Vinyl chloride-silicone graft copolymer and method for producing the same

Abstract

To provide a vinyl chloride-silicone copolymer having sliding properties, water repellency, alcohol resistance, substrate adhesion, and transparency.SOLUTION: A vinyl chloride-silicone graft copolymer is a copolymer of (A) an organopolysiloxane of formula (1) and (B) vinyl chloride, wherein a 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).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Conventionally, silicone-based resins are known as resins that can impart slidability to a substrate. However, when a silicone-based resin is used alone, there are problems such as poor adhesion to the substrate.

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

[0004] For example, Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2020-90563) discloses a silicone acrylic graft copolymer resin having slidability and a method for producing the same. Further, Patent Document 2 (Japanese Unexamined Patent Application Publication No. 2022-131528) discloses a vinyl acetate-silicone copolymer resin having slidability, substrate adhesion, and organic solvent solubility, and a method for producing the same.

[0005] On the other hand, it is also known that vinyl chloride resin is copolymerized with another monomer and used. For example, a vinyl chloride-vinyl acetate copolymer resin in which vinyl chloride and vinyl acetate are copolymerized can be mentioned. Patent Document 3 (Japanese Unexamined Patent Application Publication No. 2001-114839) etc. disclose a vinyl chloride-vinyl acetate copolymer resin and a method for producing the same, and it is known that color developability and adhesion can be enhanced by using it for a substrate such as an ink material or an acceptance layer.

[0006] Although it has been known to react and copolymerize silicone-based resins or vinyl chloride resins with different monomers respectively, attempts to copolymerize vinyl chloride and organopolysiloxanes (silicone-based resins) have rarely been made because they are originally incompatible with each other. Also, even if silicone and vinyl chloride are copolymerized, it has not been considered that a resin that makes use of the respective performances can be obtained.

[0007] Patent Document 4 (Japanese Patent Laid-Open 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 field related to fresh foods and medical blood bags. However, it has low practicality for use in sheet-forming roll kneaded materials for such applications and there is room for improvement.

[0008] Also, Patent Document 5 (Japanese Patent Laid-Open No. 07-102146) discloses that the use of a block copolymer resin composed of vinyl chloride and a siloxane block improves peelability during calender roll processing. Patent Document 6 (Japanese Patent Laid-Open No. 09-255705) discloses polymerizing vinyl chloride in the presence of a copolymer resin of siloxane and acrylic. These are uses as additives during the production of vinyl chloride resins, and little research has been conducted on vinyl chloride-silicone copolymer resins until now.

[0009] Furthermore, a method of mixing a silicone resin emulsion and a vinyl chloride resin emulsion to obtain a coating agent is also conceivable, but in the mixture, the silicone component bleeds out and the desired performance cannot be obtained, and there is room for improvement.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0012] As a result of intensive studies to achieve the above object, the present inventors have found that a vinyl chloride-silicone graft copolymer obtained by graft copolymerizing the following (A) organopolysiloxane and (B) vinyl chloride has slidability, water repellency, alcohol resistance, substrate adhesion, and transparency, and have 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 an emulsion of the graft copolymer.

[0014] [1] (A) A graft copolymer of an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride, wherein the mass ratio of the (A) organopolysiloxane to the (B) vinyl chloride is (A):(B)=5:95 to 95:5. A vinyl chloride-silicone graft copolymer. [Chemical Formula] (In formula (1), R 1is a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different and may be substituted or unsubstituted, and R 2 is a radical-reactive functional group. X is a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different and may be substituted or unsubstituted, 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) A method for producing a vinyl chloride-silicone graft copolymer, which comprises a step of polymerizing an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride at a mass ratio of (A):(B) = 5:95 to 95:5. [Chemical formula] (In the formula (1), R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different and may be substituted or unsubstituted, and R 2 is a radical-reactive functional group. X is a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different and may be substituted or unsubstituted, 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 containing the vinyl chloride-silicone graft copolymer according to [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 [1]. [Advantages of the Invention]

[0015] The vinyl chloride-silicone graft copolymer of the present invention has slidability, water repellency, alcohol resistance, substrate adhesion, and transparency. Therefore, the composition containing the vinyl chloride-silicone graft copolymer of the present invention is suitably used for coating agents for various substrates, adhesives, exterior and interior paints for structures and building materials, cosmetics, and the like.

Mode for Carrying Out the Invention

[0016] Vinyl chloride-silicone graft copolymer The present invention relates to a vinyl chloride-silicone graft copolymer obtained by graft copolymerizing (A) an organopolysiloxane and (B) vinyl chloride.

[0017] The (A) organopolysiloxane in the present invention is represented by the following formula (1).

Chemical formula

[0018] Here, R 1is a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different and may be substituted or unsubstituted. Specifically, it includes alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, etc.; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.; alkenyl groups such as vinyl group, allyl group, etc.; aryl groups such as phenyl group, tolyl group, naphthyl group, etc.; alkenylaryl groups such as vinylphenyl group, etc.; aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, etc.; alkenylaralkyl groups such as vinylbenzyl group, vinylphenylpropyl group, etc. Also included are those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., acryloxy group, methacryloxy group, carboxyl group, alkoxy group, alkenyloxy group, amino group, alkyl or alkoxy or (meth)acryloxy-substituted amino group, etc. R 1 is preferably a methyl group.

[0019] R 2 is a radical-reactive functional group, and a mercapto group or an alkyl group having 1 to 8 carbon atoms substituted with an ethylenic double bond-containing group is preferred. Specifically, it is an alkyl group having 1 to 8 carbon atoms substituted with a vinyl group, styryl group, mercapto group, acryloxy group or methacryloxy group. Examples include vinyl group, styryl group, octenyl group, methacryloxyoctyl group, mercaptopropyl group, acryloxypropyl group, methacryloxypropyl group, methacryloxyoctylvinyl group, etc.

[0020] X is a monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a hydroxyl group, which may be the same or different and may be substituted or unsubstituted. As the unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 1Those identical to those exemplified above can be exemplified, and as the alkoxy group having 1 to 20 carbon atoms, specifically, 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. can be mentioned. Among these, a hydroxyl group, a methyl group, a butyl group, and a phenyl group are preferable.

[0021] Y is X or -[O-Si(X)2] d It is the same or different groups represented by -X. As the X, those identical to those exemplified above can be exemplified.

[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 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, more preferably a number from 0 to 200. When constituting the a unit, the lower limit is preferably 0.5. When a is greater than 10,000, the strength of the coating film obtained when using the composition containing the component (A) as a coating film may be insufficient. b is a number from 100 to 10,000, preferably a number from 1,000 to 5,000. When b is less than 100, the flexibility of the coating film may be poor, and when it is greater than 10,000, its tear strength may decrease. c is a number from 0.0001 to 100, and when it exceeds 100, the sliding effect may not be exhibited. Here, c / (a + b + c)×100 is preferably from 0.0001 to 10, more preferably from 0.001 to 10. d is a number from 1 to 1,000, and a number from 1 to 200 is preferable.

[0024] The organopolysiloxane represented by the above formula (1) is preferably used in the form of an emulsion, and a commercially available product may be used or it may be synthesized. When synthesizing, it can be synthesized by a known emulsion polymerization method. For example, cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, etc., and a silane coupling agent represented by the following formula (2) are emulsified and dispersed in water using an anionic surfactant, and then, if necessary, a polymerization catalyst such as an acid is added to carry out a polymerization reaction, whereby it can be easily synthesized. The cyclic organosiloxane may have a fluorine atom, (meth)acryloxy group, carboxyl group, hydroxyl group, or amino group. [Chemical formula] (In formula (2), R 3 is a radical-reactive functional group. In particular, it represents an acryloxy group, methacryloxy group, vinyl group, or a C1-C8 alkyl group substituted with a mercapto group, or a styryl group or a vinyl group. R 4 is a C1-C4 alkyl group or a hydroxyl group, R 5 is a C1-C4 alkyl group, 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, 1,3,5,7 - tetra(3 - methacryloxypropyl)tetramethylcyclotetrasiloxane, 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, 1,3,5,7 - tetra(N,N - bis(lauroyl)-3 - aminopropyl)tetramethylcyclotetrasiloxane, etc. Preferably, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are used.

[0026] As silane coupling agents, specifically, vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane; acrylic silanes such as γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropyltriisopropoxysilane, γ-(meth)acryloxypropyltributoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxypropylmethyldiisopropoxysilane, γ-(meth)acryloxypropylmethyldibutoxysilane; mercapto silanes such as γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane; styryl silanes such as styryltrimethoxysilane and the like can be mentioned. Further, oligomers obtained by condensation polymerization of these may be more preferable as the generation of alcohol is suppressed. Here, (meth)acryloxy represents acryloxy or methacryloxy. These silane coupling agents are preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, or alkoxysilane.

[0027] By copolymerizing cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, and a silane coupling agent, an organopolysiloxane having a unit ([Si(R 2 )(Z)O] represented by the unit) in the repeating number c in the above formula (1) is obtained, and (B) vinyl chloride can be graft polymerized.

[0028] As the polymerization catalyst, a known polymerization catalyst may be used. Among them, strong acids are preferred, and hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid are exemplified. Preferably, it is dodecylbenzenesulfonic acid having surface activity. The amount of the acid catalyst used is preferably 0.01 to 10 parts by mass, more preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, or alkoxysilane.

[0029] Further, as the anionic surfactant, sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N-acyl taurine salt, aliphatic soap, alkyl phosphate, sodium lauroyl methyl taurine, sodium myristoyl methyl taurine, etc. are preferred. More preferably, they are N-acyl amino acid salt, N-acyl taurine salt, aliphatic soap, alkyl phosphate, sodium lauroyl methyl taurine, sodium myristoyl methyl taurine, and particularly preferably, 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, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, or alkoxysilane.

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

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

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

[0034] Here, the weight average molecular weight (Mw) of the organopolysiloxane, as measured by viscosity, 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 the solution) ηsp = [η] + 0.3[η] 2 [η] = 0.215 × 10 -4 M 0.65 Specifically, 20 g of the emulsion is mixed with 20 g of IPA (isopropyl alcohol), the emulsion is destroyed, the IPA is discarded, and the remaining rubbery organopolysiloxane is dried at 60 °C overnight. This is used as a toluene solution of the organopolysiloxane at a concentration of 1 g / 100 ml, and measurement is carried out at 25 °C using an Ubbelohde viscometer. The molecular weight can be determined by substituting the viscosity into the above formula (References: Nakamuta, Nippon Kasei Kagaku Kaishi, 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 production method of the vinyl chloride - silicone graft copolymer of the present invention has a step of graft - polymerizing the organopolysiloxane of formula (1) ((A) component) and vinyl chloride ((B) component) at a mass ratio (mass ratio of the organopolysiloxane of formula (1) to the vinyl chloride unit) 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 as described above, the sliding effect may not be exhibited.

[0037] Examples of the radical initiator used in the production of the vinyl chloride-silicone graft copolymer of the present invention include persulfates such as potassium persulfate and ammonium persulfate, persulfuric acid hydrate, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, a redox compound in which a reducing agent such as sodium acid sulfite, Rongalit, L-ascorbic acid, tartaric acid, saccharides, and amines is used in combination can also be used. Further, the amount of the radical initiator used is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, based on (B) vinyl chloride.

[0038] The polymerization temperature of the (B) component with respect to the (A) component 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 thereof 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, more preferably 0.3 to 0.8 part by mass, per 100 parts by mass of the monomer.

[0040] The vinyl chloride-silicone graft copolymer thus obtained is a polymer in which (B) vinyl chloride is randomly bonded to (A) organopolysiloxane, and is a polymer in which various structures are mixed, and it is impossible to directly specify the product by its structure or properties.

[0041] The manufacturing method of the vinyl chloride-silicone graft copolymer of the present invention preferably has a step of emulsion polymerization of an organopolysiloxane ((A) component) of formula (1) and vinyl chloride ((B) component) at a mass ratio (the mass ratio of the organopolysiloxane of formula (1) to the vinyl chloride unit) of 5:95 to 95:5, preferably 20:80 to 85:15. It is sufficiently graft-polymerizable with the surfactant contained in the organopolysiloxane emulsion, but as an anionic surfactant for improving stability, sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N-acyl taurine salt, aliphatic soap, alkyl phosphate, etc. can be added. Also, nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can be added. The usage amount when adding a surfactant is preferably 0.1 to 5% by mass of (B) vinyl chloride.

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

[0043] The vinyl chloride-silicone graft copolymer of the present invention can also be granulated from the emulsion by the methods listed below to form a powder. That is, freeze pulverization, spray drying, airflow drying, etc. can be mentioned, but spray drying is preferred considering productivity. The smaller the average particle diameter of the obtained powder particles, the better, preferably 1 to 50 μm, and more preferably 1 to 30 μm. The particle diameters of the above emulsion and powder can be measured as the cumulative mass average value D50 in 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, ultraviolet absorbers, antifreezing agents, pH adjusters, preservatives, defoaming agents, antibacterial agents, fungicides, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, surfactants and / or organic solvents (film-forming aids, etc.), etc., as a composition containing a vinyl chloride-silicone graft copolymer, it can be used as a coating agent for various substrates such as synthetic resins, metals, glasses, ceramics, gypsum, papers, woods, leathers, lightweight concretes, lightweight cellular concretes, mortars, calcium silicate boards, slates, gypsum boards, etc.; an adhesive; an exterior and interior paint binder for structures and building materials, etc.; a paper processing agent; a fiber treatment agent; a cosmetic, etc.

[0045] The composition containing the vinyl chloride-silicone graft copolymer of the present invention preferably contains the vinyl chloride-silicone graft copolymer in a solid content of 10 to 60% by mass, more preferably 20 to 50% by mass, and particularly preferably 30 to 50% by mass based on the total mass of the composition.

[0046] When an organic solvent is mixed with the composition containing the above vinyl chloride-silicone graft copolymer, 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; dimethyl sulfoxide and the like. The organic solvent 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 vinyl chloride-silicone graft copolymer and other components can be mixed and dissolved by a known mixing and preparation method such as a propeller stirrer, a homogenizer, a ball mill, or a bead mill to obtain a coating agent. When the coating agent is applied or immersed on one or both sides of a substrate such as glass or resin and dried, slidability and substrate adhesion can be imparted.

Examples

[0048] Hereinafter, examples and comparative examples will be shown to specifically explain the present invention, but the present invention is not limited to the following examples. In addition, the molecular weights described below are weight average molecular weights (Mw) determined by viscosity measurement obtained from the specific viscosity of a toluene solution of organopolysiloxane at a concentration of 1 g / 100 ml. In the following examples, "parts" and "%" indicate parts by mass and mass%, respectively.

[0049] [Example 1] 1200 g of octamethylcyclotetrasiloxane, 4.8 g of γ-methacryloxypropylmethyldimethoxysilane, a solution prepared by dissolving 12 g of sodium lauryl sulfate in 108 g of pure water, and a solution prepared by dissolving 12 g of dodecylbenzenesulfonic acid in 108 g of pure water were charged into a 4 L polyethylene beaker, emulsified uniformly with a homomixer, and then gradually diluted by adding 728 g of water. The mixture was passed through a high-pressure homogenizer twice at a pressure of 300 kgf / cm 2 to obtain a uniform white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and subjected to a polymerization reaction 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. The non-volatile content (solid content) of this emulsion after drying at 105°C for 3 hours was 44%, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel. This emulsion (silicone composition) had a structure represented by the following formula (A) with a molecular weight of about 250,000 determined from the viscosity of the toluene solution. In formula (A), R 2 is a γ-methacryloxypropyl group. The structure of the organopolysiloxane obtained by the above polymerization reaction was 1 confirmed by 1H-NMR (frequency 600 MHz, room temperature, number of integrations 128 times) and 29 29Si-NMR (frequency 60 MHz, room temperature, number of integrations 5000 times) (apparatus name: JNM-ECA600, measurement solvent: CDCl3). [Chemical formula] 1207 g of the above emulsion was transferred to a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet. 59 g of vinyl chloride and ammonium persulfate were added, and the reaction was carried out at 60°C for 8 hours to graft-copolymerize vinyl chloride onto the above silicone composition, obtaining an emulsion of a vinyl chloride-silicone graft copolymer with a non-volatile content of 30%. The obtained vinyl chloride-silicone graft copolymer was a vinyl chloride-silicone graft copolymer in which vinyl chloride was grafted onto R 2 of formula (A).

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

[0051] [Example 3] An emulsion of a silicone-vinyl chloride graft copolymer with a non-volatile content of 30% was obtained in the same manner except that the amount of vinyl chloride in Example 1 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, emulsified uniformly with a homomixer, then 728 g of water was gradually added for dilution, and passed through a high-pressure homogenizer at a pressure of 300 kgf / cm 2 twice to obtain a uniform white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, a thermometer and a reflux condenser, and subjected to a polymerization reaction at 55 °C for 24 hours, aged at 15 °C for 24 hours, and then neutralized to pH 7 with a 10% aqueous sodium carbonate solution. The non-volatile content (solid content) of this emulsion after drying at 105 °C for 3 hours was 45%, and the organopolysiloxane in the emulsion was a non-flowing soft gel. This emulsion (silicone composition) had a structure represented by the following formula (B) with a molecular weight of about 250,000 from the viscosity of the toluene solution. In formula (B), R 2 is a γ-methacryloxypropyl group. [Chemical formula] Transfer 1198 g of the above emulsion to a polymerization vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet, add 231 g of vinyl chloride and ammonium persulfate, and carry out a reaction at 60 °C for 8 hours to graft-copolymerize vinyl chloride to the above silicone composition, thereby obtaining an emulsion of a vinyl chloride-silicone graft copolymer having a non-volatile content of 30%. The obtained vinyl chloride-silicone graft copolymer was a vinyl chloride-silicone graft copolymer in which vinyl chloride was grafted to R in the formula (B). 2 It was a vinyl chloride-silicone graft copolymer in which vinyl chloride was grafted to the above.

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

[0054] [Example 6] An emulsion of a vinyl chloride-silicone graft copolymer having a non-volatile content of 30% was obtained in the same manner except that the amount of vinyl chloride in Example 1 was changed to 1232 g.

[0055] [Example 7] An emulsion of a vinyl chloride-silicone graft copolymer having a non-volatile content of 30% was obtained in the same manner except that the amount of vinyl chloride in Example 1 was changed to 4752 g.

[0056] [Comparative Example 1] Dissolve 1200 g of octamethylcyclotetrasiloxane, 4.8 g of γ-methacryloxypropylmethyldimethoxysilane, 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water in a 4 L polyethylene beaker, emulsify uniformly with a homomixer, then gradually add 728 g of water for dilution, and a pressure of 300 kgf / cm 2It was passed through a high-pressure homogenizer twice to obtain a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, a thermometer, and a reflux condenser, and a polymerization reaction was carried out 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. The non-volatile content (solid content) of this emulsion after drying at 105 °C for 3 hours was 44%, and the organopolysiloxane in the emulsion was in a non-flowing soft gel form. This emulsion (silicone composition) had a structure represented by the above formula (A) with a molecular weight of about 250,000 based on the viscosity of the toluene solution.

[0057] [Comparative Example 2] Into a polymerization vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet, 840 g of vinyl chloride, 16.8 g of 2-hydroxyethyl methacrylate, and potassium peroxodisulfate were added, and a reaction was carried out at 45 °C for 30 hours to obtain an emulsion of a copolymer with a non-volatile content of 40%.

[0058] [Comparative Example 3] A solution prepared by dissolving 1200 g of octamethylcyclotetrasiloxane, 0.96 g of γ-methacryloxypropylmethyldimethoxysilane, 12 g of sodium lauryl sulfate in 108 g of pure water, and a solution prepared by dissolving 12 g of dodecylbenzenesulfonic acid in 108 g of pure water were charged into a 2-L polyethylene beaker, emulsified uniformly with a homomixer, and then gradually diluted by adding 400 g of water. After passing through a high-pressure homogenizer twice at a pressure of 300 kgf / cm 2 a uniform white emulsion was obtained. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, a thermometer, and a reflux condenser, and a polymerization reaction was carried out 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. The non-volatile content of this emulsion after drying at 105 °C for 3 hours was 45%, and the organopolysiloxane in the emulsion was in a non-flowing soft gel form. This emulsion (silicone composition) had a structure represented by formula (B) with a molecular weight of about 250,000. Furthermore, 226.8 g of methyl methacrylate and 4.6 g of 2-hydroxyethyl methacrylate were added dropwise to this emulsion over 3 to 5 hours while reacting at 27°C using t-butyl hydroperoxide to graft copolymerize acrylic onto the above silicone composition, obtaining an emulsion of an acrylic-silicone graft copolymer with a non-volatile content of 30%.

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

[0060] The emulsions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 above were evaluated by the following method. The results are shown in Tables 1 and 2.

[0061] [Solid Content Measurement Method] Approximately 1 g of the sample was accurately weighed into a dish made of aluminum foil, placed in a dryer maintained at approximately 105°C, heated for 1 hour, taken out of the dryer, cooled in a desiccator, the weight of the aluminum foil dish containing the dried sample was measured, and the solid content (evaporation residue) was calculated by the following formula. [Equation] R: Solid content (evaporation residue) (%) W: Mass of the aluminum foil dish containing the sample before drying (g) L: Mass of the aluminum foil dish (g) T: Mass of the aluminum foil dish containing the dried sample (g) Dimensions of the aluminum foil dish: 65φ×23h (mm)

[0062] [Viscosity Measurement Method] The liquid temperature of the sample was maintained at 23 ± 0.5°C and measured with a rotational viscometer (No. 1 rotor, 6 rpm, manufactured by Toki Sangyo Co., Ltd.: product name: VISCOMETER TVB-10).

[0063] [Average Particle Size] The average particle diameter was measured by weighing 0.01 g of the sample and using a laser diffraction particle size distribution analyzer (manufactured by Horiba, Ltd., product name: LA-950V2) to measure the average particle diameter (the particle diameter value corresponding to 50% of the particle size cumulative distribution) under the 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

[0064] <Measurement of the 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 Seisakusho) in which a heating source and a cooling source were installed at a certain distance was used. 1 μl of the emulsion was applied to an aluminum foil, and the state of the coating film after 2 hours was observed using the device. The emulsion was dried under temperature control to form a film, and the boundary temperature between the transparent part and the non-film-forming part was measured as the minimum film formation temperature (MFT, °C). Considering the dryness during film formation, an MFT of 100 °C or lower is desirable.

[0065] <Measurement of Static and Kinetic 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 such that the film thickness after drying was approximately 10 μm. Using HEIDON TYPE-38 (manufactured by Shinto Kagaku Co., Ltd.), a 200 g metal pressure head was brought into perpendicular contact with the above coating film, and the frictional force when moving at 3 cm / min was measured, and the friction coefficient was calculated from the frictional force. The preferable ranges of the static and kinetic friction coefficients under the above conditions are that the static friction coefficient is 0.2 or less and the kinetic friction coefficient is 0.1 or less.

[0066] <Adhesion to Substrate> The emulsions of each example and comparative example were applied to a soft vinyl chloride film using a bar coater and dried at 105 °C for 3 minutes to form a coating film such that the film thickness after drying was approximately 10 μm. Cellophane tape was attached to the coating film and peeled off all at once, and the adhesion was visually evaluated. ○: No peeling from the substrate ×: Detachment from the substrate

[0067] <Alcohol resistance> 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 such that the film thickness after drying was approximately 10 μm. 98% ethanol was dropped onto the coating film and air-dried at room temperature overnight. The change in the coating film after air-drying was visually evaluated. ○: No change in appearance △: Traces remain but no whitening ×: Whitening

[0068] <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 such that the film thickness after drying was approximately 10 μm. 2 μl of pure water was dropped onto the coating film, and the contact angle values after 1 second and 30 seconds were measured using a contact angle meter CA-D type manufactured by Kyowa Interface Science Co., Ltd. Considering the prevention of adhesion of aqueous stains due to water repellency, a contact angle of 80° (degrees) or more is preferable.

[0069]

Table 1

[0070]

Table 2

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, wherein the mass ratio of (A) the organopolysiloxane to (B) vinyl chloride is (A):(B) = 5:95 to 95:

5. 【Chemical 1】 (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 X or -[O-Si(X) 2 d -X, which is the same or different group. 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 at a mass ratio of (A):(B) = 5:95 to 95:

5. [Chemical 2] (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 X or -[O-Si(X) 2 d -X, which is the same or different group. 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 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.

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