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

Abstract

The present invention provides a vinyl chloride-silicone copolymer having slidability, water repellency, alcohol resistance, substrate adhesion, and transparency. A vinyl chloride-silicone graft copolymer, which is a copolymer of (A) an organopolysiloxane of the following formula (1) and (B) vinyl chloride, wherein the mass ratio (A):(B) = 5:95 to 95:5. In formula (1), R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 is a radical-reactive functional group. 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. Y is X or a group represented by -[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 0 to 10,000, b is 100 to 10,000, c is 0.0001 to 100, and d is 1 to 1,000.

Description

Technical Field

[0001] This invention relates to graft copolymers of organopolysiloxanes and vinyl chloride and methods for manufacturing the same, and more specifically, to vinyl chloride-organosilicone graft copolymers having properties of slip resistance, water repellency, alcohol resistance, substrate adhesion, and transparency, and methods for manufacturing the same. Background Technology

[0002] Previously, silicone resins were known to impart sliding properties to substrates. However, when silicone resins are used alone, problems such as poor adhesion to the substrate exist.

[0003] Therefore, a method was adopted to copolymerize silicone resins with other monomers such as acrylic resins, polyurethane resins (urethane resins), or vinyl acetate resins. Copolymers of acrylic silicones, polyurethane silicones, etc., can impart advantages such as weather resistance, heat resistance, cold resistance, water repellency, air permeability, and lubricity to silicone resins based on the properties of acrylic or polyurethane resins.

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

[0005] On the other hand, it is known that vinyl chloride resins are also used in copolymerization with other monomers. For example, vinyl chloride-vinyl acetate copolymer resins, which are copolymerized from vinyl chloride and vinyl acetate, can be cited. Patent document 3 (Japanese Patent Application Publication No. 2001-114839) and other documents disclose vinyl chloride-vinyl acetate copolymer resins and methods for manufacturing the same, and it is known that by using them in substrates such as ink materials and receiving layers, color development and adhesion can be improved.

[0006] It is known that silicone resins or vinyl chloride resins can be copolymerized by reacting them with other monomers. However, for the combination of vinyl chloride and organopolysiloxanes (silicone resins), since the two are inherently incompatible, attempts to copolymerize them have been almost nonexistent. Furthermore, even when silicone and vinyl chloride are copolymerized, it has not been considered possible to obtain resins that can fully utilize their respective properties.

[0007] Patent document 4 (Japanese Patent Application Publication No. 59-166520) discloses a resin obtained by graft polymerization of vinyl chloride resin and organosilicon, which has good oxygen permeability. The use of this resin in the field of packaging related to fresh food or in medical blood bags has been studied. However, the practicality of using the roller compound to form sheets in this application is low, and there is still room for improvement.

[0008] Furthermore, Patent Document 5 (Japanese Patent Application Publication No. 07-102146) discloses an improvement in release properties (peelability) during calendering by using a block copolymer resin composed of vinyl chloride and siloxane blocks. Patent Document 6 (Japanese Patent Application Publication No. 09-255705) discloses the polymerization of vinyl chloride in the presence of a copolymer resin of siloxane and acrylic acid. This is its use as an additive in the manufacture of vinyl chloride resin; research on it as a vinyl chloride-organosilicon copolymer resin has been almost non-existent until now.

[0009] In addition, a method of mixing silicone resin emulsion with vinyl chloride resin emulsion to obtain a coating agent was also considered, but the silicone component would seep out from the mixture, and the desired performance could not be obtained, so there is still room for improvement.

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: Japanese Patent Application Publication No. 2020-90563

[0013] Patent Document 2: Japanese Patent Application Publication No. 2022-131528

[0014] Patent Document 3: Japanese Patent Application Publication No. 2001-114839

[0015] Patent Document 4: Japanese Patent Application Publication No. 59-166520

[0016] Patent Document 5: Japanese Patent Application Publication No. 07-102146

[0017] Patent Document 6: Japanese Patent Application Publication No. 09-255705 Summary of the Invention

[0018] The problem that the invention aims to solve

[0019] Therefore, the object of the present invention is to provide a vinyl chloride-organosilicon graft copolymer with sliding properties, water repellency, alcohol resistance, substrate adhesion, and transparency.

[0020] Methods for solving problems

[0021] In order to achieve the above objectives, the inventors conducted in-depth research and found that the vinyl chloride-organosilicon graft copolymer obtained by graft copolymerization of (A) organopolysiloxane and (B) vinyl chloride has sliding properties, water repellency, alcohol resistance, substrate adhesion and transparency, thereby completing the present invention.

[0022] That is, the present invention provides the following vinyl chloride-organosilicon graft copolymer, the method for manufacturing the same, and compositions and emulsions of the graft copolymer.

[0023] [1] A vinyl chloride-organosilicon 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) organopolysiloxane to (B) vinyl chloride is (A): (B) = 5:95 to 95:5.

[0024] [Chemistry 1]

[0025]

[0026] (In equation (1), R) 1 R is a monovalent hydrocarbon group with 1 to 20 carbon atoms, which may be the same or different, substituted or unsubstituted. 2 It is a free radical reactive functional group. X is a monovalent hydrocarbon group, alkoxy group, or hydroxyl group with 1 to 20 carbon atoms, either substituted or unsubstituted, and may be the same or different. Y is X or composed of -[O-Si(X)2] d -X represents the same or different groups. Z is an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 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.

[0027] [2] A method for manufacturing a vinyl chloride-organosilicon graft copolymer, comprising a step of polymerizing (A) an organopolysiloxane represented by the following formula (1) with (B) vinyl chloride at a mass ratio of (A):(B)=5:95 to 95:5.

[0028] [Chemistry 2]

[0029]

[0030] (In equation (1), R) 1 R is a monovalent hydrocarbon group with 1 to 20 carbon atoms, which may be the same or different, substituted or unsubstituted. 2 It is a free radical reactive functional group. X is a monovalent hydrocarbon group, alkoxy group, or hydroxyl group with 1 to 20 carbon atoms, either substituted or unsubstituted, and may be the same or different. Y is X or composed of -[O-Si(X)2] d -X represents the same or different groups. Z is an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 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.

[0031] [3] A composition containing 10 to 60% by weight of the vinyl chloride-organosilicon graft copolymer described in [1] relative to the total weight of the composition in terms of solid content.

[0032] [4][1] The emulsion of the vinyl chloride-organosilicon graft copolymer.

[0033] Invention Effects

[0034] The vinyl chloride-organosilicon graft copolymer of the present invention possesses properties such as slip resistance, water repellency, alcohol resistance, substrate adhesion, and transparency. Therefore, compositions containing the vinyl chloride-organosilicon graft copolymer of the present invention are suitable for use as coatings, adhesives, exterior / interior coatings for structures or building materials, cosmetics, etc., on various substrates. Detailed Implementation

[0035] Vinyl chloride-organosilicon graft copolymer

[0036] The present invention is a vinyl chloride-organosilicon graft copolymer obtained by graft copolymerization of (A) organopolysiloxane and (B) vinyl chloride.

[0037] The organopolysiloxane (A) in this invention is represented by the following formula (1).

[0038] [Chemistry 3]

[0039]

[0040] (In equation (1), R) 1 R is a monovalent hydrocarbon group with 1 to 20 carbon atoms, which may be the same or different, substituted or unsubstituted. 2 It is a free radical reactive functional group. X is a monovalent hydrocarbon group, alkoxy group, or hydroxyl group with 1 to 20 carbon atoms, either substituted or unsubstituted, and may be the same or different. Y is X or composed of -[O-Si(X)2] d -X represents the same or different groups. Z is an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 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.

[0041] Here, R 1These are monovalent hydrocarbon groups with 1 to 20 carbon atoms, either substituted or unsubstituted, and specifically include: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc.; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, etc.; alkenyl groups such as vinyl, allyl, etc.; aryl groups such as phenyl, tolyl, naphthyl, etc.; alkenyl aryl groups such as vinylphenyl, etc.; aralkyl groups such as benzyl, phenylethyl, phenylpropyl, etc.; alkenyl aralkyl groups such as vinylbenzyl, vinylphenylpropyl, etc.; and groups in which some or all of the hydrogen atoms are substituted by halogen atoms such as fluorine, bromine, chlorine, acryloyloxy, methacryloyloxy, carboxyl, alkoxy, alkenyloxy, amino, alkyl or alkoxy or (meth)acryloyloxy amino groups. As R 1 Preferably, it is methyl.

[0042] R 2 Examples of free radical reactive functional groups include: alkyl groups with 1 to 8 carbon atoms substituted with a mercapto or an olefinic double bond, such as alkyl groups, vinyl groups, or styryl groups. Specific examples of alkyl groups with 1 to 8 carbon atoms substituted with a mercapto or an olefinic double bond include: alkyl groups with 1 to 8 carbon atoms substituted with mercapto, vinyl, styryl, acryloyloxy, or methacryloyloxy groups. As R 2 Examples of free radical reactive functional groups include: vinyl, styryl, octenyl, methacryloyloxyoctyl, mercaptopropyl, acryloyloxypropyl, methacryloyloxyoctylvinyl, etc. R 2 It can be one type or a combination of two or more types.

[0043] X is a monovalent hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, or an alkoxy or hydroxyl group with 1 to 20 carbon atoms. Examples of unsubstituted or substituted monovalent hydrocarbon groups with 1 to 20 carbon atoms, such as R, can be found. 1 The same group exemplified herein, as an alkoxy group having 1 to 20 carbon atoms, can be specifically exemplified by: methoxy, ethoxy, propoxy, butoxy, hexoxy, heptoxy, octoxy, decoxy, tetradecyloxy, etc. Among these, hydroxyl, methyl, butyl, and phenyl are preferred.

[0044] Y is either X or composed of -[O-Si(X)2] d -X represents the same or different groups. As X, the same groups exemplified above may be used.

[0045] Z is an alkyl group, an alkoxy group, or a hydroxy group with 1 to 4 carbon atoms, preferably a hydroxyl or methyl group.

[0046] a is a number from 0 to 10,000, preferably from 0 to 1,000, and more preferably from 0 to 200. When constituting a unit, its lower limit is 0.5. If a is greater than 10,000, the strength of the resulting coating may be insufficient when the composition containing component (A) is used as a coating film.

[0047] b is a number from 100 to 10,000, preferably from 1,000 to 10,000, and more preferably from 1,000 to 5,000. If b is less than 100, the flexibility of the coating may sometimes be reduced; if b is greater than 10,000, its tear strength may sometimes be reduced.

[0048] c is a number between 0.0001 and 100. If it exceeds 100, the sliding effect may not work.

[0049] Here, c / (a+b+c)×100 is preferably 0.0001 to 10, more preferably 0.001 to 10, even more preferably 0.001 or more and less than 4, and particularly preferably 0.001 to 2.

[0050] d is a number from 1 to 1,000, preferably a number from 1 to 200.

[0051] The organopolysiloxane represented by formula (1) above is preferably used in the form of an emulsion. It can be a commercially available product or synthesized. In synthesis, it can be synthesized by a known emulsion polymerization method. For example, an anionic surfactant can be used to emulsify and disperse the cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, etc., with the silane coupling agent represented by formula (2) below in water. Then, a polymerization catalyst such as an acid is added as needed to carry out the polymerization reaction, thereby easily synthesizing the cyclic organosiloxane. The cyclic organosiloxane may have fluorine atoms, (meth)acryloyloxy groups, carboxyl groups, hydroxyl groups, and amino groups.

[0052] [Chemistry 4]

[0053]

[0054] (In equation (2), R) 3 It is a free radical reactive functional group, specifically representing an acryloyloxy, methacryloxy, vinyl or mercapto-substituted alkyl group having 1 to 8 carbon atoms, or a styryl or vinyl group. R 4 R is an alkyl or hydroxyl group having 1 to 4 carbon atoms. 5 (Alkyl groups having 1 to 4 carbon atoms, where e is 2 or 3, f is 0 or 1, and e+f is 2 or 3.)

[0055] Examples of the aforementioned cyclic organosiloxanes include: hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecylcyclohexasiloxane (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-methacryloyloxypropyl)tetramethylcyclotetrasiloxane. Oxyalkane, 1,3,5,7-tetra(3-acryloyloxypropyl)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. Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are preferred.

[0056] Specific examples of silane coupling agents include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and other vinyl silanes; γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, γ-(meth)acryloyloxypropyltripropoxysilane, γ-(meth)acryloyloxypropyltriisopropoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriprop ... Acrylic silanes such as γ-(meth)acryloyloxypropylmethyldimethoxysilane, γ-(meth)acryloyloxypropylmethyldiethoxysilane, γ-(meth)acryloyloxypropylmethyldipropoxysilane, γ-(meth)acryloyloxypropylmethyldiisopropoxysilane, and γ-(meth)acryloyloxypropylmethyldibutoxysilane; mercaptosilanes such as γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropyltrimethoxysilane; and styryl silanes such as styryltrimethoxysilane. Furthermore, oligomers obtained by condensation polymerization of these compounds are sometimes preferred because they can suppress alcohol formation. Here, (meth)acryloyloxy refers to acryloyloxy or methacryloyloxy.

[0057] These silane coupling agents are preferably used in 0.01 to 20 parts by weight relative to 100 parts by weight of cyclic organosiloxanes or α,ω-dihydroxysiloxane oligomers, α,ω-dialkoxysiloxane oligomers, or alkoxysilanes, and more preferably in 0.01 to 5 parts by weight.

[0058] By copolymerizing cyclic organosiloxanes or α,ω-dihydroxysiloxane oligomers, α,ω-dialkoxysiloxane oligomers, alkoxysilanes with silane coupling agents, units having the repeating number c in the above formula (1) can be obtained (from [Si(R 2 (Z)O] represents an organopolysiloxane, which is capable of grafting polymerizing (B) vinyl chloride.

[0059] As the polymerization catalyst, any known polymerization catalyst may be used. Strong acids are preferred, examples of which include hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid. Dodecylbenzenesulfonic acid, which has surface-active properties, is particularly preferred.

[0060] The amount of polymerization catalyst used is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, or alkoxysilane, more preferably 0.2 to 2 parts by mass.

[0061] Furthermore, sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyl taurate, aliphatic soaps, alkyl phosphates, sodium lauroyl methyl taurate, and sodium myristoyl methyl taurate are preferred as anionic surfactants. N-acyl amino acid salts, N-acyl taurate, aliphatic soaps, alkyl phosphates, sodium lauroyl methyl taurate, and sodium myristoyl methyl taurate are more preferred, and sodium lauroyl methyl taurate, sodium myristoyl methyl taurate, and sodium lauryl sulfate are particularly preferred.

[0062] It should be noted that the amount of anionic surfactant used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, or alkoxysilane.

[0063] The polymerization temperature is preferably 50–75°C, and the polymerization time is preferably 10 hours or more, more preferably 15 hours or more. It is particularly preferred that the product be cured at 5–30°C for 10 hours or more after polymerization.

[0064] After the polymerization reaction is completed, the pH can be neutralized to 2.5-14, preferably 4-11, using a neutralizing agent (such as a 10% sodium carbonate aqueous solution).

[0065] From the perspective of sliding effect, the weight-average molecular weight (Mw) of (A) organopolysiloxane based on viscosity measurement is preferably 10,000 to 1,000,000, more preferably 100,000 to 500,000.

[0066] Here, the weight-average molecular weight (Mw) of organopolysiloxane based on viscosity determination is calculated from the specific viscosity ηsp (25°C) of a toluene solution of organopolysiloxane with a concentration of 1 g / 100 ml.

[0067] ηsp = (η / η0) - 1

[0068] (η0: viscosity of toluene, η: viscosity of the solution)

[0069] ηsp = [η] + 0.3[η] 2

[0070] [η]=0.215×10 -4 M 0.65

[0071] Specifically, 20g of organopolysiloxane emulsion was mixed with 20g of IPA (isopropanol). After the emulsion was broken up, the IPA was discarded, and the remaining rubbery organopolysiloxane was dried at 60°C overnight. A toluene solution of organopolysiloxane with a concentration of 1g / 100ml was prepared and measured using an Ubbelohde viscometer at 25°C. The molecular weight could be calculated by substituting the viscosity into the above formula (References: Nakamuta, Nippon Kagaku, 77 858

[1956] , Doklady Akad. Nauk. USSR 89 65

[1953] ).

[0072] Manufacturing method

[0073] The vinyl chloride-organosilicon graft copolymer of the present invention can be obtained by grafting (A) organopolysiloxane with (B) vinyl chloride.

[0074] The method for manufacturing the vinyl chloride-organosilicon graft copolymer of the present invention includes a step of grafting polymerization of the organopolysiloxane (component (A)) of formula (1) and vinyl chloride (component (B)) at a mass ratio (mass ratio of organopolysiloxane to vinyl chloride unit of formula (1)) of 5:95 to 95:5, preferably 20:80 to 85:15. If the proportion of organopolysiloxane component of formula (1) is less than 5 as described above, the sliding effect may sometimes not be achieved.

[0075] Examples of free radical initiators used in the manufacture of the vinyl chloride-organosilicon graft copolymer of the present invention include: persulfates such as potassium persulfate and ammonium persulfate, peroxysulfuric acid solution, tert-butyl hydroperoxide, and hydrogen peroxide. Redox compounds, in combination with reducing agents such as acidic sodium sulfite, sodium dithionite, L-ascorbic acid, tartaric acid, sugars, and amines, may also be used as needed.

[0076] Furthermore, the amount of free radical initiator used is preferably 0.1 to 5% by mass of (B) vinyl chloride, more preferably 0.5 to 3% by mass.

[0077] The polymerization temperature of component (B) and component (A) is preferably 25–85°C, more preferably 55–85°C. Furthermore, the polymerization time is preferably 2–20 hours, more preferably 3–10 hours.

[0078] In addition, 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 thiols such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan.

[0079] The amount of chain transfer agent used relative to 100 parts by weight of monomer (vinyl chloride) is preferably 0.1 to 1 part by weight, more preferably 0.3 to 0.8 parts by weight.

[0080] The resulting vinyl chloride-organosilicon graft copolymer is a polymer formed by random bonding of vinyl chloride (B) to organopolysiloxane (A), and is a polymer with a mixture of multiple structures. This substance cannot be directly identified by its structure or properties.

[0081] The method for manufacturing the vinyl chloride-organosilicon graft copolymer of the present invention preferably includes a step of emulsion polymerization of the organopolysiloxane ((A) component) of formula (1) and the vinyl chloride ((B) component) at a mass ratio (mass ratio of organopolysiloxane to vinyl chloride unit of formula (1)) of 5:95 to 95:5, preferably 20:80 to 85:15.

[0082] In the case of emulsion polymerization, the organopolysiloxane of component (A) is used in the form of an emulsion. The surfactant contained in the organopolysiloxane emulsion is sufficient for graft polymerization. However, to improve stability, sodium lauryl sulfate, sodium lauryl ether sulfate, N-acyl amino acid salts, N-acyl taurate, aliphatic soaps, alkyl phosphates, etc., can be added as anionic surfactants. In addition, nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can also be added. The preferred amount of surfactant used is 0.1 to 5% by mass of vinyl chloride (B).

[0083] Thus, the vinyl chloride-organosilicon graft copolymer obtained by emulsion polymerization can also be obtained in the form of an emulsion, that is, as an emulsion of the vinyl chloride-organosilicon graft copolymer.

[0084] Furthermore, the solids content of the vinyl chloride-organosilicon graft copolymer emulsion is preferably 25-40% by mass. Additionally, the viscosity (25°C) of the emulsion is preferably 1-500 mPa·s, more preferably 1-200 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). It should be noted that the average particle size is a value measured using a dynamic light scattering particle size distribution measuring device.

[0085] The vinyl chloride-organosilicon graft copolymer of the present invention can also be powdered by emulsion granulation using the methods listed below. Examples include: freeze pulverization, spray drying, and airflow drying; spray drying is preferred for productivity considerations. The smaller the average particle size of the resulting powder particles, the better, preferably 1 to 50 μm, more preferably 1 to 30 μm. It should be noted that the particle size of the emulsion and powder described above can be determined as the cumulative mass average value D50 in a laser diffraction particle size analyzer.

[0086] By combining the vinyl chloride-organosilicon graft copolymer (copolymer resin) of the present invention with other resins, pigments, fillers, matting agents, antioxidants, ultraviolet absorbers, antifreeze agents, pH adjusters, preservatives, defoamers, antibacterial agents, mildew inhibitors, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, surfactants and / or organic solvents (film-forming aids, etc.), it can be used as a composition containing vinyl chloride-organosilicon graft copolymer for coatings, adhesives, external / internal coatings and adhesives for structures or building materials, paper processing agents, fiber treatment agents, cosmetics, etc.

[0087] The composition containing the vinyl chloride-organosilicon graft copolymer of the present invention preferably contains 10 to 60% by weight of the vinyl chloride-organosilicon graft copolymer relative to the total weight of the composition, more preferably 20 to 50% by weight, and particularly preferably 30 to 50% by weight.

[0088] To clarify, when an organic solvent is mixed into a composition containing the aforementioned vinyl chloride-organosilicon graft 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; tetrahydrofuran, dimethyl ethyl ketone ... Ethers such as alkanes, 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; nitrile compounds 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, etc. Organic solvents can be used alone or in mixtures.

[0089] Compositions containing the vinyl chloride-organosilicon graft copolymer of the present invention can be used as coating agents. In this case, the coating agent can be obtained by dissolving the vinyl chloride-organosilicon graft copolymer with other components using known mixing preparation methods such as propeller mixers, homogenizers, ball mills, and bead mills. When the coating agent is applied to or impregnated on one or both sides of a substrate such as glass or resin and dried, it can impart slip properties and substrate adhesion.

[0090] Example

[0091] The present invention will be specifically described below with examples and comparative examples, but the present invention is not limited to the examples described below. Furthermore, the molecular weights described below are weight-average molecular weights (Mw) determined based on viscosity measurements from the specific viscosity of a toluene solution of organopolysiloxane at a concentration of 1 g / 100 ml. It should be noted that in the examples below, parts and % represent parts by mass and mass%, respectively.

[0092] [Example 1]

[0093] In a 4L polyethylene beaker, a mixture containing 1200g of octamethylcyclotetrasiloxane, 4.8g of γ-methacryloyloxypropylmethyldimethoxysilane, and 12g of sodium lauryl sulfate dissolved in 108g of pure water, and a mixture containing 12g of dodecylbenzenesulfonic acid dissolved in 108g of pure water were added. After homogenizing the mixture using a homogenizer, 728g of water was gradually added for dilution. The mixture was then subjected to a pressure of 300 kgf / cm². 2 The mixture was homogenized twice using a high-pressure homogenizer to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirrer, thermometer, and reflux condenser, and subjected to polymerization at 55°C for 24 hours, followed by aging at 15°C for 24 hours. It was then neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the non-volatile component (solids) of the emulsion was 44%, and the organopolysiloxane in the emulsion was a non-flowing soft gel. This emulsion (organosilicon composition) has a structure represented by the following formula (A) with a molecular weight of approximately 250,000, determined based on the viscosity of the toluene solution. In formula (A), R... 2It is γ-methacryloyloxypropyl. The structure of the organopolysiloxane obtained by the above polymerization reaction is determined by... 1 H-NMR (frequency 600MHz, room temperature, cumulative count 128 times) and 29 The results were confirmed by Si-NMR (60MHz, room temperature, 5000 times) (device name: JNM-ECA600, solvent: CDCl3).

[0094] [Chemistry 5]

[0095]

[0096] 1207g of the above emulsion was transferred to a polymerization container equipped with a stirrer, condenser, thermometer, and nitrogen inlet. 59g of vinyl chloride and ammonium persulfate were added, and the reaction was carried out at 60°C for 8 hours, thereby grafting vinyl chloride onto the above organosilicon composition to obtain an emulsion of a vinyl chloride-organosilicon graft copolymer with a non-volatile content of 30%. The resulting vinyl chloride-organosilicon graft copolymer is derived from R in formula (A). 2 A vinyl chloride-organosilicon graft copolymer with vinyl chloride grafted onto it.

[0097] [Example 2]

[0098] Except that the amount of vinyl chloride in Example 1 was changed to 132g, the same method was used to obtain an emulsion of vinyl chloride-organosilicon graft copolymer with 30% non-volatile components.

[0099] [Example 3]

[0100] Except that the amount of vinyl chloride in Example 1 was changed to 226g, the same method was used to obtain an emulsion of organosilicon vinyl chloride graft copolymer with 30% non-volatile components.

[0101] [Example 4]

[0102] In a 4L polyethylene beaker, a mixture containing 1200g of octamethylcyclotetrasiloxane, 0.96g of γ-methacryloyloxypropylmethyldimethoxysilane, and 12g of sodium lauryl sulfate dissolved in 108g of pure water, and a mixture containing 12g of dodecylbenzenesulfonic acid dissolved in 108g of pure water were added. After homogenizing the mixture using a homogenizer, 728g of water was gradually added for dilution. The mixture was then subjected to a pressure of 300 kgf / cm². 2The mixture was homogenized twice using a high-pressure homogenizer to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours, followed by aging at 15°C for 24 hours. It was then neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the non-volatile component (solids) of the emulsion was 45%, and the organopolysiloxane in the emulsion was a non-flowing soft gel. This emulsion (organosilicon composition) has the structure represented by the following formula (B) with a molecular weight of approximately 250,000, determined based on the viscosity of the toluene solution. In formula (B), R... 2 It is γ-methacryloxypropyl.

[0103] [Chemistry 6]

[0104]

[0105] 1198g of the above emulsion was transferred to a polymerization container equipped with a stirrer, condenser, thermometer, and nitrogen inlet. 231g of vinyl chloride and ammonium persulfate were added, and the reaction was carried out at 60°C for 8 hours, thereby grafting the above organosilicon composition with copolymerized vinyl chloride to obtain an emulsion of vinyl chloride-organosilicon graft copolymer with a non-volatile content of 30%. The obtained vinyl chloride-organosilicon graft copolymer is derived from R in formula (B). 2 A vinyl chloride-organosilicon graft copolymer with vinyl chloride grafted onto it.

[0106] [Example 5]

[0107] Except that the amount of vinyl chloride in Example 1 was changed to 528g, the same method was used to obtain an emulsion of vinyl chloride-organosilicon graft copolymer with 30% non-volatile components.

[0108] [Example 6]

[0109] Except that the amount of vinyl chloride in Example 1 was changed to 1232g, the same method was used to obtain an emulsion of vinyl chloride-organosilicon graft copolymer with 30% non-volatile components.

[0110] [Example 7]

[0111] Except that the amount of vinyl chloride in Example 1 was changed to 4752g, the same method was used to obtain an emulsion of vinyl chloride-organosilicon graft copolymer with 30% non-volatile components.

[0112] [Comparative Example 1]

[0113] In a 4L polyethylene beaker, a mixture containing 1200g of octamethylcyclotetrasiloxane, 4.8g of γ-methacryloyloxypropylmethyldimethoxysilane, and 12g of sodium lauryl sulfate dissolved in 108g of pure water, and a mixture containing 12g of dodecylbenzenesulfonic acid dissolved in 108g of pure water were added. After homogenizing the mixture using a homogenizer, 728g of water was gradually added for dilution. The mixture was then subjected to a pressure of 300 kgf / cm². 2 The mixture was homogenized twice using a high-pressure homogenizer to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours, followed by aging at 15°C for 24 hours. It was then neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the non-volatile component (solids) of the emulsion was 44%, and the organopolysiloxane in the emulsion was a non-flowing soft gel. This emulsion (organosilicon composition) has the structure represented by the above formula (A) with a molecular weight of approximately 250,000, determined based on the viscosity of the toluene solution.

[0114] [Comparative Example 2]

[0115] In a polymerization container equipped with a stirrer, condenser, thermometer, and nitrogen inlet, 840g of vinyl chloride, 16.8g of 2-hydroxyethyl methacrylate, and potassium persulfate were added. The mixture was reacted at 45°C with an additional 2530g of vinyl chloride for 30 hours to obtain an emulsion of copolymer with 40% non-volatile components.

[0116] [Comparative Example 3]

[0117] In a 2L polyethylene beaker, a mixture containing 1200g of octamethylcyclotetrasiloxane, 0.96g of γ-methacryloyloxypropylmethyldimethoxysilane, and 12g of sodium lauryl sulfate dissolved in 108g of pure water, and a mixture containing 12g of dodecylbenzenesulfonic acid dissolved in 108g of pure water were added. After homogenizing the mixture using a homogenizer, 400g of water was gradually added for dilution. The mixture was then subjected to a pressure of 300 kgf / cm². 2 The mixture was homogenized twice using a high-pressure homogenizer to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours, followed by aging at 15°C for 24 hours. It was then neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the emulsion contained 45% non-volatile components, and the organopolysiloxanes in the emulsion were in a non-flowing, soft gel state. This emulsion (organosilicon composition) has the structure represented by formula (B) with a molecular weight of approximately 250,000, determined based on the viscosity of the toluene solution.

[0118] Then, while adding 231.4 g of methyl methacrylate dropwise to the emulsion over 3 to 5 hours, a reaction was carried out at 27°C using tert-butyl hydrogen peroxide, thereby grafting acrylic acid onto the above-mentioned organosilicon composition, thus obtaining an emulsion of acrylic acid-organosilicon graft copolymer with a non-volatile content of 44.4%.

[0119] [Comparative Example 4]

[0120] 160g of the silicone emulsion obtained in Comparative Example 1 and 75g of the vinyl chloride emulsion obtained in Comparative Example 2 were stirred and mixed for 1 hour to obtain a mixed emulsion with a non-volatile component of 42.7%.

[0121] [Comparative Example 5]

[0122] In a 2L polyethylene beaker, a mixture containing 1200g of octamethylcyclotetrasiloxane, 0.96g of γ-methacryloyloxypropylmethyldimethoxysilane, and 12g of sodium lauryl sulfate dissolved in 108g of pure water, and a mixture containing 12g of dodecylbenzenesulfonic acid dissolved in 108g of pure water were added. After homogenizing the mixture using a homogenizer, 400g of water was gradually added for dilution. The mixture was then subjected to a pressure of 300 kgf / cm². 2 The mixture was homogenized twice using a high-pressure homogenizer to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours, followed by aging at 15°C for 24 hours. It was then neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the emulsion contained 45% non-volatile components, and the organopolysiloxanes in the emulsion were in a non-flowing, soft gel state. This emulsion (organosilicon composition) has the structure represented by formula (B) with a molecular weight of approximately 250,000, determined based on the viscosity of the toluene solution.

[0123] Then, while adding 231.1g of styrene dropwise to the emulsion over 3 to 5 hours, a reaction was carried out at 27°C using tert-butyl hydrogen peroxide, thereby grafting copolystyrene onto the above-mentioned organosilicon composition to obtain an emulsion of styrene-organosilicon graft copolymer with a non-volatile content of 44.0%.

[0124] [Comparative Example 6]

[0125] In a 2L polyethylene beaker, a mixture containing 1200g of octamethylcyclotetrasiloxane, 0.96g of γ-methacryloyloxypropylmethyldimethoxysilane, and 12g of sodium lauryl sulfate dissolved in 108g of pure water, and a mixture containing 12g of dodecylbenzenesulfonic acid dissolved in 108g of pure water were added. After homogenizing the mixture using a homogenizer, 400g of water was gradually added for dilution. The mixture was then subjected to a pressure of 300 kgf / cm². 2The mixture was homogenized twice using a high-pressure homogenizer to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours, followed by aging at 15°C for 24 hours. It was then neutralized to pH 7 with a 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the emulsion contained 45% non-volatile components, and the organopolysiloxanes in the emulsion were in a non-flowing, soft gel state. This emulsion (organosilicon composition) has the structure represented by formula (B) with a molecular weight of approximately 250,000, determined based on the viscosity of the toluene solution.

[0126] Subsequently, while adding 231.1 g of acrylonitrile dropwise to the emulsion over 3–5 hours, a reaction was carried out at 27°C using tert-butyl hydrogen peroxide. However, gelation occurred during the dropwise addition process, and the target acrylonitrile-organosilicon copolymer was not obtained.

[0127] The emulsions obtained in Examples 1-7 and Comparative Examples 1-5 were evaluated as follows. The results are shown in Tables 1 and 2.

[0128] <Methods for Determination of Solid Components>

[0129] Accurately weigh approximately 1g of sample into an aluminum foil dish, place it in a desiccator maintained at approximately 105°C, heat for 1 hour, remove it from the desiccator, allow it to cool naturally in a desiccator, weigh the aluminum foil dish containing the dried sample, and calculate the solid composition (evaporation residue) using the following formula.

[0130] [Number 1]

[0131]

[0132] R: Solid content (evaporation residue) (%)

[0133] W: Mass of the aluminum foil dish containing the sample before drying (g)

[0134] L: Mass of the aluminum foil dish (g)

[0135] T: Mass of the dried aluminum foil dish containing the sample (g)

[0136] Aluminum foil dish size: 65 ×23h (mm)

[0137] <Viscosity Measurement Methods>

[0138] The sample liquid temperature was maintained at 23±0.5℃, and the measurement was performed using a rotational viscometer (No.1 rotor, 6rpm, manufactured by Toki Sangyosha: trade name: VISCOMETER TVB-10).

[0139] <Average Particle Size>

[0140] The average particle size was determined by weighing 0.01g of sample and using a laser diffraction particle size distribution measuring device (manufactured by Horiba Corporation, trade name: LA-950V2) under the conditions of a circulation flow rate of 2 and a stirring speed of 2. The average particle size was equivalent to the particle size value of 50% of the cumulative particle size distribution.

[0141] [Measurement Conditions]

[0142] Measurement temperature: 25±1℃

[0143] Solvent: Ion-exchanged water

[0144] <Determination of Minimum Film Formation Temperature (MFT)>

[0145] The minimum film-forming temperature (MFT, °C) of the emulsion was determined according to JIS K-6828-2. Specifically, a simple film-forming temperature measuring device (manufactured by Imoto Manufacturing Co., Ltd.) with a heating source and a cooling source positioned at a certain interval was used. 1 μl of the emulsion was coated onto an aluminum foil, and the coating state was observed using this device after 2 hours. The emulsion was dried and formed into a film using a temperature gradient, and the boundary temperature between the transparent and unfilmed portions was measured as the minimum film-forming temperature (MFT, °C). Considering the drying properties during film formation, an MFT below 100 °C was desirable.

[0146] <Determination of Static / Dynamic Friction Coefficient>

[0147] The emulsions of each embodiment and comparative example were coated onto a PET film using a bar coater and dried at 105°C for 3 minutes to form a film with a thickness of approximately 10 μm after drying.

[0148] Using a HEIDON TYPE-38 (manufactured by Shin-To Science Co., Ltd.), a 200g metal indenter was brought into perpendicular contact with the coating, and the frictional force was measured when the indenter moved at a speed of 3 cm / min. The coefficient of friction was calculated from the frictional force. It should be noted that the preferred range for the static / dynamic coefficients of friction measured under the above conditions is: static coefficient of friction ≤ 0.2 and dynamic coefficient of friction ≤ 0.1.

[0149] <Substrate Adhesion>

[0150] The emulsions of each embodiment and comparative example were coated onto a soft vinyl chloride membrane using a bar coater and dried at 105°C for 3 minutes to form a coating with a thickness of approximately 10 μm after drying.

[0151] Stick cellophane tape onto the coating, peel it off in one go, and visually evaluate the adhesion.

[0152] ○: Not peeled off from the substrate

[0153] ×: There is peeling from the substrate

[0154] <Alcohol Resistance>

[0155] The emulsions of each embodiment and comparative example were coated onto a PET film using a bar coater and dried at 105°C for 3 minutes to form a film with a thickness of approximately 10 μm after drying.

[0156] Add 98% ethanol to the coating and let it air dry overnight at room temperature. Visually evaluate the changes in the coating after drying.

[0157] ○: No change in appearance

[0158] △: Marks remain but no whitening

[0159] ×: Albinism

[0160] <Water Contact Angle Measurement>

[0161] The emulsions of each embodiment and comparative example were coated onto a PET film using a bar coater and dried at 105°C for 3 minutes to form a film with a thickness of approximately 10 μm after drying.

[0162] Add 2 μl of pure water to the coating and measure the contact angle after 1 second and 30 seconds using a contact angle meter (CA-D type) manufactured by Kyowa Interface Science Co., Ltd. Considering the prevention of water-based fouling by water repellency, the contact angle is preferably 80° or higher.

[0163] [Table 1]

[0164]

[0165] [Table 2]

[0166]

Claims

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

5. [Chemistry 1] In equation (1), R 1 R is a monovalent hydrocarbon group with 1 to 20 carbon atoms, which may be the same or different, substituted or unsubstituted. 2 X is a free radical reactive functional group, where X is a monovalent hydrocarbon group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, or a hydroxyl group, and Y is X or a group consisting of -[O-Si(X)2]. d -X represents the same or different groups, Z is an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, or 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 manufacturing a vinyl chloride-organosilicon graft copolymer, comprising a step of polymerizing (A) an organopolysiloxane represented by formula (1) below with (B) vinyl chloride at a mass ratio of (A):(B) = 5:95 to 95:

5. [Chemistry 2] In equation (1), R 1 R is a monovalent hydrocarbon group with 1 to 20 carbon atoms, which may be the same or different, substituted or unsubstituted. 2 X is a free radical reactive functional group, where X is a monovalent hydrocarbon group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, or a hydroxyl group, and Y is X or a group consisting of -[O-Si(X)2]. d -X represents the same or different groups, Z is an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, or a is a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000.

3. A composition comprising 10 to 60% by weight of the vinyl chloride-organosilicon graft copolymer according to claim 1, based on the amount of solids relative to the total composition.

4. The emulsion of the vinyl chloride-organosilicon graft copolymer according to claim 1.

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