Vinyl chloride-silicone graft copolymer and method for producing same

Abstract

The present invention provides a vinyl chloride-silicone copolymer having sliding properties, water repellency, alcohol resistance, substrate adhesion properties, and transparency.　Provided is a vinyl chloride-silicone graft copolymer of (A) an organopolysiloxane of formula (1) and (B) vinyl chloride, wherein the mass ratio (A):(B) is 5:95 to 95:5. (In formula (1), R1 is a C1-20 monovalent hydrocarbon group, and R2 is a radical reactive functional group. X is a C1-20 monovalent hydrocarbon group, a C1-20 alkoxy group, or a hydroxyl group. Y is X or a group represented by -[O-Si(X)2]d-X. Z is a C1-4 alkyl group, a C1-4 alkoxy group, or a hydroxyl group. a is 0-10,000, b is 100-10,000, c is 0.0001-100, and d is 1-1,000.)

Description

Vinyl chloride-silicone graft copolymer and its manufacturing method

[0001] The present invention relates to a graft copolymer of organopolysiloxane and vinyl chloride and a method for producing the same. More specifically, the present invention relates to a vinyl chloride-silicone graft copolymer that has sliding properties, water repellency, alcohol resistance, substrate adhesion, and transparency, and a method for producing the same.

[0002] Silicone resins have been known as resins that can impart slidability to substrates, but when used alone, silicone resins have drawbacks such as poor adhesion to substrates.

[0003] Therefore, a method has been used in which a silicone resin is copolymerized with another monomer such as an acrylic resin, a urethane resin, or a vinyl acetate resin. Copolymers such as acrylic silicone and urethane silicone can impart the advantages of silicone resin, such as weather resistance, heat resistance, cold resistance, water repellency, gas permeability, and sliding properties, to the properties of acrylic resin and urethane resin.

[0004] For example, Patent Document 1 (JP 2020-90563 A) discloses a silicone acrylic graft copolymer resin having sliding properties and a method for producing the same. Furthermore, Patent Document 2 (JP 2022-131528 A) discloses a vinyl acetate-silicone copolymer resin having sliding properties, substrate adhesion, and organic solvent solubility and a method for producing the same.

[0005] On the other hand, it is known that vinyl chloride resins are also copolymerized with other monomers for use. For example, vinyl chloride-vinyl acetate copolymer resins, which are copolymers of vinyl chloride and vinyl acetate, are exemplified. Patent Document 3 (JP 2001-114839 A) and the like disclose vinyl chloride-vinyl acetate copolymer resins and methods for producing the same, and it is known that their use in substrates such as ink materials and receiving layers can improve color development and adhesion.

[0006] Although it is known that silicone resins or vinyl chloride resins can be copolymerized by reacting each with a different monomer, few attempts have been made to copolymerize vinyl chloride and organopolysiloxane (silicone resin) because they are inherently incompatible. Furthermore, it was not thought that copolymerizing silicone and vinyl chloride would result in a resin that utilizes the properties of both.

[0007] Patent Document 4 (Japanese Patent Laid-Open Publication No. 59-166520) discloses that a resin obtained by graft polymerizing silicone onto a vinyl chloride resin has good oxygen permeability, and the resin has been considered for use in the packaging of fresh foods and in medical blood bags. However, the roll-kneaded product is not very practical for use in these applications in the form of a sheet, and there is room for improvement.

[0008] Furthermore, Patent Document 5 (JP 07-102146 A) discloses that the use of a block copolymer resin consisting of vinyl chloride and siloxane blocks improves releasability during calender roll processing. Patent Document 6 (JP 09-255705 A) discloses polymerizing vinyl chloride in the presence of a copolymer resin of siloxane and acrylic. These are used as additives during the production of vinyl chloride resin, and little research has been conducted to date on vinyl chloride-silicone copolymer resins.

[0009] Furthermore, it is possible to obtain a coating agent by mixing a silicone resin emulsion with a vinyl chloride resin emulsion, but the silicone component bleeds out when the mixture is used, making it impossible to obtain the desired performance, leaving room for improvement.

[0010] Japanese Patent Application Laid-Open No. 2020-90563 Japanese Patent Application Laid-Open No. 2022-131528 Japanese Patent Application Laid-Open No. 2001-114839 Japanese Patent Application Laid-Open No. 59-166520 Japanese Patent Application Laid-Open No. 07-102146 Japanese Patent Application Laid-Open No. 09-255705

[0011] Therefore, an object of the present invention is to provide a vinyl chloride-silicone graft copolymer that has sliding properties, water repellency, alcohol resistance, substrate adhesion, and transparency.

[0012] As a result of extensive research conducted by the present inventors in order to achieve the above-mentioned object, they discovered that a vinyl chloride-silicone graft copolymer obtained by graft copolymerizing the following (A) organopolysiloxane with (B) vinyl chloride has excellent sliding properties, water repellency, alcohol resistance, adhesion to substrates, and transparency, and have thus completed the present invention.

[0013] That is, the present invention provides the following vinyl chloride-silicone graft copolymer, a method for producing the same, and a composition and emulsion of the graft copolymer.

[0014] [1] A vinyl chloride-silicone graft copolymer, which is a graft copolymer of (A) an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride, wherein the mass ratio of the organopolysiloxane (A) to the vinyl chloride (B) is (A):(B) = 5:95 to 95:5: (In formula (1), R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 is a radical reactive functional group. X is the same or different, substituted or unsubstituted, monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, or hydroxyl group. Y is X or -[O-Si(X)] d -X, which may be the same or different. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000.) [2] A method for producing a vinyl chloride-silicone graft copolymer, comprising a step of polymerizing (A) an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride in a mass ratio of (A):(B) = 5:95 to 95:5: (In formula (1), R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 is a radical reactive functional group. X is the same or different, substituted or unsubstituted, monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, or hydroxyl group. Y is X or -[O-Si(X)]d -X. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000.) [3] A composition containing the vinyl chloride-silicone graft copolymer according to [1] in an amount of 10 to 60% by mass in terms of solid content, based on the mass of the total composition. [4] An emulsion of the vinyl chloride-silicone graft copolymer according to [1].

[0015] The vinyl chloride-silicone graft copolymer of the present invention possesses sliding properties, water repellency, alcohol resistance, substrate adhesion, and transparency. For these reasons, compositions containing the vinyl chloride-silicone graft copolymer of the present invention are suitable for use in coating agents for various substrates, adhesives, exterior and interior paints for structures and building materials, and cosmetics.

[0016] Vinyl Chloride-Silicone Graft Copolymer The present invention is a vinyl chloride-silicone graft copolymer obtained by graft copolymerizing (A) an organopolysiloxane and (B) vinyl chloride.

[0017] The organopolysiloxane (A) in the present invention is represented by the following formula (1). (In formula (1), R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 is a radical reactive functional group. X is the same or different, substituted or unsubstituted, monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, or hydroxyl group. Y is X or -[O-Si(X)] d -X, which may be the same or different. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000.

[0018] Here, R 1are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and specifically 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; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl, tolyl, and naphthyl groups; Examples of such groups include alkenylaryl groups such as a phenyl group, aralkyl groups such as a benzyl group, a phenylethyl group, and a phenylpropyl group, and alkenylaralkyl groups such as a vinylbenzyl group and a vinylphenylpropyl group, as well as groups in which some or all of the hydrogen atoms have been substituted with a halogen atom such as a fluorine, bromine, or chlorine atom, an acryloxy group, a methacryloxy group, a carboxyl group, an alkoxy group, an alkenyloxy group, an amino group, or an alkyl-, alkoxy-, or (meth)acryloxy-substituted amino group. 1 is preferably a methyl group.

[0019] R 2 is a radical reactive functional group, and examples thereof include a mercapto group or an alkyl group having 1 to 8 carbon atoms substituted with an ethylenic double bond-containing group, a vinyl group, or a styryl group. Specific examples of the alkyl group having 1 to 8 carbon atoms substituted with a mercapto group or an ethylenic double bond-containing group include mercapto groups, vinyl groups, styryl groups, and alkyl groups having 1 to 8 carbon atoms substituted with an acryloxy group or methacryloxy group. R 2 Examples of the radical reactive functional group represented by R include a vinyl group, a styryl group, an octenyl group, a methacryloxyoctyl group, a mercaptopropyl group, an acryloxypropyl group, a methacryloxypropyl group, and a methacryloxyoctylvinyl group. 2 R may be one type. 2 may be a combination of two or more.

[0020] X is the same or different, 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 unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms is preferably R 1Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, a tetradecyloxy group, etc. Among these, a hydroxyl group, a methyl group, a butyl group, and a phenyl group are preferred.

[0021] Y is X or —[O—Si(X)2] d -X is the same or different group. Examples of X include the same groups as those exemplified above.

[0022] Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and is preferably a hydroxyl group or a methyl group.

[0023] a is a number from 0 to 10,000, preferably a number from 0 to 1,000, and more preferably a number from 0 to 200. When a units are constituted, the lowest limit is preferably 0.5. If a is greater than 10,000, when a composition containing component (A) is used as a coating film, the strength of the resulting film may be insufficient. b is a number from 100 to 10,000, preferably a number from 1,000 to 10,000, and more preferably a number from 1,000 to 5,000. If b is less than 100, the flexibility of the coating may be poor, and if it is greater than 10,000, the tear strength may be reduced. c is a number from 0.0001 to 100, and if it exceeds 100, the sliding effect may not be exhibited. Here, c / (a+b+c)×100 is preferably 0.0001 to 10, more preferably 0.001 to 10, even more preferably 0.001 or more and less than 4, and particularly preferably 0.001 to 2. d is a number from 1 to 1,000, and preferably a number from 1 to 200.

[0024] The organopolysiloxane represented by formula (1) is preferably used in the form of an emulsion, and may be a commercially available product or may be synthesized. When synthesized, it can be easily synthesized by a known emulsion polymerization method, for example, by emulsifying and dispersing a cyclic organosiloxane, an α,ω-dihydroxysiloxane oligomer, an α,ω-dialkoxysiloxane oligomer, an alkoxysilane, or the like, and a silane coupling agent represented by formula (2) below in water using an anionic surfactant, and then adding a polymerization catalyst such as an acid as needed to carry out a polymerization reaction. The cyclic organosiloxane may have a fluorine atom, a (meth)acryloxy group, a carboxyl group, a hydroxyl group, or an amino group. (In formula (2), R 3 is a radical reactive functional group, particularly an acryloxy group, a methacryloxy group, a vinyl group, or a mercapto group-substituted alkyl group having 1 to 8 carbon atoms, or a styryl group or a vinyl group. 4 is an alkyl group or a hydroxy group having 1 to 4 carbon atoms, and R 5 is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, and e+f is 2 or 3.

[0025] Examples of the cyclic organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane, and 1,3,5,7-tetra(3-methacryloxypropyl)tetramethylsiloxane. Examples include chlorotetrasiloxane, 1,3,5,7-tetra(3-acryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-carboxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-vinyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(p-vinylphenyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra[3-(p-vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(N-acryloyl-N-methyl-3-aminopropyl)tetramethylcyclotetrasiloxane, and 1,3,5,7-tetra(N,N-bis(lauroyl)-3-aminopropyl)tetramethylcyclotetrasiloxane. Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are preferred.

[0026] Specific examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrippropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane; γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropyltriisopropoxysilane, and γ-(meth)acryloxypropyltributoxysilane; Examples of suitable silanes include acrylic silanes such as γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxypropylmethyldiisopropoxysilane, and γ-(meth)acryloxypropylmethyldibutoxysilane; mercaptosilanes such as γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropyltrimethoxysilane; and styrylsilanes such as styryltrimethoxysilane. Oligomers obtained by condensation polymerization of these silanes may be more preferred because they suppress the generation of alcohol. Here, (meth)acryloxy refers to acryloxy or methacryloxy. These silane coupling agents are preferably used in an amount of 0.01 to 20 parts by mass, and more preferably 0.01 to 5 parts by mass, per 100 parts by mass of cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, or alkoxysilane.

[0027] By copolymerizing a cyclic organosiloxane, an α,ω-dihydroxysiloxane oligomer, an α,ω-dialkoxysiloxane oligomer, or an alkoxysilane with a silane coupling agent, the repeating number c of the unit ([Si(R 2 )(Z)O]), which can be graft-polymerized with vinyl chloride (B).

[0028] Any known polymerization catalyst may be used as the polymerization catalyst. Among these, strong acids are preferred, such as hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid. Dodecylbenzenesulfonic acid, which has surfactant properties, is preferred. The amount of polymerization 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 the cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, or alkoxysilane.

[0029] Furthermore, preferred anionic surfactants include sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyltaurate salts, aliphatic soaps, alkyl phosphates, sodium lauroyl methyl taurine, sodium myristoyl methyl taurine, etc. More preferred are N-acyl amino acid salts, N-acyltaurate salts, aliphatic soaps, alkyl phosphates, sodium lauroyl methyl taurine, and sodium myristoyl methyl taurine, and particularly preferred are sodium lauroyl methyl taurine, sodium myristoyl methyl taurine, and sodium lauryl sulfate.

[0030] The amount of the anionic surfactant used is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, or alkoxysilane.

[0031] The polymerization temperature is preferably 50 to 75° C., and the polymerization time is preferably 10 hours or more, more preferably 15 hours or more. Furthermore, it is particularly preferable to age the mixture after polymerization at 5 to 30° C. for 10 hours or more.

[0032] After the polymerization reaction is completed, the reaction mixture may be neutralized to a pH of 2.5 to 14, preferably 4 to 11, using a neutralizing agent (such as a 10% aqueous sodium carbonate solution).

[0033] The weight average molecular weight (Mw) of the organopolysiloxane (A) as determined by viscosity measurement is preferably 10,000 to 1,000,000, and more preferably 100,000 to 500,000, from the viewpoint of sliding effect.

[0034] Here, the weight average molecular weight (Mw) of an organopolysiloxane determined by viscosity measurement is calculated from the specific viscosity ηsp (25°C) of a toluene solution of the organopolysiloxane at a concentration of 1 g / 100 ml: ηsp = (η / η0) - 1 (η0: viscosity of toluene, η: viscosity of solution), ηsp = [η] + 0.3[η] 2 [η]=0.215×10 -4 M 0.65 Specifically, 20 g of organopolysiloxane emulsion was mixed with 20 g of IPA (isopropyl alcohol), the emulsion was broken, the IPA was discarded, and the remaining rubbery organopolysiloxane was dried overnight at 60°C. This was made into a toluene solution of organopolysiloxane at a concentration of 1 g / 100 ml, and the viscosity was measured at 25°C using an Ubbelohde viscometer. The molecular weight can be calculated by substituting the viscosity into the above formula (References: Nakamuta, Nikka, 77 858

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

[1953] ).

[0035] Production Method The vinyl chloride-silicone graft copolymer of the present invention can be obtained by graft polymerizing (A) an organopolysiloxane and (B) vinyl chloride.

[0036] The method for producing the vinyl chloride-silicone graft copolymer of the present invention comprises the step of graft polymerizing an organopolysiloxane of formula (1) (component (A)) with vinyl chloride (component (B)) in a mass ratio (mass ratio of organopolysiloxane of formula (1) to vinyl chloride units) of 5:95 to 95:5, preferably 20:80 to 85:15. If the proportion of the organopolysiloxane component of formula (1) is less than 5, sliding effect may not be achieved.

[0037] Radical initiators used in the production of the vinyl chloride-silicone graft copolymer of the present invention include persulfates such as potassium persulfate and ammonium persulfate, aqueous hydrogen persulfate, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, redox compounds can be used in combination with reducing agents such as sodium sulfite, Rongalite, L-ascorbic acid, tartaric acid, sugars, and amines. The amount of radical initiator used is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, of the vinyl chloride (B).

[0038] The polymerization temperature for component (B) relative to component (A) is preferably 25 to 85° C., more preferably 55 to 85° C. The polymerization time is preferably 2 to 20 hours, more preferably 3 to 10 hours.

[0039] Furthermore, a chain transfer agent can be added to adjust the molecular weight and polymerization rate of the polymer. Examples of such an agent include halogenated hydrocarbons such as chloroform and carbon tetrachloride; and mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan. The amount of the chain transfer agent used is preferably 0.1 to 1 part by mass, and more preferably 0.3 to 0.8 parts by mass, per 100 parts by mass of the monomer (vinyl chloride).

[0040] The vinyl chloride-silicone graft copolymer obtained in this manner is a polymer in which vinyl chloride, component (B), is randomly bonded to organopolysiloxane, component (A), and is a polymer containing a mixture of many different structures, making it impossible to directly identify the product by its structure or properties.

[0041] The method for producing the vinyl chloride-silicone graft copolymer of the present invention preferably includes a step of emulsion polymerization of an organopolysiloxane of formula (1) (component (A)) with vinyl chloride (component (B)) in a mass ratio (mass ratio of organopolysiloxane of formula (1) to vinyl chloride units) of 5:95 to 95:5, preferably 20:80 to 85:15. When carrying out emulsion polymerization, the organopolysiloxane of component (A) is used in the form of an emulsion, and the surfactant contained in the organopolysiloxane emulsion is sufficient for graft polymerization. However, to improve stability, anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acylamino acid salts, N-acyltaurine salts, aliphatic soaps, and alkyl phosphates can be added. Nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can also be added. When a surfactant is added, its amount is preferably 0.1 to 5% by mass of the vinyl chloride (B). In this manner, the vinyl chloride-silicone graft copolymer obtained by emulsion polymerization can also be obtained in the form of an emulsion, i.e., as an emulsion of the vinyl chloride-silicone graft copolymer.

[0042] Furthermore, the vinyl chloride-silicone graft copolymer preferably has a solids content of 25 to 40% by mass in the emulsion. Furthermore, the viscosity of this emulsion (at 25°C) is preferably 1 to 500 mPa·s, more preferably 1 to 200 mPa·s. The viscosity can be measured using a rotational viscometer. The average particle size of the emulsion is preferably 0.1 μm (100 nm) to 0.5 μm (500 nm). The average particle size is a value measured using a dynamic light scattering particle size distribution analyzer.

[0043] The vinyl chloride-silicone graft copolymer of the present invention can also be granulated from the emulsion and powdered by the following methods. These include freeze-grinding, spray-drying, and airflow drying, but spray-drying is preferred from the viewpoint of productivity. The smaller the average particle size of the resulting powder particles, the better, with 1 to 50 μm being preferred, and 1 to 30 μm being more preferred. The particle sizes of the emulsion and powder can be measured as the cumulative mass average value D50 using a laser diffraction particle size analyzer.

[0044] By using the vinyl chloride-silicone graft copolymer (copolymer resin) of the present invention in combination with other resins, pigments, fillers, matting agents, antioxidants, UV absorbers, antifreeze agents, pH adjusters, preservatives, antifoaming agents, antibacterial agents, antifungal agents, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, surfactants and / or organic solvents (such as film-forming aids), etc., compositions containing the vinyl chloride-silicone graft copolymer can be used in coating agents for various substrates such as synthetic resins, metals, glass, ceramics, gypsum, paper, wood, leather, lightweight concrete, lightweight aerated concrete, mortar, calcium silicate board, slate, gypsum board, etc.; adhesives; paint binders for exterior and interior use of structures and building materials, etc.; paper processing agents; fiber treatment agents; cosmetics, etc.

[0045] The vinyl chloride-silicone graft copolymer-containing composition of the present invention preferably contains the vinyl chloride-silicone graft copolymer in an amount of 10 to 60 mass %, more preferably 20 to 50 mass %, and particularly preferably 30 to 50 mass %, in terms of solids content, relative to the mass of the entire composition.

[0046] When an organic solvent is mixed with the vinyl chloride-silicone graft copolymer-containing composition, examples of the organic solvent include aromatic hydrocarbons such as styrene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane and cyclohexane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and anisole; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohols such as methanol, ethanol, isopropanol, and n-butanol; nitriles such as acetonitrile, propionitrile, butyronitrile, and benzonitrile; amide compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; chloroform; and dimethyl sulfoxide. The organic solvents may be used alone or in combination.

[0047] The composition containing the vinyl chloride-silicone graft copolymer of the present invention can be used as a coating agent. In this case, the coating agent can be obtained by mixing and dissolving the vinyl chloride-silicone graft copolymer and other components using a known mixing and preparation method such as a propeller stirrer, homogenizer, ball mill, or bead mill. When this coating agent is applied to or immersed in one or both surfaces of a substrate such as glass or resin and then dried, it can impart sliding properties and substrate adhesion.

[0048] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Furthermore, the molecular weights shown below are weight-average molecular weights (Mw) determined by viscosity measurement from the specific viscosity of a toluene solution of the organopolysiloxane at a concentration of 1 g / 100 ml. In the following examples, parts and % represent parts by mass and % by mass, respectively.

[0049] Example 1 1200 g of octamethylcyclotetrasiloxane, 4.8 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 4 L polyethylene beaker, and after uniformly emulsifying using a homomixer, 728 g of water was gradually added to dilute the mixture, and the mixture was stirred under a pressure of 300 kgf / cm. 2 The emulsion was passed through a high-pressure homogenizer twice at 105°C, yielding a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours. After aging at 15°C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. After drying at 105°C for 3 hours, the emulsion had a non-volatile content (solids content) of 44%, and the organopolysiloxane in the emulsion was in the form of a non-flowable soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a molecular weight of approximately 250,000 and a structure represented by the following formula (A): 2 is a γ-methacryloxypropyl group. The structure of the organopolysiloxane obtained by the above polymerization reaction is 1 H-NMR (frequency 600 MHz, room temperature, accumulation number 128) and 29 The results were confirmed by Si-NMR (frequency 60 MHz, room temperature, 5000 accumulations) (apparatus name: JNM-ECA600, measurement solvent: CDCl3). 1207 g of the emulsion was transferred to a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet, and 59 g of vinyl chloride and ammonium persulfate were added. The reaction was carried out at 60°C for 8 hours to graft copolymerize vinyl chloride onto the silicone composition, yielding an emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30%. The obtained vinyl chloride-silicone graft copolymer was 2 The copolymer was a vinyl chloride-silicone graft copolymer, with vinyl chloride grafted onto it.

[0050] Example 2 An emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30% was obtained in the same manner as in Example 1, except that the amount of vinyl chloride was changed to 132 g.

[0051] Example 3 An emulsion of silicone vinyl chloride graft copolymer with a nonvolatile content of 30% was obtained in the same manner as in Example 1, except that the amount of vinyl chloride was changed to 226 g.

[0052] Example 4 1200 g of octamethylcyclotetrasiloxane, 0.96 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 4 L polyethylene beaker, and after uniformly emulsifying using a homomixer, 728 g of water was gradually added to dilute the mixture, and the mixture was stirred under a pressure of 300 kgf / cm. 2 The emulsion was passed through a high-pressure homogenizer twice at 105°C, yielding a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours. After aging at 15°C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. After drying at 105°C for 3 hours, the emulsion had a non-volatile content (solids content) of 45%, and the organopolysiloxane in the emulsion was in the form of a non-flowable soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a molecular weight of approximately 250,000 and a structure represented by the following formula (B): 2 is a γ-methacryloxypropyl group. 1,198 g of the emulsion was transferred to a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet, and 231 g of vinyl chloride and ammonium persulfate were added. The reaction was carried out at 60°C for 8 hours to graft copolymerize vinyl chloride onto the silicone composition, yielding an emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30%. The obtained vinyl chloride-silicone graft copolymer was 2 The copolymer was a vinyl chloride-silicone graft copolymer, with vinyl chloride grafted onto it.

[0053] Example 5 An emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30% was obtained in the same manner as in Example 1, except that the amount of vinyl chloride was changed to 528 g.

[0054] Example 6 An emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30% was obtained in the same manner as in Example 1, except that the amount of vinyl chloride was changed to 1,232 g.

[0055] Example 7 An emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30% was obtained in the same manner as in Example 1, except that the amount of vinyl chloride was changed to 4,752 g.

[0056] Comparative Example 1 1200 g of octamethylcyclotetrasiloxane, 4.8 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 4 L polyethylene beaker, and after uniformly emulsifying using a homomixer, 728 g of water was gradually added to dilute the mixture, and the mixture was stirred under a pressure of 300 kgf / cm. 2 The emulsion was passed through a high-pressure homogenizer twice at 105°C, yielding a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours. After aging at 15°C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. After drying at 105°C for 3 hours, the nonvolatile content (solids content) of this emulsion was 44%, and the organopolysiloxane in the emulsion was in the form of a non-flowable soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a molecular weight of approximately 250,000 and a structure represented by formula (A) above.

[0057] Comparative Example 2 840 g of vinyl chloride, 16.8 g of 2-hydroxyethyl methacrylate, and potassium peroxodisulfate were added to a polymerization vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet, and the mixture was reacted for 30 hours at 45°C while adding 2530 g of vinyl chloride, thereby obtaining a copolymer emulsion with a non-volatile content of 40%.

[0058] Comparative Example 3 1200 g of octamethylcyclotetrasiloxane, 0.96 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 2 L polyethylene beaker, and after uniformly emulsifying using a homomixer, 400 g of water was gradually added to dilute the mixture, and the mixture was stirred under a pressure of 300 kgf / cm. 2 The emulsion was passed through a high-pressure homogenizer twice at 105°C, yielding a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, thermometer, and reflux condenser and polymerized at 55°C for 24 hours. After aging at 15°C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. After drying at 105°C for 3 hours, this emulsion had a non-volatile content of 45%, and the organopolysiloxane in the emulsion was in the form of a non-flowable soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a molecular weight of approximately 250,000 and a structure represented by formula (B). Furthermore, 231.4 g of methyl methacrylate was added dropwise to this emulsion over 3 to 5 hours while the reaction was carried out using t-butyl hydroperoxide at 27°C, thereby graft-copolymerizing acrylic onto the silicone composition, yielding an emulsion of acrylic-silicone graft copolymer with a non-volatile content of 44.4%.

[0059] Comparative Example 4 160 g of the silicone emulsion obtained in Comparative Example 1 and 75 g of the vinyl chloride emulsion obtained in Comparative Example 2 were mixed with stirring for 1 hour to obtain a mixed emulsion with a nonvolatile content of 42.7%.

[0060] Comparative Example 5 1200 g of octamethylcyclotetrasiloxane, 0.96 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 2 L polyethylene beaker, uniformly emulsified using a homomixer, and then diluted by gradually adding 400 g of water. The mixture was then heated under a pressure of 300 kgf / cm. 2The emulsion was passed through a high-pressure homogenizer twice at 105°C, yielding a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, thermometer, and reflux condenser and polymerized at 55°C for 24 hours. After aging at 15°C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. After drying at 105°C for 3 hours, this emulsion had a nonvolatile content of 45%, and the organopolysiloxane in the emulsion was in the form of a non-flowable soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a molecular weight of approximately 250,000 and a structure represented by formula (B). Furthermore, 231.1 g of styrene was added dropwise to this emulsion over 3 to 5 hours while the reaction was carried out using t-butyl hydroperoxide at 27°C, thereby graft-copolymerizing styrene onto the silicone composition, yielding an emulsion of styrene-silicone graft copolymer with a nonvolatile content of 44.0%.

[0061] Comparative Example 6 1,200 g of octamethylcyclotetrasiloxane, 0.96 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 2-liter polyethylene beaker, and after uniformly emulsifying using a homomixer, 400 g of water was gradually added to dilute the mixture, and the mixture was stirred under a pressure of 300 kgf / cm. 2 The emulsion was passed through a high-pressure homogenizer twice at 105°C, yielding a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, thermometer, and reflux condenser and polymerized at 55°C for 24 hours. After aging at 15°C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. After drying at 105°C for 3 hours, this emulsion had a nonvolatile content of 45%, and the organopolysiloxane in the emulsion was in the form of a non-flowable soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a molecular weight of approximately 250,000 and a structure represented by formula (B). Furthermore, a reaction was carried out using t-butyl hydroperoxide at 27°C while 231.1 g of acrylonitrile was added dropwise to this emulsion over 3 to 5 hours. However, gelation occurred during the dropwise addition, and the desired acrylonitrile-silicone copolymer was not obtained.

[0062] The emulsions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were evaluated by the following methods. The results are shown in Tables 1 and 2.

[0063] <Method for measuring solid content> Approximately 1 g of sample was accurately weighed onto an aluminum foil dish, placed in a dryer maintained at approximately 105°C, heated for 1 hour, then removed from the dryer and allowed to cool in a desiccator. The aluminum foil dish containing the dried sample was weighed, and the solid content (evaporation residue) was calculated using the following formula. R: Solid content (evaporation residue) (%) W: Mass (g) of aluminum foil dish containing sample before drying L: Mass (g) of aluminum foil dish T: Mass (g) of aluminum foil dish containing sample after drying Dimensions of aluminum foil dish: 65φ×23h (mm)

[0064] <Viscosity Measurement Method> The liquid temperature of the sample was kept at 23±0.5° C., and the viscosity was measured using a rotational viscometer (No. 1 rotor, 6 rpm, manufactured by Toki Sangyo Co., Ltd.: trade name: VISCOMETER TVB-10).

[0065] <Average particle size> The average particle size (particle size value corresponding to 50% of the cumulative particle size distribution) was measured by weighing 0.01 g of a sample and using a laser diffraction particle size distribution analyzer (manufactured by Horiba, Ltd., product name: LA-950V2) under conditions of a circulation flow rate of 2 and a stirring speed of 2. [Measurement conditions] Measurement temperature: 25±1°C Solvent: ion-exchanged water

[0066] <Measurement of minimum film formation temperature (MFT)> The minimum film formation temperature (MFT, °C) of the emulsion was measured by a method conforming to JIS K-6828-2. Specifically, a simple film formation temperature measuring device (manufactured by Imoto Manufacturing Co., Ltd.) was used, in which a heating source and a cooling source were installed at a fixed distance. 1 μl of emulsion was applied to aluminum foil, and the state of the coating after 2 hours was observed using the device. The emulsion was dried under a temperature gradient, and the boundary temperature between the transparent part where a film was formed and the part where no film was formed was measured, and this was taken as the minimum film formation temperature (MFT, °C). Considering the drying property during coating formation, an MFT of 100°C or less is desirable.

[0067] <Measurement of static and dynamic friction coefficients> The emulsions of each example and comparative example were applied to a PET film using a bar coater and dried at 105°C for 3 minutes to form a coating film with a dry thickness of approximately 10 μm. Using a HEIDON TYPE-38 (manufactured by Shinto Scientific Co., Ltd.), a 200 g metal indenter was brought into contact with the coating film perpendicularly and moved at a speed of 3 cm / min, and the friction force was measured, and the friction coefficient was calculated from the friction force. Note that the preferred ranges for the static and dynamic friction coefficients under the above conditions are a static friction coefficient of 0.2 or less and a dynamic friction coefficient of 0.1 or less.

[0068] <Adhesion to substrate> Each emulsion of the examples and comparative examples was applied to a soft vinyl chloride film using a bar coater and dried at 105°C for 3 minutes to form a coating film with a thickness of approximately 10 µm after drying. Cellophane tape was applied to the coating film and peeled off in one go, and the adhesion was evaluated visually. ○: No peeling from the substrate ×: Peeling from the substrate

[0069] <Alcohol resistance> Each emulsion of the Examples and Comparative Examples was applied to a PET film using a bar coater and dried at 105°C for 3 minutes to form a coating film with a thickness of approximately 10 µm after drying. 98% ethanol was dropped onto the coating film and air-dried overnight at room temperature. The change in the coating film after air-drying was evaluated visually. ○: No change in appearance △: Traces remained but no whitening ×: Whitening

[0070] <Water Contact Angle Measurement> The emulsions of each Example and Comparative Example were applied to a PET film using a bar coater and dried at 105°C for 3 minutes to form a coating film with a dry thickness of approximately 10 μm. 2 μl of pure water was dropped onto the coating film, and the contact angle values ​​were measured after 1 second and 30 seconds using a contact angle meter CA-D model manufactured by Kyowa Interface Science Co., Ltd. Considering the prevention of water-based stains due to water repellency, a contact angle of 80° or more is preferred.

[0071]

[0072]

Claims

1. A vinyl chloride-silicone graft copolymer which is a graft copolymer of (A) an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride, and the mass ratio of (A) the organopolysiloxane to (B) vinyl chloride is (A):(B) = 5:95 to 95:

5. (In formula (1), R 1 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 2 is a radical-reactive functional group. X is the same or different 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. Y is the same or different group represented by X or -[O-Si(X)2] d -X. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. a is a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000.) 2. A method for producing a vinyl chloride-silicone graft copolymer, comprising a step of polymerizing (A) an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride in a mass ratio of (A):(B) = 5:95 to 95:

5. (In formula (1), R 1 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 2 is a radical-reactive functional group. X is the same or different 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. Y is the same or different group represented by X or -[O-Si(X)2] d -X. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000.) 3. A composition comprising the vinyl chloride-silicone graft copolymer according to claim 1 in a solid content of 10 to 60% by mass based on the total mass of the composition.

4. An emulsion of the vinyl chloride-silicone graft copolymer according to claim 1.

Images