Vinyl chloride-silicone core-shell polymer and method for producing same

Abstract

Provided is a vinyl chloride-silicone copolymer which has slidability and water repellency.　Provided is a vinyl chloride-silicone core-shell polymer which is a copolymer of (A) an organopolysiloxane of formula (1) and (B) vinyl chloride, and which has a mass ratio (A):(B) of 5:95 to 90:10. (In the formula, R1 is an unsubstituted alkyl group having 1 to 20 carbon atoms; R2 is a phenyl group; each X is independently a hydroxy group or an unsubstituted alkyl group having 1 to 20 carbon atoms or the like; each Y is independently an unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group; at least one of the groups represented by Y is a hydroxy group or an alkoxy group; a is a number of 0-10,000; b is a number that is equal to 30-100% of the sum of a, b, c, and e; c is a number that is equal to 0-60% of the sum of a, b, c, and e; and e is a number that is equal to 0-10% of the sum of a, b, c, and e.)

Description

Vinyl chloride / silicone core-shell polymer and method for producing the same

[0001] The present invention relates to a core-shell polymer of organopolysiloxane and vinyl chloride and a method for producing the same, and more specifically, to a vinyl chloride-silicone core-shell polymer having sliding properties, water repellency, alcohol resistance, substrate adhesion, and transparency, and a method for producing the same.

[0002] Silicone resins have traditionally been known as resins that can impart sliding properties to substrates. However, when silicone resins are used alone, problems such as poor adhesion to the substrate have been observed.

[0003] Therefore, a method is used in which silicone is copolymerized with another monomer such as acrylic, urethane, or vinyl acetate. 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 resins and urethane resins. Known methods such as graft polymerization, block polymerization, and core-shell polymerization are used as copolymerization methods.

[0004] For example, Patent Document 1 (Japanese Unexamined Patent Publication No. 2021-63214) discloses a silicone acrylic core-shell resin having sliding properties and a method for producing the same. Patent Document 2 (Japanese Unexamined Patent Publication No. 2022-131528) 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, vinyl chloride is also known to be used by copolymerizing it with other monomers. For example, vinyl chloride-vinyl acetate copolymer resins, which are obtained by copolymerizing vinyl chloride and vinyl acetate, are available. Patent document 3 (Japanese Patent Application Publication No. 2001-114839) and others disclose vinyl chloride-vinyl acetate copolymer resins and methods for producing the same, and it is known that using them in substrates such as ink materials and receiving layers improves color development and adhesion.

[0006] While copolymerization of silicone or vinyl chloride with other monomers was known, attempts to copolymerize vinyl chloride and organopolysiloxanes (silicones) had been rare due to their inherent incompatibility. Furthermore, it was not believed that copolymerizing silicone and vinyl chloride would yield a resin that leveraged the properties of both materials.

[0007] Patent Document 4 (Japanese Unexamined Patent Publication No. 59-166520) discloses that a resin obtained by graft polymerization of silicone onto polyvinyl chloride has good oxygen permeability. While this resin has been considered for use in packaging for fresh foods and medical blood bags, its practicality for use in these applications, where it is formed into sheets from rolled kneaded material, is low, and there is room for improvement.

[0008] Furthermore, Patent Document 5 (Japanese Unexamined Patent Publication No. 07-102146) discloses that using a block copolymer resin consisting of vinyl chloride and siloxane blocks improves release properties during calender roll processing. Patent Document 6 (Japanese Unexamined Patent Publication No. 09-255705) discloses polymerizing vinyl chloride in the presence of a copolymer resin of siloxane and acrylic. These are used as additives in the production of vinyl chloride resin, and little research has been conducted on vinyl chloride-silicone copolymer resins to date.

[0009] Furthermore, another method is to obtain a coating agent by mixing a silicone resin emulsion and a vinyl chloride resin emulsion. However, in this mixture, the silicone component bleeds out, and the desired performance cannot be obtained, leaving room for improvement.

[0010] Japanese Patent Publication No. 2021-63214, Japanese Patent Publication No. 2022-131528, Japanese Patent Publication No. 2001-114839, Japanese Patent Publication No. 59-166520, Japanese Patent Publication No. 07-102146, Japanese Patent Publication No. 09-255705

[0011] Therefore, the present invention aims to provide a vinyl chloride-silicone core-shell polymer having sliding properties and water repellency.

[0012] As a result of diligent research to achieve the above objective, the inventors of the present invention have found that a vinyl chloride-silicone core-shell polymer obtained by core-shell polymerization of (A) organopolysiloxane and (B) vinyl chloride has sliding properties and water repellency, and have completed the present invention.

[0013] In other words, the present invention provides the following vinyl chloride-silicone core-shell polymer, a method for producing the same, and compositions and emulsions of the core-shell polymer.

[0014] [1] A vinyl chloride-silicone core-shell polymer comprising (A) 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 90:10. (In the formula, R 1 R is an unsubstituted alkyl group having 1 to 20 carbon atoms. 2 X is a phenyl group, each X is independently an unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group, each Y is independently an unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group, and at least one of the groups represented by Y is a hydroxyl group or an alkoxy group, a is a number from 0 to 10,000, b is a number that is 30 to 100% of the total number of a, b, c, and e, c is a number that is 0 to 60% of the total number of a, b, c, and e, and e is a number that is 0 to 10% of the total number of a, b, c, and e. ) [2] A method for producing a vinyl chloride-silicone core-shell polymer, comprising the 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 90:10. (In the formula, R 1 R is an unsubstituted alkyl group having 1 to 20 carbon atoms. 2) is a phenyl group, X is independently an unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group, Y is independently an unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group, and at least one of the groups represented by Y is a hydroxyl group or an alkoxy group, a is a number from 0 to 10,000, b is a number that is 30 to 100% of the total number of a, b, c, and e, c is a number that is 0 to 60% of the total number of a, b, c, and e, and e is a number that is 0 to 10% of the total number of a, b, c, and e.) [3] A composition containing 10 to 60% by solid content of the vinyl chloride / silicone core-shell polymer described in [1] with respect to the total mass of the composition. [4] An emulsion of the vinyl chloride / silicone core-shell polymer described in [1].

[0015] The vinyl chloride-silicone core-shell polymer of the present invention has sliding properties and water repellency. For this reason, compositions containing the vinyl chloride-silicone core-shell polymer of the present invention are suitably used as coating agents for various substrates, adhesives, exterior and interior paints for structures and building materials, and cosmetics.

[0016] The present invention relates to a vinyl chloride-silicone core-shell polymer obtained by core-shell polymerization of (A) organopolysiloxane and (B) vinyl chloride.

[0017] In the present invention, (A) organopolysiloxane is represented by the following formula (1). In the formula, R 1 R is an unsubstituted alkyl group having 1 to 20 carbon atoms. 2is a phenyl group, X is each independently an unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group, Y is each independently an unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group, at least one of the groups represented by Y is a hydroxy group or an alkoxy group, a is a number from 0 to 10,000, b is a number that is 30 to 100% of the total of a, b, c and e, c is a number that is 0 to 60% of the total of a, b, c and e, and e is a number that is 0 to 10% of the total of a, b, c and e.

[0018] Here, R 1 is the same or different unsubstituted alkyl group having 1 to 20 carbon atoms. Specifically, 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. can be mentioned. R 1 is preferably a methyl group.

[0019] X is the same or different unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a hydroxyl group. As the unsubstituted alkyl group having 1 to 20 carbon atoms, the same ones as exemplified by R 1 can be exemplified. As the aryl group having 6 to 20 carbon atoms, phenyl group, tolyl group, xylyl group, naphthyl group, etc. can be mentioned. As the alkoxy group having 1 to 20 carbon atoms, specifically, methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, tetradecyloxy group, etc. can be mentioned. Among these, hydroxyl group, methyl group, butyl group, phenyl group are preferable.

[0020] Y is an unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group, and the same examples as those exemplified as X above can be used, and at least one of the groups represented by Y is a hydroxyl group or an alkoxy group. (A) If the organopolysiloxane has an a unit, it is preferable that at least one of the groups represented by Y is a hydroxyl group or an alkoxy group.

[0021] a is a number between 0 and 10,000, preferably between 0 and 1,000, and more preferably between 0 and 200. When forming an a unit, it is preferable to set the lower limit to 0.5. If a is greater than 10,000, the strength of the coating obtained when a composition containing component (A) is used as a coating film may be insufficient. b is a number such that b / (a+b+c+e)×100 is between 30% and 100%, preferably between 50% and 100%, and more preferably between 70% and 100%. If b / (a+b+c+e)×100 is less than 30%, the water repellency of the coating may decrease when a composition containing component (A) is used as a coating film. c is a number such that c / (a+b+c+e)×100 is between 0% and 60%, preferably between 0% and 40%, and more preferably between 0% and 20%. If c / (a+b+c+e)×100 is greater than 60%, the water repellency of the coating may decrease when a composition containing component (A) is used as a coating film. e is a number such that e / (a+b+c+e)×100 is between 0% and 10%, preferably between 0% and 3%, and more preferably between 0.01% and 1%. If e / (a+b+c+e)×100 is greater than 10%, the sliding properties and water repellency of the coating may decrease when a composition containing component (A) is used as a coating film. Furthermore, the sum of a+b+c+e is preferably between 10% and 100,000, more preferably between 100% and 30,000, and even more preferably between 1,000% and 7,000.

[0022] The organopolysiloxane represented by formula (1) above is preferably used in emulsion form, and may be a commercially available product or synthesized. If synthesized, it can be synthesized by a known emulsion polymerization method, for example, R in formula (1)1 , R 2 It can be produced by using one or more cyclic organopolysiloxanes having desired groups for each of the X and Y groups as raw materials, and performing ring-opening polymerization using an anionic surfactant and a polymerization catalyst. The above cyclic organopolysiloxanes 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)tetramethyl Examples include cyclotetrasiloxane, 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. Preferably, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are used.

[0023] As the polymerization catalyst, any known polymerization catalyst may be used. Among these, strong acids are preferred, with hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid being examples. 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 cyclic organopolysiloxane.

[0024] Furthermore, preferred anionic surfactants include sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyl taurate salts, aliphatic soaps, alkyl phosphates, sodium lauroyl methyl taurate, and sodium myristoyl methyl taurate. More preferably, N-acyl amino acid salts, N-acyl taurate salts, aliphatic soaps, alkyl phosphates, sodium lauroyl methyl taurate, and sodium myristoyl methyl taurate, and particularly preferably, sodium lauroyl methyl taurate, sodium myristoyl methyl taurate, and sodium lauryl sulfate.

[0025] The amount of 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 cyclic organosiloxane.

[0026] The polymerization temperature for producing the organopolysiloxane represented by formula (1) is preferably 50 to 75°C, and the polymerization time is preferably 10 hours or more, and more preferably 15 hours or more. Furthermore, it is particularly preferable to age the product at 5 to 30°C for 10 hours or more after polymerization.

[0027] After the polymerization reaction is complete, the solution 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).

[0028] (A) The weight-average molecular weight (Mw) of the organopolysiloxane, as determined by viscosity measurement, is preferably 10,000 to 1,000,000, and more preferably 100,000 to 500,000, in terms of sliding effect.

[0029] Here, the weight-average molecular weight (Mw) of the organopolysiloxane, determined by viscosity measurement, is calculated from the specific viscosity ηsp (at 25°C) of a toluene solution of 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 organopolysiloxane emulsion is mixed with 20 g of IPA (isopropyl alcohol). After the emulsion is broken down, the IPA is discarded, and the remaining rubbery organopolysiloxane is dried overnight at 60°C. This is then prepared as a toluene solution of organopolysiloxane at a concentration of 1 g / 100 ml, and its viscosity is measured at 25°C using an Ubbelohde viscometer. The molecular weight 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] ).

[0030] Manufacturing Method The vinyl chloride / silicone core-shell polymer of the present invention can be obtained by polymerizing (A) organopolysiloxane and (B) vinyl chloride, preferably by radical polymerization, and more preferably by emulsion polymerization.

[0031] The present invention provides a method for producing a vinyl chloride-silicone core-shell polymer, comprising the step of polymerizing an organopolysiloxane of formula (1) (component (A)) and vinyl chloride (component (B)) in a mass ratio (mass ratio of organopolysiloxane of formula (1) to vinyl chloride units) of 5:95 to 90:10, preferably 20:80 to 85:15. If the proportion of the organopolysiloxane component of formula (1) is less than the lower limit of 5, the sliding effect may not be achieved.

[0032] As the radical initiator used in the production of the vinyl chloride-silicone core-shell polymer of the present invention, there may be mentioned persulfates such as potassium persulfate and ammonium persulfate, persulfuric acid hydrate, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, redox compounds in which reducing agents such as sodium acid sulfite, Rongalit, L-ascorbic acid, tartaric acid, saccharides, and amines are used in combination can also be used. 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.

[0033] The polymerization temperature of component (B) with respect 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.

[0034] Further, a chain transfer agent can be added to adjust the molecular weight and polymerization rate of the polymer. For example, halogenated hydrocarbons such as chloroform and carbon tetrachloride; mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan can be exemplified. 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 (vinyl chloride monomer).

[0035] The vinyl chloride-silicone core-shell polymer thus obtained is a polymer having a structure in which the organopolysiloxane of component (A) serves as core particles and the vinyl chloride of component (B) polymerizes in the presence of the organopolysiloxane of component (A) to form a shell layer, and is a polymer in which polymers of various structures are mixed, and it is impossible to directly specify the substance by its structure or properties.

[0036] The method for producing a vinyl chloride-silicone core-shell polymer 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 (mass ratio of the organopolysiloxane of formula (1) to vinyl chloride units) of 5:95 to 90:10, preferably 20:80 to 85:15. When carrying out emulsion polymerization, the organopolysiloxane of the (A) component is used in the form of an emulsion, and it is sufficiently polymerizable with the surfactant contained in the organopolysiloxane emulsion. However, for improving stability, as an anionic surfactant, sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N-acyl taurolate, aliphatic soap, alkyl phosphate, etc. can be added. Also, nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can be added. The amount used when adding a surfactant is preferably 0.1 to 5% by mass of (B) vinyl chloride. In this way, the vinyl chloride-silicone core-shell polymer obtained from emulsion polymerization can also be obtained in the form of an emulsion, that is, as an emulsion of the vinyl chloride-silicone core-shell polymer.

[0037] Further, the vinyl chloride-silicone core-shell polymer preferably has an emulsion solid content of 25 to 40% by mass. Also, 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.

[0038] The vinyl chloride-silicone core-shell polymer of the present invention can also be granulated and powdered from an emulsion by the following methods: cryogenic pulverization, spray drying, and airflow drying. However, considering productivity, spray drying is preferred. The average particle size of the resulting powder particles should be as small as possible, preferably 1 to 50 μm, and more preferably 1 to 30 μm. The particle size of the emulsion and powder can be measured as the cumulative mass average value D50 using a laser diffraction particle size analyzer.

[0039] By using the vinyl chloride-silicone core-shell polymer (core-shell resin) of the present invention in combination with other resins, pigments, fillers, matting agents, antioxidants, UV absorbers, antifreeze agents, pH adjusters, preservatives, defoamers, antibacterial agents, antifungal agents, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, surfactants, and / or organic solvents (such as film-forming aids), a composition containing the vinyl chloride-silicone core-shell polymer can be used as a coating agent for various substrates such as synthetic resins, metals, glass, ceramics, gypsum, paper, wood, leather, lightweight concrete, lightweight aerated concrete, mortar, calcium silicate boards, slate, and gypsum boards; an adhesive; a paint binder for exterior and interior use of structures and building materials; a paper processing agent; a fiber processing agent; and cosmetics.

[0040] The composition containing the vinyl chloride-silicone core-shell polymer of the present invention preferably contains 10 to 60% by mass of the vinyl chloride-silicone core-shell polymer in solid content relative to the total mass of the composition, more preferably 20 to 50% by mass, and particularly preferably 30 to 50% by mass.

[0041] When an organic solvent is mixed with the above-mentioned vinyl chloride / silicone core-shell polymer composition, examples of organic solvents 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 solvent may be used alone or in combination.

[0042] The composition containing the vinyl chloride-silicone core-shell polymer 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 core-shell polymer and other components using known mixing and preparation methods such as a propeller-type stirrer, homogenizer, ball mill, or bead mill. When this coating agent is applied to one or both sides of a substrate such as glass or resin, and then dried, it can impart sliding properties and adhesion to the substrate.

[0043] 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. Furthermore, the molecular weights described below are weight-average molecular weights (Mw) determined by viscosity measurement from the specific viscosity of a toluene solution of organopolysiloxane at a concentration of 1 g / 100 ml. In the following examples, parts and % refer to parts by mass and mass%, respectively.

[0044] [Example 1] 1200 g of octamethylcyclotetrasiloxane and 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 were placed in a 4 L polyethylene beaker, and after being uniformly emulsified with a homomixer, 728 g of water was gradually added to dilute the mixture, and the pressure was 300 kgf / cm². 2 The mixture was passed twice through a high-pressure homogenizer 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 polymerization was carried out at 55°C for 24 hours. After maturation at 15°C for 24 hours, it was neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the non-volatile content (solids) of the emulsion was 44%, and the organopolysiloxane in the emulsion was a non-flowing, soft gel. The structure of this emulsion (silicone composition) was represented by the following formula (A) with a molecular weight of approximately 250,000, based on the viscosity of the toluene solution. The structure of the organopolysiloxane obtained by the above polymerization reaction is 1 H-NMR (frequency 600 MHz, room temperature, 128 integration cycles) and 29 Confirmation was made by Si-NMR (frequency 60 MHz, room temperature, 5000 integration cycles) (instrument name: JNM-ECA600, measurement solvent: CDCl3). 1207 g of the above emulsion was transferred to a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet. 228 g of vinyl chloride monomer and ammonium persulfate were added, and the reaction was carried out at 60°C for 8 hours to perform core-shell polymerization of vinyl chloride into the silicone composition, obtaining an emulsion of a vinyl chloride-silicone core-shell polymer with a non-volatile content of 30%. The obtained vinyl chloride-silicone core-shell polymer was a vinyl chloride-silicone core-shell polymer in which the composition of formula (A) was in the core part and polyvinyl chloride was in the shell part.

[0045] [Example 2] An emulsion of vinyl chloride / silicone core-shell polymer with a non-volatile content of 30% was obtained by the same method as in Example 1, except that the amount of vinyl chloride monomer was replaced with 531 g.

[0046] [Example 3] An emulsion of vinyl chloride / silicone core-shell polymer with a non-volatile content of 30% was obtained by the same method as in Example 1, except that the amount of vinyl chloride monomer was replaced with 1239 g.

[0047] [Comparative Example 1] 1200 g of octamethylcyclotetrasiloxane and 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 were placed in a 4 L polyethylene beaker, uniformly emulsified with a homomixer, and then diluted by gradually adding 728 g of water at a pressure of 300 kgf / cm². 2 The mixture 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, thermometer, and reflux condenser, and polymerization was carried out at 55°C for 24 hours. After maturation at 15°C for 24 hours, it was neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the non-volatile content (solids) of the emulsion was 44%, and the organopolysiloxane in the emulsion was a non-flowing, soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a structure represented by the above formula (A) with a molecular weight of approximately 250,000.

[0048] [Comparative Example 2] In a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet, 840 g of vinyl chloride monomer, 16.8 g of 2-hydroxyethyl methacrylate, and potassium peroxodisulfate were added, and the reaction was carried out at 45°C for 30 hours while adding 2530 g of vinyl chloride monomer to obtain a copolymer emulsion with a non-volatile content of 40%.

[0049] [Comparative Example 3] An emulsion of vinyl chloride / silicone core-shell polymer with a non-volatile content of 30% was obtained by the same method as in Example 1, except that the amount of vinyl chloride monomer was changed to 28 g.

[0050] The emulsions obtained in Examples 1-3 and Comparative Examples 1-3 were evaluated by the following method. The results are shown in Tables 1 and 2.

[0051] <Method for measuring solid content> Approximately 1 g of the sample 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 aluminum foil dish containing the dried sample was measured, and the solid content (evaporation residue) was calculated using the following formula. 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 sample after drying (g) Dimensions of the aluminum foil dish: 65φ × 23h (mm)

[0052] <Viscosity Measurement Method> The sample liquid temperature was maintained 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.: product name: VISCOMETER TVB-10).

[0053] <Average Particle Size> The average particle size was measured by weighing 0.01 g of the sample and using a laser diffraction particle size distribution analyzer (Horiba, Ltd., product name: LA-950V2) under conditions of circulation flow rate 2 and stirring speed 2 (the value of the particle size corresponding to 50% of the cumulative particle size distribution). [Measurement Conditions] Measurement temperature: 25 ± 1℃ Solvent: Ion-exchanged water

[0054] <Measurement of Minimum Film Formation Temperature (MFT)> The minimum film formation temperature (MFT, °C) of the emulsion was measured according to the method in accordance with JIS K-6828-2. Specifically, a simple film formation temperature measuring device (manufactured by Imoto Seisakusho) was used, in which the heating source and cooling source were installed at a certain distance apart. 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 film-formed area and the unfilm-formed area was measured to determine the minimum film formation temperature (MFT, °C). Considering the drying properties during film formation, an MFT of 100°C or lower is desirable.

[0055] <Measurement of Static and Dynamic Friction Coefficients> The emulsions of each example and comparative example were diluted with pure water to adjust the solid content to approximately 30%. The emulsions with adjusted solid content for each example and comparative example were applied to a PET film (Toyo Lelmiller T60) using a bar coater No. 13 (RD-SPECIALTIES), dried at 105°C for 3 minutes, and a coating film was formed with a thickness of approximately 10 μm after drying. A 200 g metal indenter was brought into contact with the coating film perpendicularly using a HEIDON TYPE-38 (manufactured by Shinto Kagaku Co., Ltd.), and the frictional force was measured when it was moved at 3 cm / min. The frictional coefficient was calculated from the frictional force. The preferred range for the static and dynamic friction coefficients under the above conditions is a static friction coefficient of 0.2 or less and a dynamic friction coefficient of 0.1 or less.

[0056] <Water Contact Angle Measurement> The emulsions of each example and comparative example were diluted with pure water to adjust the solid content to approximately 30%. The emulsions with the adjusted solid content of each example and comparative example were applied to a PET film (Toyo Lelmiller T60) using a bar coater No. 13 (RD-SPECIALTIES), and dried at 105°C for 3 minutes to form a coating film with a thickness of approximately 10 μm after drying. 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 manufactured by Kyowa Interface Science Co., Ltd. A contact angle of 80° or higher is preferable considering the prevention of water-based stain adhesion due to water repellency.

[0057]

[0058]

Claims

1. A vinyl chloride-silicone core-shell polymer comprising (A) 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 90:

10. (In the formula, R 1 R is an unsubstituted alkyl group having 1 to 20 carbon atoms. 2 X is a phenyl group, each X is independently an unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group, and each Y is independently an unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group, with at least one of the groups represented by Y being a hydroxyl group or an alkoxy group, and a is a number from 0 to 10,000, b is a number that is 30 to 100% of the total number of a, b, c, and e, c is a number that is 0 to 60% of the total number of a, b, c, and e, and e is a number that is 0 to 10% of the total number of a, b, c, and e.

2. A method for producing a vinyl chloride-silicone core-shell polymer, comprising the 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 90:

10. (In the formula, R 1 R is an unsubstituted alkyl group having 1 to 20 carbon atoms. 2 X is a phenyl group, each X is independently an unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group, and each Y is independently an unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group, with at least one of the groups represented by Y being a hydroxyl group or an alkoxy group, and a is a number from 0 to 10,000, b is a number that is 30 to 100% of the total number of a, b, c, and e, c is a number that is 0 to 60% of the total number of a, b, c, and e, and e is a number that is 0 to 10% of the total number of a, b, c, and e.

3. A composition comprising 10 to 60% by mass, in terms of solid content, of the vinyl chloride / silicone core-shell polymer described in claim 1, relative to the total mass of the composition.

4. An emulsion of the vinyl chloride / silicone core-shell polymer according to claim 1.

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