Vinyl chloride / silicone block copolymer and production method therefor

Abstract

Provided is a vinyl chloride / silicone copolymer having sliding properties, water repellency, alcohol resistance, substrate adhesion, and transparency.　This vinyl chloride / silicone block copolymer is a copolymer of (A) an organopolysiloxane of formula (1) and (B) vinyl chloride and has an (A):(B) mass ratio of 5:95 to 90:10. (In formula (1), the R1 moieties and the Y moieties are the same or different and are each a substituted or unsubstituted C1-C20 monovalent hydrocarbon group; the X moieties are each a radical-reactive functional group, a hydrogen atom, or a methyl group, provided that at least one of the X moieties is the radical-reactive functional group; the R2 moieties are the same or different and are each a substituted or unsubstituted C1-C20 monovalent hydrocarbon group, a C1-C20 alkoxy group, or a hydroxyl group; a is a number of 10-10,000; and b is a number of 0-10,000.)

Description

Vinyl chloride / silicone block copolymer and method for producing the same

[0001] The present invention relates to a block copolymer of organopolysiloxane and vinyl chloride and a method for producing the same, and more specifically, to a vinyl chloride-silicone block copolymer 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. 2020-90563) discloses a silicone acrylic graft copolymer resin having sliding properties and a method for producing the same. Furthermore, 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. 2020-90563, 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 block copolymer having sliding properties, water repellency, alcohol resistance, substrate adhesion, and transparency.

[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 block copolymer obtained by block copolymerizing (A) organopolysiloxane and (B) vinyl chloride has sliding properties, water repellency, alcohol resistance, substrate adhesion, and transparency, and have completed the present invention.

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

[0014] [1] A vinyl chloride / silicone block copolymer 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 formula (1), R 1 And Y are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and X is a radical-reactive functional group, a hydrogen atom, or a methyl group; however, at least one of X is a radical-reactive functional group. 2 (A) 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. (a) is a number from 10 to 10,000, and b) is a number from 0 to 10,000.) [2] A method for producing a vinyl chloride / silicone block copolymer, 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 formula (1), R 1 And Y are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and X is a radical-reactive functional group, a hydrogen atom, or a methyl group; however, at least one of X is a radical-reactive functional group. 2(Is the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, or hydroxyl groups. a is a number from 10 to 10,000, and b is a number from 0 to 10,000.) [3] A composition containing 10 to 60% by mass in solid content of the vinyl chloride / silicone block copolymer described in [1] with respect to the total mass of the composition. [4] An emulsion of the vinyl chloride / silicone block copolymer described in [1].

[0015] The vinyl chloride-silicone block copolymer of the present invention possesses sliding properties, water repellency, alcohol resistance, substrate adhesion, and transparency. For this reason, compositions containing the vinyl chloride-silicone block copolymer 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 block copolymer obtained by block copolymerizing (A) organopolysiloxane and (B) vinyl chloride.

[0017] In the present invention, (A) organopolysiloxane is represented by the following formula (1). In formula (1), R 1 And Y are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and X is a radical-reactive functional group, a hydrogen atom, or a methyl group; however, at least one of X is a radical-reactive functional group. 2 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. a is a number from 10 to 10,000, and b is a number from 0 to 10,000.

[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. And 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] X is a radical-reactive functional group, a hydrogen atom (H) or a methyl group, and at least one of the two Xs in formula (1) is a radical-reactive functional group. Examples of the radical-reactive functional group 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 mercapto group or an alkyl group having 1 to 8 carbon atoms substituted with an ethylenic double bond-containing group include a mercapto group, a vinyl group, a styryl group, an acryloxy group or a methacryloxy group-substituted alkyl group having 1 to 8 carbon atoms. Examples of the radical-reactive functional group represented by X include a vinyl group, a styryl group, an octenyl group, a methacryloxyoctyl group, a mercaptopropyl group, an acryloxypropyl group, a methacryloxypropyl group, a methacryloxyoctylvinyl group, etc.

[0020] Y 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 the same as those exemplified for R 1 can be exemplified. R 2R 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. As for unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, 1 Examples identical to those exemplified above can be given, and specific examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and tetradecyloxy groups. Among these, hydroxyl, methyl, butyl, and phenyl groups are preferred. 2 Preferably, at least one of these is an alkoxy group or a hydroxyl group having 1 to 20 carbon atoms.

[0021] a is a number between 10 and 10,000, preferably between 100 and 5,000, and more preferably between 1,000 and 4,000. If a is less than 10, the strength of the coating may be insufficient, and if it is greater than 10,000, the sliding properties of the coating obtained when a composition containing component (A) is used as a coating film may be insufficient. b is a number between 0 and 10,000, preferably between 0 and 1,000. If b is greater than 10,000, its tear strength may decrease.

[0022] The organopolysiloxane represented by formula (1) above is preferably used in emulsion form and may be a commercially available product or synthesized. When synthesized, it can be synthesized by a known emulsion polymerization method. For example, at least one of a cyclic organosiloxane as shown in formula (2) below or a linear organopolysiloxane as shown in formula (3) below can be emulsified and dispersed in water using an anionic surfactant and polymerized, and then the polymerization reaction can be stopped using a silane coupling agent shown in formula (4) below. In formula (2), R 3 c is a monovalent hydrocarbon group, alkoxy group, or hydroxyl group having 1 to 20 carbon atoms, either identical or different substituted or unsubstituted. c is a number between 3 and 10. In formula (3), R 3is the same or different substituted or unsubstituted monovalent hydrocarbon group, alkoxy group, or hydroxyl group having 1 to 20 carbon atoms. d is a number from 1 to 10,000. In formula (4), Y is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a radical-reactive functional group, a hydrogen atom, or a methyl group, and Z is a hydroxyl group or a chloro group.

[0023] Furthermore, the organopolysiloxane represented by formula (1) can also be prepared by polycondensing an organopolysiloxane, such as the one represented by formula (5), with the siloxane represented by formula (2) and / or formula (3) after cleaving the siloxane bond using a catalyst or the like. In formula (5), R 5 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 substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms; X is a radical-reactive functional group, a hydrogen atom, or a methyl group; however, at least one of X is a radical-reactive functional group. e is a number from 0 to 10,000.

[0024] R in equation (2) 3 As a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, the above R 1 The same group as the one exemplified above can be exemplified, and as an alkoxy group having 1 to 20 carbon atoms, the above R 2Examples of the same groups as those exemplified above can be cited. Examples of cyclic organosiloxanes represented by formula (2) 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)tetra Examples include methylcyclotetrasiloxane, 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.

[0025] R in equation (3) 3 As a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, the above R 1 The same group as the one exemplified above can be exemplified, and as an alkoxy group having 1 to 20 carbon atoms, the above R 2Examples of the same groups as those exemplified in the previous example can be used. Examples of linear organopolysiloxanes represented by formula (3) include dimethylpolysiloxane, diethylpolysiloxane, methylethylpolysiloxane, methylpropylpolysiloxane, methylhexylpolysiloxane, methyloctylpolysiloxane, methyldecylpolysiloxane, methyldodecylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, dimethoxypolysiloxane, and methylhydroxypolysiloxane, all of which have silanol groups blocked at both ends.

[0026] Examples of silane coupling agents represented by formula (4) include vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinyldimethylpropoxysilane, vinyldimethylisopropoxysilane; γ-(meth)acryloxypropyldimethylmethoxysilane, γ-(meth)acryloxypropyldimethylethoxysilane, γ-(meth)acryloxypropyldimethylpropoxysilane, γ-(meth)acryloxypropyldimethylisopropoxysilane, γ-(meth)acryloxypropyldimethylbutoxysilane; mercaptosilanes such as γ-mercaptopropyldimethylmethoxysilane; styrylsilanes such as styryldimethylmethoxysilane, etc. Furthermore, oligomers obtained by condensation polymerization of these may be more preferable because alcohol generation is suppressed. Here, (meth)acryloxy refers to acryloxy or methacryloxy. These silane coupling agents are preferably used in amounts of 0.01 to 20 parts by mass, and more preferably in amounts of 0.01 to 5 parts by mass, per 100 parts by mass of the total of cyclic organosiloxanes such as those represented by formula (2) and linear organopolysiloxanes such as those represented by formula (3).

[0027] R in equation (5) 5 As a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, the above R 1 The same group as the one exemplified above can be exemplified, and as an alkoxy group having 1 to 20 carbon atoms, the above R 2The same groups as those exemplified can be exemplified. As X and Y in formula (5), the same groups as those exemplified for X and Y in formula (1) can be exemplified. As the organopolysiloxane represented by formula (5), specifically, vinyl-terminated dimethylpolysiloxane, methacryl-terminated dimethylpolysiloxane, mercapto-terminated dimethylpolysiloxane, acrylo-terminated dimethylpolysiloxane, and methacryl-terminated dimethylpolysiloxane at one end are used.

[0028] The silane coupling agent represented by formula (4) or the organopolysiloxane represented by formula (5) can be block copolymerized with vinyl chloride by having a radical-reactive functional group, particularly a vinyl group, styryl group, octenyl group, methacryloxyoctyl group, mercaptopropyl group, acryloxypropyl group, methacryloxypropyl group, or methacryloxyoctyl vinyl group.

[0029] 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 polymerization 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 linear organopolysiloxane.

[0030] 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, 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.

[0031] 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, relative to 100 parts by mass of the cyclic organosiloxane or linear organopolysiloxane.

[0032] 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 preferable to age at 5 to 30 ° C for 10 hours or more after the polymerization.

[0033] 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).

[0034] The weight average molecular weight (Mw) of the organopolysiloxane (A) measured by viscosity is preferably 10,000 to 1,000,000, more preferably 100,000 to 500,000, in terms of the sliding effect.

[0035] Here, the weight average molecular weight (Mw) of the organopolysiloxane 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 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 broken, 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 the 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 (Reference: Nakamuta, Nika, 77 858

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

[1953] ).

[0036] Production method The vinyl chloride-silicone block copolymer of the present invention can be obtained by block copolymerizing (A) an organopolysiloxane and (B) vinyl chloride.

[0037] The present invention provides a method for producing a vinyl chloride-silicone block copolymer, comprising the step of block 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 above 5, the sliding effect may not be achieved.

[0038] Radical initiators used in the production of the vinyl chloride-silicone block copolymer of the present invention include persulfates such as potassium persulfate and ammonium persulfate, hydrogen persulfate solution, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, redox compounds using reducing agents such as sodium acidic sulfite, rongalit, L-ascorbic acid, tartaric acid, sugars, and amines can also be used. The amount of radical initiator used is preferably 0.1 to 5% by mass of (B) vinyl chloride, and more preferably 0.5 to 3% by mass.

[0039] The polymerization temperature of component (B) relative to component (A) is preferably 25 to 85°C, and more preferably 55 to 85°C. The polymerization time is preferably 2 to 20 hours, and more preferably 3 to 10 hours.

[0040] Furthermore, chain transfer agents can be added to adjust the molecular weight and polymerization rate of the polymer. Examples 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 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 monomer (vinyl chloride monomer).

[0041] The vinyl chloride-silicone block copolymer obtained in this manner is a polymer in which the vinyl chloride of component (B) is polymerized to one or both ends of the organopolysiloxane of component (A), and is a polymer composed of a mixture of various structures, making it impossible to directly identify the product by its structure or properties.

[0042] The present invention provides a method for producing a vinyl chloride-silicone block copolymer, which preferably includes a step of emulsion polymerization of 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. Although sufficient block polymerization is possible with the surfactant contained in the organopolysiloxane emulsion, anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyl taurine salts, aliphatic soaps, and alkyl phosphates can be added to improve stability. Nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can also be added. When a surfactant is added, the amount used is preferably 0.1 to 5% by mass of vinyl chloride (B).

[0043] Furthermore, the vinyl chloride-silicone block copolymer preferably has a solid content of 25 to 40% by mass in the emulsion. The viscosity of this emulsion (at 25°C) is preferably 1 to 500 mPa·s, and 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 the value measured using a dynamic light scattering particle size distribution analyzer.

[0044] The vinyl chloride-silicone block copolymer of the present invention can also be granulated and powdered from an emulsion by the following methods: cryopreservation, spray drying, and airflow drying. However, spray drying is preferred in terms of productivity. 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.

[0045] By using the vinyl chloride-silicone block copolymer (copolymer 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 block copolymer 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.

[0046] The composition containing the vinyl chloride-silicone block copolymer of the present invention preferably contains 10 to 60% by mass of the vinyl chloride-silicone block copolymer in terms of solid content, more preferably 20 to 50% by mass, and particularly preferably 30 to 50% by mass, based on the total mass of the composition.

[0047] When an organic solvent is mixed with the above-mentioned vinyl chloride-silicone block copolymer, 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.

[0048] The composition containing the vinyl chloride-silicone block 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 block copolymer 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.

[0049] 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.

[0050] [Example 1] (A1) Terminal vinyl group organopolysiloxane: A commercially available organopolysiloxane emulsion having the following structure (non-volatile content: 45%) was used. 1207 g of the above emulsion was transferred to a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet. 233 g of vinyl chloride monomer, ammonium persulfate, and pure water were added, and the reaction was carried out at 60°C for 8 hours to block copolymerize vinyl chloride into the emulsion (organopolysiloxane), obtaining an emulsion of vinyl chloride-silicone block copolymer with a non-volatile content of 29%. The obtained vinyl chloride-silicone block copolymer was a vinyl chloride-silicone block copolymer in which vinyl chloride was copolymerized to a vinyl base of formula (A).

[0051] [Example 2] (A2) Terminal methacrylate organopolysiloxane: A commercially available organopolysiloxane emulsion having the following structure (non-volatile content: 45%) was used. R = C3H6 1207 g of the above emulsion was transferred to a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet. 233 g of vinyl chloride monomer, ammonium persulfate, and pure water were added, and the reaction was carried out at 60°C for 8 hours to block copolymerize vinyl chloride into the emulsion (organopolysiloxane), obtaining an emulsion of vinyl chloride-silicone block copolymer with a non-volatile content of 30%. The obtained vinyl chloride-silicone block copolymer was a vinyl chloride-silicone block copolymer in which vinyl chloride was copolymerized to a methacrylic base of formula (B).

[0052] [Example 3] An emulsion of vinyl chloride / silicone block copolymer with a non-volatile content of 30% was obtained in the same manner as in Example 1, except that the amount of vinyl chloride monomer was replaced with 544 g.

[0053] [Example 4] An emulsion of vinyl chloride / silicone block copolymer with a non-volatile content of 30% was obtained in the same manner as in Example 2, except that the amount of vinyl chloride monomer was replaced with 544 g.

[0054] [Example 5] An emulsion of vinyl chloride / silicone block copolymer with a non-volatile content of 29% was obtained in the same manner as in Example 1, except that the amount of vinyl chloride monomer was replaced with 61 g.

[0055] [Example 6] An emulsion of vinyl chloride / silicone block copolymer with a non-volatile content of 30% was obtained in the same manner as in Example 2, except that the amount of vinyl chloride monomer was replaced with 61 g.

[0056] [Comparative Example 1] A commercially available organopolysiloxane emulsion having the structure represented by the above formula (A) (non-volatile content: 45%) was used.

[0057] [Comparative Example 2] A commercially available organopolysiloxane emulsion having the structure represented by the above formula (B) (non-volatile content: 45%) was used.

[0058] [Comparative Example 3] In a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet, 840 g of vinyl chloride, 16.8 g of 2-hydroxyethyl methacrylate, potassium peroxodisulfate, and pure water 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%.

[0059] [Comparative Example 4] 1207 g of the emulsion from Comparative Example 1 was transferred to a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet. 28.6 g of vinyl chloride monomer, ammonium persulfate, and pure water were added, and the reaction was carried out at 60°C for 8 hours to block copolymerize vinyl chloride into the emulsion (organopolysiloxane), obtaining an emulsion of vinyl chloride-silicone block copolymer with a non-volatile content of 30%. The obtained vinyl chloride-silicone block copolymer was a vinyl chloride-silicone block copolymer in which vinyl chloride was block copolymerized to a vinyl base of formula (A).

[0060] The emulsions obtained in Examples 1-6 and Comparative Examples 1-4 were evaluated using the following method. The results are shown in Tables 1 and 2.

[0061] <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)

[0062] <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).

[0063] <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

[0064] <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.

[0065] <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 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), 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.

[0066] <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.

[0067]

[0068]

Claims

1. A vinyl chloride / silicone block copolymer comprising (A) an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride, wherein the mass ratio of (A) organopolysiloxane to (B) vinyl chloride is (A):(B) = 5:95 to 90:

10. (In formula (1), R 1 And Y are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and X is a radical-reactive functional group, a hydrogen atom, or a methyl group; however, at least one of X is a radical-reactive functional group. 2 (where a is a monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and where a is a number from 10 to 10,000, and b is a number from 0 to 10,000.) 2. A method for producing a vinyl chloride / silicone block copolymer, 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 formula (1), R 1 And Y are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and X is a radical-reactive functional group, a hydrogen atom, or a methyl group; however, at least one of X is a radical-reactive functional group. 2 (where a is a monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and where a is a number from 10 to 10,000, and b is a number from 0 to 10,000.) 3. A composition comprising 10 to 60% by mass, in terms of solid content, of the vinyl chloride / silicone block copolymer described in claim 1, relative to the total mass of the composition.

4. An emulsion of vinyl chloride / silicone block copolymer according to claim 1.

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