invention provides a silicone acrylic graft copolymer resin emulsion 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, independently of each other, which is 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 ３is 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) ≦ 0.24.) (II) An emulsion containing a graft copolymer resin with an acrylic acid ester monomer and / or a methacrylic acid ester monomer, 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, the mass ratio is (I): (II) = 60 to 99: 1 to 40, and the silicone acrylic graft copolymer resin emulsion is characterized in that the content of octamethylcyclotetrasiloxane in the emulsion is 3,000 ppm or less and the average particle size is 1 μm or less.

[0009] For the silicone acrylic graft copolymer resin emulsion of the present invention, a silicone acrylic graft copolymer resin emulsion with reduced octamethylcyclotetrasiloxane can be provided.

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

[0011] By the polyorganosiloxane of (I) having the above molecular weight, a coating agent that imparts good slipperiness peculiar to silicone can be obtained.

[0012] Further, it is preferable that the viscosity of an emulsion containing 35 to 55% of the solid content containing the polyorganosiloxane of (I) is less than 1,000 mPa·s.

[0013] The emulsion containing the polyorganosiloxane of (I) preferably has such a viscosity.

[0014] Furthermore, the present invention can provide a coating composition containing the silicone acrylic graft copolymer resin emulsion in an amount of 10 to 60% by mass in terms of solid content relative to the total mass of the composition.

[0015] The coating composition comprising the silicone acrylic graft copolymer resin emulsion of the present invention can impart excellent tactile properties, water repellency, and sliding properties to the substrate surface when applied to the substrate surface and dried.

[0016] Furthermore, the present invention can provide a coating composition comprising: (A) the silicone acrylic graft copolymer resin emulsion of the present invention: 1 to 40% by mass in terms of solid content; and (B) at least one resin emulsion selected from vinyl chloride resin emulsion, acrylic resin emulsion, acrylic silicone resin emulsion, urethane resin emulsion, alkyd resin emulsion, and epoxy resin emulsion: 60 to 99% by mass in terms of solid content.

[0017] The silicone acrylic graft copolymer resin emulsion of the present invention, when applied to a substrate and dried, can impart excellent tactile properties, water repellency, and sliding properties to the substrate surface.

[0018] Furthermore, the present invention provides a method for producing a silicone acrylic graft copolymer resin emulsion, comprising the step of adding the acrylic acid ester monomer and / or methacrylic acid ester monomer of (II) to the emulsion containing the polyorganosiloxane of (I) and polymerizing it.

[0019] By using the manufacturing method of the present invention, a silicone acrylic graft copolymer resin emulsion with reduced octamethylcyclotetrasiloxane content can be produced.

[0020] As described above, in the silicone acrylic graft copolymer resin emulsion and the method for producing the same according to the present invention, by reducing octamethylcyclotetrasiloxane, not only can the regulation of persistent organic pollutants be considered, but also by applying a coating composition using the silicone acrylic graft copolymer resin emulsion of the present invention to a substrate, excellent touch feeling, abrasion resistance, transparency, water repellency, and storage stability can be imparted.

[0021] As described above, the development of a silicone acrylic graft copolymer resin emulsion with reduced octamethylcyclotetrasiloxane has been demanded.

[0022] As a result of intensive studies to achieve the above object, the present inventor has found that in a specific polyorganosiloxane emulsion, a graft copolymer resin obtained by graft-polymerizing a (meth)acrylate monomer at a specific blending ratio, a silicone acrylic graft copolymer resin emulsion containing the graft copolymer resin can reduce octamethylcyclotetrasiloxane, and a coating composition using the silicone acrylic graft copolymer resin emulsion of the present invention can impart excellent touch feeling, water repellency, and slidability to the surface of a substrate when applied to the substrate and dried, and thus the present invention has been completed.

[0023] That is, the present invention is a silicone acrylic graft copolymer resin emulsion, (I) a polyorganosiloxane represented by the following general formula (1), (In the formula, R １ are each independently 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 are each independently an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which a part of the hydrogen atoms bonded to the carbon atom is substituted with a mercapto group, a vinyl group, an acryloxy group or a methacryloxy group, R ３ are each independently a phenyl group or the group defined by the above R １ , 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 silicone acrylic graft copolymer resin emulsion comprising 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 emulsion is 3,000 ppm or less, and the average particle size is 1 μm or less.

[0024] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0025] [Silicone Acrylic Graft Copolymer Resin Emulsion] The silicone acrylic graft copolymer resin emulsion of the present invention is an emulsion containing a graft copolymer resin of (I) a polyorganosiloxane represented by the following general formula (1) and (II) 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 set to 100 is (I):(II) = 60 to 99:1 to 40, and the content of octamethylcyclotetrasiloxane in the emulsion is 3,000 ppm or less, and the average particle size is 1 μm or less.

[0026] (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, independently of each other, which is 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 (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.)

[0027] More specifically, it is a silicone acrylic graft copolymer resin emulsion obtained by emulsion graft polymerization 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.

[0028] 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, component (I) is 70 to 95 parts by mass and component (II) is 5 to 30 parts by mass.

[0029] [(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, independently of each other, which is 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 (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.)

[0030] The above R １ These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl groups; aryl groups such as tolyl and naphthyl groups; alkenylaryl groups such as vinylphenyl groups; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups; alkenylaralkyl groups such as vinylbenzyl and vinylphenylpropyl groups; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, and chlorine, carboxyl groups, alkoxy groups, alkenyloxy groups, amino groups, and alkyl or alkoxy groups. １ The group is preferably an unsubstituted alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.

[0031] The above R２ 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.

[0032] 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.

[0033] The above X is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, or a hydroxyl group. The above R is an example of 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.

[0034] 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, 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 relative 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) relative to the total number of a to d, 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) relative to the total number of a to d, 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.

[0035] 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 provides a coating agent that imparts the excellent lubricity characteristic of silicone.

[0036] 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

[0037] 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] ).

[0038] As mentioned above, it is preferable to emulsion-graft polymerization of (I) polyorganosiloxane and (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.

[0039] 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.

[0040] 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.

[0041] 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.)

[0042] 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 alcohol generation. Here, (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.

[0043] By copolymerizing the above silane coupling agent, the effect of grafting the monomer of component (II) can be obtained.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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 resin emulsion was measured using a laser diffraction / scattering particle size distribution analyzer LA-950 (manufactured by Horiba, Ltd.).

[0055] 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.

[0056] 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.

[0057] [(II) Acrylic acid monomers and / or methacrylic acid monomers] The (II) acrylic acid monomers and / or methacrylic acid monomers used in the present invention (hereinafter sometimes referred to as acrylic components) are based on linear and branched esters having 1 to 20 carbon atoms and include those having functional groups such as amide groups, vinyl groups, carboxyl groups, and hydroxyl groups.

[0058] 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.

[0059] 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.

[0060] [Method for producing silicone acrylic graft copolymer resin emulsion] The method for producing the silicone acrylic graft copolymer resin emulsion of the present invention comprises the step of adding the acrylic acid ester monomer and / or methacrylic acid ester monomer of (II) to the emulsion containing the polyorganosiloxane of (I) and polymerizing it.

[0061] 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.

[0062] 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, by using a radical initiator.

[0063] 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.

[0064] 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.

[0065] Furthermore, a chain transfer agent can be added to adjust the molecular weight.

[0066] Furthermore, the solid content of the silicone acrylic graft copolymer resin emulsion of the present invention is preferably 35 to 55% by mass. The viscosity (at 25°C) is preferably 1,000 mPa·s or less, more preferably 500 mPa·s or less, and particularly preferably 20 to 300 mPa·s. The viscosity is measured using a rotational viscometer. The average particle diameter is 1 μm or less, preferably 0.1 to 0.5 μm, and more preferably 0.15 to 0.35 μm. If the average particle diameter exceeds 1 μm, whitening may occur.

[0067] The content of octamethylcyclotetrasiloxane in the silicone acrylic graft copolymer resin emulsion of the present invention is 3,000 ppm or less.

[0068] [Coating Composition] The coating composition of the present invention preferably comprises: (A) the silicone acrylic graft copolymer resin emulsion described above: 1 to 40% by mass in terms of solid content; and (B) at least one resin emulsion selected from vinyl chloride resin emulsion, acrylic resin emulsion, acrylic silicone resin emulsion, urethane resin emulsion, alkyd resin emulsion, and epoxy resin emulsion: 60 to 99% by mass in terms of solid content.

[0069] The above component (B) is a resin emulsion other than component (A), namely at least one resin emulsion selected from vinyl chloride resin emulsion, acrylic resin emulsion, acrylic silicone resin emulsion, urethane resin emulsion, alkyd resin emulsion, and epoxy resin emulsion. More specifically, it is a vinyl chloride resin emulsion, an acrylic resin emulsion using (meth)acrylic monomers such as (meth)acrylic acid and (meth)acrylic acid ester, an acrylic silicone resin emulsion, a urethane resin emulsion, and an alkyd resin emulsion. Preferably, it is a resin emulsion that has film-forming ability. Film-forming ability means that at a certain temperature or higher, the particulate nature of the coating surface after drying disappears and fine cracks do not occur during drying. The drying temperature (MFT) range for film formation is not particularly limited. The hardness of the paint film when the above (B) resin emulsion is dried was measured according to JIS K 5400-5-4, and although not particularly limited, it is preferably 2B to 2H on the pencil hardness scale.

[0070] Furthermore, depending on the purpose of the present invention, the coating composition of the present invention may also contain pigments, antioxidants, ultraviolet absorbers, antifreeze agents, pH adjusters, preservatives, defoamers, antibacterial agents, antifungal agents, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, surfactants, organic solvents such as film-forming aids, and other resins.

[0071] The coating composition of the present invention is obtained by mixing the above (A) silicone acrylic graft copolymer resin emulsion and the above (B) resin emulsion in an aqueous system using known mixing and preparation methods such as a propeller-type stirrer, homogenizer, ball mill, bead mill, or disper mixer.

[0072] For example, the coating composition of the present invention can be obtained by adding component (A) to a mixture of component (B) being stirred at 500 rpm in a disper mixer and stirring at 1,000 rpm for 30 minutes.

[0073] By applying or immersing the coating composition obtained in this manner onto one or both sides of a substrate such as a resin substrate, ceramic substrate, ceramic building material (such as sizing board), concrete, wood substrate, metal substrate, or mortar substrate, and then drying it, the advantages of the silicone resin, such as water repellency, weather resistance, heat resistance, cold resistance, gas permeability, and sliding properties, can be imparted over a long period of time while maintaining the advantages of the substrate.

[0074] Examples of resin substrates used include poly(meth)acrylic acid esters such as polymethyl methacrylate, polycarbonate, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyester, cellulose, diethylene glycol bisallyl carbonate polymer, acrylonitrile-butadiene-styrene polymer, polyurethane, and epoxy resin. Drying methods include leaving the material at room temperature for 1 to 10 days, but from the viewpoint of rapid curing, heating at a temperature of 20 to 150°C for 1 second to 10 hours is preferred. Furthermore, if the resin substrate is made of a material that is prone to deformation or discoloration due to heating, drying at a relatively low temperature of 20 to 100°C is preferred.

[0075] Examples of the ceramic substrates mentioned above include fired products such as oxides, carbides, and nitrides.

[0076] Examples of the ceramic building materials mentioned above include sizing boards.

[0077] As the above-mentioned wood substrate, wood from families such as Aceraceae, Betulaceae, Lauraceae, Chestnutaceae, Scrophulariaceae, Araucariaceae, Ulmaceae, Bignoniaceae, Rosaceae, Cupressaceae, Dipterocarpaceae, Myrtaceae, Fagaceae, Pinaceae, Fabaceae, and Oleaceae can be used. A method of hot air drying at 20 to 150°C, particularly 50 to 150°C for 0.5 to 5 hours, is preferred. Furthermore, discoloration of the coating can be avoided if the drying temperature is kept below 120°C.

[0078] Examples of the above-mentioned metal substrates include Si, Cu, Fe, Ni, Co, Au, Ag, Ti, Al, Zn, Sn, Zr, and their alloys.

[0079] The method for applying the coating composition of the present invention to a substrate is not particularly limited, but examples include application methods using various coaters such as gravure coaters, bar coaters, blade coaters, roll coaters, air knife coaters, screen coaters, and curtain coaters, as well as spray application, dipping, and brush application.

[0080] The amount of the above coating composition applied to the substrate is not particularly limited, but usually, from the viewpoint of stain resistance and workability, it is preferably 1 to 300 g / m² in terms of solid content. ２ More preferably 5 to 100 g / m ２ The film is formed in the range of 1 to 500 μm, preferably 5 to 100 μm, and then dried by natural drying or by heating to 100 to 200°C.

[0081] Furthermore, the coating composition of the present invention may contain a silicone acrylic graft copolymer resin emulsion in an amount of 10 to 60% by mass in terms of solid content relative to the total mass of the composition. Such a coating composition is preferable because it can be expected to significantly improve abrasion resistance and tactile feel.

[0082] 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.

[0083] <(I) Production of polyorganosiloxane → (A) Production of silicone acrylic graft copolymer resin emulsion> [Example 1] Viscosity of 700 mm ２ Organopolysiloxane (A-1) having a silanol group at the end of the molecular chain of / s (in general formula (1), R １92.09 parts of (methyl group, octamethylcyclotetrasiloxane content 50 ppm or less) 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. Then, 0.46 parts of sodium carbonate dissolved in deionized water were added to the resulting 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 composition. The resulting emulsion had the following properties in general formula (1): a = 99.866, b = 0.078, c = 0, d = 0.056, a solid content of 53.6%, an octamethylcyclotetrasiloxane content of 800 ppm, a viscosity of 105 mPa·s, an average particle size of 0.28 μm, and a molecular weight (M) of 300,000.

[0084] 59.0 parts of the obtained silicone 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 emulsion had a solid content of 44.9%, an octamethylcyclotetrasiloxane content of 640 ppm, and an average particle size of 0.25 μm.

[0085] [Example 2] Viscosity of 700 mm ２Organopolysiloxane (A-1) having a silanol group at the end of the molecular chain of / s (in general formula (1), R １ 92.09 parts of (methyl group, octamethylcyclotetrasiloxane content 50 ppm or less) 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 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 composition. In general formula (1), the obtained emulsion had a=99.866, b=0.078, c=0, and d=0.056, a solid content of 53.6%, an octamethylcyclotetrasiloxane content of 800 ppm, a viscosity of 105 mPa·s, an average particle size of 0.28 μm, and a molecular weight (M) of 300,000.

[0086] 59.0 parts of the obtained silicone emulsion were placed in a reaction vessel and diluted with 13.2 parts of deionized water. After adjusting the temperature to 30°C, 3.2 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 emulsion had a solid content of 44.5%, an octamethylcyclotetrasiloxane content of 950 ppm, and an average particle size of 0.24 μm.

[0087] [Example 3] Viscosity of 700 mm ２94.29 parts of organopolysiloxane (A-1) 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 composition. In general formula (1), the obtained emulsion had a=99.868, b=0.076, c=0, and d=0.056, with a solid content of 53.1%, an octamethylcyclotetrasiloxane content of 860 ppm, a viscosity of 285 mPa·s, an average particle size of 0.68 μm, and a molecular weight (M) of 300,000.

[0088] 59.0 parts of the obtained silicone 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 emulsion had a solid content of 45.0%, an octamethylcyclotetrasiloxane content of 860 ppm, and an average particle size of 0.72 μm.

[0089] [Example 4] Viscosity of 700 mm ２92.09 parts of organopolysiloxane (A-1) 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 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 53.8%, an octamethylcyclotetrasiloxane content of 2,240 ppm, a viscosity of 1,420 mPa·s, an average particle size of 0.32 μm, and a molecular weight (M) of 300,000.

[0090] 59.0 parts of the obtained silicone 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 emulsion had a solid content of 44.2%, an octamethylcyclotetrasiloxane content of 1,200 ppm, and an average particle size of 0.32 μm.

[0091] [Example 5] Viscosity of 700 mm ２91.98 parts of organopolysiloxane (A-1) 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 general formula (1), the obtained emulsion had a=99.797, b=0.076, c=0, and d=0.127, with a solid content of 52.9%, an octamethylcyclotetrasiloxane content of 1,180 ppm, a viscosity of 92 mPa·s, an average particle size of 0.22 μm, and a molecular weight (M) of 170,000.

[0092] 59.0 parts of the obtained silicone 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 emulsion had a solid content of 44.8%, an octamethylcyclotetrasiloxane content of 710 ppm, and an average particle size of 0.22 μm.

[0093] [Example 6] Viscosity of 700 mm ２ Organopolysiloxane (A-1) having a silanol group at the end of the molecular chain of / s (in general formula (1), R １92.09 parts of (methyl group, octamethylcyclotetrasiloxane content 50 ppm or less) 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 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 composition. In general formula (1), the obtained emulsion had a=99.866, b=0.078, c=0, and d=0.056, a solid content of 53.6%, an octamethylcyclotetrasiloxane content of 800 ppm, a viscosity of 105 mPa·s, an average particle size of 0.28 μm, and a molecular weight (M) of 300,000.

[0094] 59.0 parts of the obtained silicone 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 emulsion had a solid content of 44.7%, an octamethylcyclotetrasiloxane content of 580 ppm, and an average particle size of 0.31 μm.

[0095] [Comparative Example 1] Viscosity of 700 mm ２ Organopolysiloxane (A-1) having a silanol group at the end of the molecular chain of / s (in general formula (1), R １92.09 parts of (methyl group, octamethylcyclotetrasiloxane content 50 ppm or less) 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 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 composition. In general formula (1), the obtained emulsion had a=99.866, b=0.078, c=0, and d=0.056, a solid content of 53.6%, an octamethylcyclotetrasiloxane content of 800 ppm, a viscosity of 105 mPa·s, an average particle size of 0.28 μm, and a molecular weight (M) of 300,000.

[0096] Performance evaluation was conducted without performing acrylic graft copolymerization.

[0097] [Comparative Example 2] Viscosity of 700 mm ２ Organopolysiloxane (A-1) having a silanol group at the end of the molecular chain of / s (in general formula (1), R １92.09 parts of (methyl group, octamethylcyclotetrasiloxane content 50 ppm or less) 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 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 composition. In general formula (1), the obtained emulsion had a=99.866, b=0.078, c=0, and d=0.056, a solid content of 53.6%, an octamethylcyclotetrasiloxane content of 800 ppm, a viscosity of 105 mPa·s, an average particle size of 0.28 μm, and a molecular weight (M) of 300,000.

[0098] 59.0 parts of the obtained silicone emulsion were placed in a reaction vessel and diluted with 71.8 parts of deionized water. After adjusting the temperature to 30°C, 31.6 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, but gelation did not occur and an emulsion could not be obtained.

[0099] [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 general formula (1), the obtained emulsion had a=99.884, b=0.060, c=0, and d=0.056, with a solid content of 45.0%, an octamethylcyclotetrasiloxane content of 24,000 ppm, a viscosity of 80 mPa·s, an average particle size of 0.30 μm, and a molecular weight (M) of 250,000.

[0100] 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 peroxide and activator, to carry out acrylic graft copolymerization by redox reaction. The obtained emulsion had a solid content of 44.3%, an octamethylcyclotetrasiloxane content of 17,000 ppm, and an average particle size of 0.33 μm.

[0101] [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 (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 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%, an octamethylcyclotetrasiloxane content of 24,000 ppm, a viscosity of 80 mPa·s, an average particle size of 0.30 μm, and a molecular weight (M) of 250,000.

[0102] 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, 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 emulsion had a solid content of 44.3%, an octamethylcyclotetrasiloxane content of 16,600 ppm, and an average particle size of 0.31 μm.

[0103] The amounts of each component used in Examples 1-6 and Comparative Examples 1-4 are shown in Tables 1 and 2, respectively.

[0104] <Method for measuring solid content> Approximately 1 g of the resin emulsion (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)

[0105] <Octamethylcyclotetrasiloxane (D4) content in the emulsion> 0.1 g of the emulsion 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.

[0106] <Viscosity Measurement> The viscosity of the emulsion was measured using a BM-type viscometer with rotor No. 2, at 25°C and 6 rpm.

[0107] <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.).

[0108] <Molecular Weight Measurement Method> The molecular weight (M) was determined from the specific viscosity of a toluene solution of polyorganosiloxane at a concentration of 1 g / 100 mL.

[0109] Specifically, 20 g of emulsion was mixed with 20 g of IPA (isopropyl alcohol). After the emulsion was broken down, the IPA was discarded, and the remaining rubbery polyorganosiloxane was dried at 105°C for 3 hours. Toluene was added to this to make a toluene solution of polyorganosiloxane at a concentration of 1 g / 100 mL, and the viscosity was measured at 25°C using an Ubbelohde viscometer. The molecular weight (M) was calculated by substituting the measured viscosity into the following formula: 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 (References: Nakamuta, Nikka, 77 858

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

[1953] )

[0110] <Preparation of individual films> Using a bar coater No. 10 or No. 12, a PET film (manufactured by Toray Industries, Inc., product number: Lumirror #125-S10) was coated so that the film thickness after drying was 10 μm, and the individual films were prepared by drying in a 105°C dryer for 5 minutes.

[0111] <Measurement of Water Contact Angle> After contacting each coating with 0.2 μL of deionized water droplets, the contact angle of the droplets was measured 10 seconds later using an automatic contact angle measuring device DMO-601 (manufactured by Kyowa Interface Chemical Co., Ltd.). In terms of water repellency, a water contact angle in the range of 70 to 150° is preferable.

[0112] <Measurement of Static and Dynamic Friction Coefficients> Using a HEIDON TYPE-38 (manufactured by Shinto Kagaku Co., Ltd.), a 200g stainless steel metal indenter was brought into contact perpendicularly with the coating films of each of the above examples and comparative examples, and the frictional force was measured when it was moved at 3 cm / min. From the frictional force, the static friction coefficient and dynamic friction coefficient were calculated. In terms of sliding properties, it is preferable that the static friction coefficient is in the range of 0.02 to 0.07 and the dynamic friction coefficient is in the range of 0.01 to 0.05.

[0113] <Tackiness> The surface of the PET film formed with the above single film was sensorily evaluated by touching it with a finger. ○: No tackiness, good slipperiness. ×: Tackiness present, resistance felt on the finger, no slipperiness.

[0114] All raw materials used are listed in parts by mass. D4: Octamethylcyclotetrasiloxane MMA: Methyl methacrylate BA: Butyl acrylate

[0115] All raw materials used are listed in parts by mass. D4: Octamethylcyclotetrasiloxane MMA: Methyl methacrylate BA: Butyl acrylate

[0116] From the results in Tables 1 and 2 above, Examples 1 to 6 using the silicone acrylic graft copolymer resin emulsion of the present invention all had an octamethylcyclotetrasiloxane content of less than 3,000 ppm and an average particle size of 1 μm or less. The coatings prepared by applying the emulsion showed good results in terms of water repellency, sliding properties, and tackiness.

[0117] On the other hand, Comparative Example 1, which did not contain component (II) of the present invention, resulted in inferior tackiness. In Comparative Example 2, where the mixing ratio of component (I) and component (II) differed from that of the present invention, gelation occurred and evaluation was not possible. In Comparative Examples 3 and 4, the emulsions also contained an amount of D4 exceeding 3000 ppm, indicating that the silicone acrylic graft copolymer resin emulsion of the present invention could not be obtained.

[0118] This specification includes the following embodiments: [1]: A silicone acrylic graft copolymer resin emulsion 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, independently of each other, which is 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 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 silicone acrylic graft copolymer resin emulsion comprising 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 emulsion is 3,000 ppm or less, and the average particle size is 1 μm or less. [2]: The silicone acrylic graft copolymer resin emulsion according to [1], wherein the molecular weight of the polyorganosiloxane of (I) is 5,000 to 500,000. [3]: A silicone acrylic graft copolymer resin emulsion according to [1] or [2], characterized in that the viscosity of the emulsion containing the polyorganosiloxane of (I) at a solid content of 35 to 55% is less than 1,000 mPa·s. [4]: ​​A coating composition characterized in that it contains 10 to 60% by mass in terms of solid content of the silicone acrylic graft copolymer resin emulsion according to any one of [1] to [3]. [5]: A coating composition characterized in that it contains (A) a silicone acrylic graft copolymer resin emulsion according to any one of [1] to [3]: 1 to 40% by mass in terms of solid content, and (B) at least one resin emulsion selected from vinyl chloride resin emulsion, acrylic resin emulsion, acrylic silicone resin emulsion, urethane resin emulsion, alkyd resin emulsion, and epoxy resin emulsion: 60 to 99% by mass in terms of solid content.[6]: A method for producing a silicone acrylic graft copolymer resin emulsion according to any one of [1] to [3], characterized by comprising the step of adding the acrylic acid ester monomer and / or methacrylic acid ester monomer of (II) to the emulsion containing the polyorganosiloxane of (I) and polymerizing it.

[0119] 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 emulsion 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 silicone acrylic graft copolymer resin emulsion comprising a graft copolymer resin with 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 emulsion is 3,000 ppm or less, and the average particle size is 1 μm or less.

2. The silicone acrylic graft copolymer resin emulsion 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 emulsion according to claim 1, characterized in that the viscosity of the emulsion containing the polyorganosiloxane of (I) at a solid content of 35 to 55% is less than 1,000 mPa·s.

4. A coating composition characterized by containing 10 to 60% by mass, in terms of solid content, of the silicone acrylic graft copolymer resin emulsion described in any one of claims 1 to 3, relative to the total mass of the composition.

5. A coating composition characterized by comprising: (A) a silicone acrylic graft copolymer resin emulsion according to any one of claims 1 to 3: 1 to 40% by mass in terms of solid content; and (B) at least one resin emulsion selected from vinyl chloride resin emulsion, acrylic resin emulsion, acrylic silicone resin emulsion, urethane resin emulsion, alkyd resin emulsion, and epoxy resin emulsion: 60 to 99% by mass in terms of solid content.

6. A method for producing a silicone acrylic graft copolymer resin emulsion according to any one of claims 1 to 3, characterized by comprising the step of adding either or both of the acrylic acid ester monomer and the methacrylic acid ester monomer according to (II) to the emulsion containing the polyorganosiloxane according to (I) and polymerizing it.

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