Resin composition comprising silicone-vinyl acetate copolymer resin and

Abstract

The present invention provides a resin composition comprising a silicone-vinyl acetate copolymer resin, the resin composition comprising (A) a copolymer resin comprising an organopolysiloxane unit derived from an organopolysiloxane represented by a specific general formula and (B) a vinyl acetate unit, and (C) a water-soluble polymer, the resin composition being characterized in that: the content of the organopolysiloxane unit in the copolymer resin is less than the content of the vinyl acetate unit in the copolymer resin; the mass ratio of the organopolysiloxane unit (A) to the vinyl acetate unit (B) is (A): (B) = 10: 90-95: 5, and the mass ratio of the vinyl acetate unit (B) to the water-soluble polymer (C) is 100: 5-50. The resin composition according to the present invention has sliding properties, base material adhesion, and organic solvent solubility, and is suitable for use as a coating agent for various base materials, an adhesive, a coating material for exterior / interior of a structure, a building material, and the like, a cosmetic material, and the like.

Description

Technical Field

[0001] The present invention relates to a resin composition comprising a resin obtained by copolymerizing an organopolysiloxane with vinyl acetate and a method for producing the same, and more particularly to an organosilicon-vinyl acetate copolymer resin having sliding properties, substrate adhesion, solvent resistance and scratch resistance and a method for producing the same. Background Art

[0002] Silicone resins are known as resins that can impart sliding properties to substrates, but when silicone resins are used alone, there are disadvantages such as poor adhesion to the substrate.

[0003] Therefore, a method of copolymerizing a silicone resin with another monomer such as an acrylic or urethane monomer is used. For example, copolymers such as acrylic silicone copolymers and urethane silicone copolymers can impart the advantages of silicone resins such as weather resistance, heat resistance, cold resistance, water repellency, gas permeability, and slippage to conventional acrylic or urethane emulsions. For example, Patent Document 1 (Japanese Patent Application Publication No. 2020-90563) discloses a silicone acrylic graft copolymer resin imparting slippage and a method for producing the same.

[0004] On the other hand, vinyl acetate resins have been used in emulsion adhesives, photosensitive materials for screen printing, cleaning pastes, gum bases, emulsifiers, and base materials for cosmetics, and are known as resins having excellent adhesion.

[0005] As a resin obtained by copolymerizing a vinyl acetate resin with another monomer, for example, an ethylene vinyl acetate copolymer obtained by copolymerizing ethylene can be cited. This copolymer is a synthetic resin having adhesiveness and flexibility derived from the vinyl acetate unit, and is used for coating materials for paper containers such as food wrapping paper and paper cups, adhesives for cloth / paper labels, emulsion adhesives, gum bases, artificial turf, sandal bases, bath mats, bathroom cleaning boots, beat boards, skipping ropes, and the like.

[0006] Silicone resin and vinyl acetate resin are resins having opposite properties. As previously disclosed in Japanese Patent Application Laid-Open No. 2022-131528, the present inventors have successfully developed a silicone-vinyl acetate copolymer resin having the properties of both silicone resin and vinyl acetate resin.

[0007] However, silicone-vinyl acetate copolymer resins have the disadvantages of being weak in solvent resistance and scratch resistance, and there is still room for improvement.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2020-90563

[0011] Patent Document 2: Japanese Patent Application Publication No. 2022-131528 Summary of the invention

[0012] Problems to be solved by the invention

[0013] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide a resin composition containing a silicone-vinyl acetate copolymer resin having sliding properties, substrate adhesion, solvent resistance and scratch resistance, and a method for producing the same.

[0014] Means for solving problems

[0015] The present inventors have conducted intensive studies to achieve the above-mentioned object and have found that a resin composition comprising a copolymer resin of (A) an organopolysiloxane unit and (B) a vinyl acetate unit and (C) a water-soluble polymer has sliding properties, substrate adhesion, solvent resistance and scratch resistance, thereby completing the present invention.

[0016] Therefore, the present invention provides a resin composition comprising the following silicone-vinyl acetate copolymer resin, a method for producing the same, and a dispersion thereof.

[0017] 1. A resin composition comprising (A) a copolymer resin of an organopolysiloxane unit represented by the following general formula (1) and (B) a vinyl acetate unit, and (C) a water-soluble polymer, wherein the mass ratio of the (A) organopolysiloxane unit to the (B) vinyl acetate unit is (A):(B)=10:90 to 95:5, and the mass ratio of the (B) vinyl acetate unit to the (C) water-soluble polymer is 100:5 to 50.

[0018] [Chemistry 1]

[0019]

[0020] (Where R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R 2 is an alkyl group having 1 to 6 carbon atoms, or a vinyl group substituted with a mercapto group, an acryloyloxy group, or a methacryloyloxy group. X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group; Y is X or -[O-Si(X)2] d-X represents the same or different groups, at least two of X and Y are hydroxyl groups, Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a positive number of 0 to 1000, b is a positive number of 100 to 10000, c is a positive number of 1 to 10, and d is a positive number of 1 to 1000.)

[0021] 2. The resin composition according to item 1 above, which is in the form of an emulsion having a viscosity (25° C.) of 1 to 500 mPa·s.

[0022] 3. The resin composition according to 1 or 2 above, wherein the organopolysiloxane represented by the formula (1) has a weight average molecular weight (Mw) of 10,000 to 1,000,000, as measured by viscosity.

[0023] 4. The resin composition according to 1 or 2 above, wherein the organopolysiloxane represented by the formula (1) is a polymer of a cyclic organosiloxane, an α,ω-dihydroxysiloxane oligomer, an α,ω-dialkoxysiloxane oligomer or an alkoxysilane and a silane coupling agent represented by the following general formula (2).

[0024] R 3 (4-e-f) R 4 f Si(OR 5 ) e (2)

[0025] (Where R 3 is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, an acryloyloxy group or a methacryloyloxy group, R 4 is an alkyl group having 1 to 4 carbon atoms, R 5 is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, and e+f is 2 or 3. )

[0026] 5. The resin composition according to 1 or 2 above, which is used as a product selected from the group consisting of a coating agent, a fiber treatment agent, an adhesive, a paint and a cosmetic.

[0027] 6. A dispersion comprising the resin composition according to 1 or 2 above.

[0028] 7. A method for producing a resin composition, characterized in that (A-1) an organopolysiloxane represented by the following general formula (1) and (B-1) vinyl acetate are emulsion polymerized in a mass ratio of (A-1):(B-1)=10:90 to 95:5, and further, during the emulsion polymerization, (C) a water-soluble polymer is polymerized in a solid content of 5 to 50 parts by mass relative to 100 parts by mass of (B-1) vinyl acetate to obtain a resin emulsion.

[0029] [Chemistry 2]

[0030]

[0031] (Where R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R 2 is an alkyl group having 1 to 6 carbon atoms, or a vinyl group substituted with a mercapto group, an acryloyloxy group, or a methacryloyloxy group. X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group; Y is X or -[O-Si(X)2] d -X represents the same or different groups, at least two of X and Y are hydroxyl groups. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a positive number of 0 to 1000, b is a positive number of 100 to 10000, c is a positive number of 1 to 10, and d is a positive number of 1 to 1000.

[0032] Effects of the Invention

[0033] The resin composition containing the organosilicon-vinyl acetate copolymer resin of the present invention has sliding properties, substrate adhesion, solvent resistance and scratch resistance. Therefore, the resin composition of the present invention is suitable for use in coating agents, adhesives, exterior / interior coatings for structures, building materials, and the like, cosmetics, and the like for various substrates. DETAILED DESCRIPTION

[0034] The present invention is a resin composition comprising (A) a copolymer resin of an organopolysiloxane unit and (B) a vinyl acetate unit, and (C) a water-soluble polymer.

[0035] The (A) organopolysiloxane unit in the present invention is derived from an organopolysiloxane represented by the following general formula (1).

[0036] [Chemistry 3]

[0037]

[0038] (Where R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R 2 is an alkyl group having 1 to 6 carbon atoms, or a vinyl group substituted with a mercapto group, an acryloyloxy group, or a methacryloyloxy group. X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group; Y is X or -[O-Si(X)2] d-X represents the same or different groups, at least two of X and Y are hydroxyl groups. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a positive number of 0 to 1000, b is a positive number of 100 to 10000, c is a positive number of 1 to 10, and d is a positive number of 1 to 1000.

[0039] Among them, R 1 R is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, vinyl, allyl, aryl groups such as phenyl, tolyl, naphthyl, alkenylaryl groups such as vinylphenyl, aralkyl groups such as benzyl, phenylethyl, phenylpropyl, alkenylaralkyl groups such as vinylbenzyl, vinylphenylpropyl, and the like, groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, or chlorine, acryloyloxy, methacryloyloxy, carboxyl, alkoxy, alkenyloxy, amino, alkyl or alkoxy or (meth)acryloyloxy substituted amino, and the like. 1 , preferably methyl.

[0040] R 2 It is a mercapto group, an alkyl group having 1 to 6 carbon atoms substituted with an acryloyloxy group or a methacryloyloxy group, or a vinyl group. Specifically, a mercaptopropyl group, an acryloyloxypropyl group, a methacryloyloxypropyl group, a vinyl group, etc. are preferred.

[0041] X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms or hydroxyl group. Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms include 1 The same groups as those exemplified in , as the alkoxy group having 1 to 20 carbon atoms, specifically, methoxy, ethoxy, propoxy, butoxy, hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, etc. X is preferably a hydroxyl group, a methyl group, a butyl group, or a phenyl group.

[0042] Y is X or -[O-Si(X)2] d -X represents the same or different groups.

[0043] Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and is preferably a hydroxyl group or a methyl group.

[0044] If a is larger than 1000, the strength of the film obtained when the resin composition containing the (A) component is used as a coating film becomes insufficient, so it is a number of 0 to 1000, preferably a number of 0 to 200. If b is less than 100, the film lacks flexibility, and if it is larger than 10000, the tear strength decreases, so it is a positive number of 100 to 10000, preferably a positive number of 1000 to 5000. c is a positive number of 1 to 10, and if it exceeds 10, there is a disadvantage that the sliding effect cannot be exerted.

[0045] d is a positive number of 1 to 1000, preferably 1 to 200. In addition, from the viewpoint of crosslinking properties, it is preferable to use a substance having at least 2, preferably 2 to 4 hydroxyl groups in one molecule and having hydroxyl groups formed at both terminals.

[0046] Such an organopolysiloxane represented by the general formula (1) is preferably used in the form of an emulsion, and a commercial product may be used or synthesized. In the case of synthesis, it can be carried out by a known emulsion polymerization method, and a cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, etc. which may have, for example, a fluorine atom, a (meth)acryloyloxy group, a carboxyl group, a hydroxyl group, an amino group, and a silane coupling agent represented by the following general formula (2) are emulsified and dispersed in water using an anionic surfactant, and then a catalyst such as an acid is added as needed to carry out a polymerization reaction, thereby making it easy to synthesize.

[0047] R 3 (4-e-f) R 4 f Si(OR 5 ) e (2)

[0048] (Where R 3 R represents a monovalent organic group having a polymerizable double bond, particularly an alkyl group having 1 to 6 carbon atoms substituted with an acryloyloxy group or a methacryloyloxy group. 4 is an alkyl group having 1 to 4 carbon atoms, R 5 is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, and e+f is 2 or 3. )

[0049] Examples of the cyclic organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane, and 1,3,5,7-tetrakis(3-methacryloxypropyl)tetramethylcyclotetrasiloxane. 1,3,5,7-tetrakis(3-acryloyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(3-carboxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(3-vinyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(p-vinylphenyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis[3-(p-vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(N-acryloyl-N-methyl-3-aminopropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetrakis(N,N-bis(lauroyl)-3-aminopropyl)tetramethylcyclotetrasiloxane, etc. Preferably, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are used.

[0050] Specific examples of the silane coupling agent include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tripropoxysilane, vinyl triisopropoxysilane, vinyl methyl dimethoxysilane, and vinyl methyl diethoxysilane; γ-(meth)acryloxypropyl trimethoxysilane, γ-(meth)acryloxypropyl triethoxysilane, γ-(meth)acryloxypropyl tripropoxysilane, γ-(meth)acryloxypropyl triisopropoxysilane, γ- Acryloylsilanes such as (meth)acryloxypropyltributoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxypropylmethyldiisopropoxysilane, and γ-(meth)acryloxypropylmethyldibutoxysilane; mercaptosilanes such as γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropyltrimethoxysilane. Alternatively, it is sometimes more preferable to suppress the production of alcohols by these condensation-polymerized oligomers. Among them, (meth)acryloxy represents an acryloyloxy group or a methacryloyloxy group. These silane coupling agents are preferably used in an amount of 0.01 to 20 parts by mass, and more preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the cyclic organosiloxane.

[0051] By copolymerizing the silane coupling agent, an organopolysiloxane having c in the following formula is obtained, thereby obtaining the effect of grafting (B-1) vinyl acetate.

[0052] [Chemistry 4]

[0053]

[0054] As the polymerization catalyst used for the polymerization, any known polymerization catalyst may be used. Among them, a strong acid is preferred, and examples thereof include hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid. Dodecylbenzenesulfonic acid having surface activation energy is preferred.

[0055] The amount of the acid catalyst used is preferably 0.01 to 10 parts by mass, more preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the cyclic organosiloxane.

[0056] In addition, as the surfactant during polymerization, as anionic surfactants, sodium dodecyl sulfate, sodium laureth sulfate, N-acylamino acid salts, N-acyl taurates, fatty soaps, alkyl phosphates, etc. can be listed, among which surfactants that are easily soluble in water and do not have a polyethylene oxide chain are preferred. N-acylamino acid salts, N-acyl taurates, fatty soaps and alkyl phosphates are more preferred, and sodium lauroyl methyl taurate, sodium myristoyl methyl taurate, and sodium dodecyl sulfate are particularly preferred.

[0057] The amount of the anionic surfactant used is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the cyclic organosiloxane.

[0058] The polymerization temperature is preferably 50 to 75° C., and the polymerization time is preferably 10 hours or longer, more preferably 15 hours or longer. Furthermore, it is particularly preferred to age the product at 5 to 30° C. for 10 hours or longer after the polymerization.

[0059] The weight average molecular weight (Mw) of the organopolysiloxane (A) thus obtained, as measured by viscosity, is 10,000 to 1,000,000, preferably 100,000 to 500,000. If it is less than 10,000, there is a disadvantage that the sliding effect cannot be exerted.

[0060] The weight average molecular weight (Mw) of the organopolysiloxane obtained by measuring the viscosity of the organopolysiloxane can be calculated from the specific viscosity ηsP (25° C.) of a toluene solution of the organopolysiloxane at a concentration of 1 g / 100 ml.

[0061] ηsP=(η / η0)-1

[0062] (η0: viscosity of toluene η: viscosity of solution)

[0063] ηsP=[η]+0.3[η] 2

[0064] [η] = 2.15 × 10 -4 M 0.65

[0065] Specifically, 20 g of the emulsion was mixed with 20 g of IPA (isopropyl alcohol), and after the emulsion was broken, the IPA was discarded, and the remaining rubbery organopolysiloxane was dried at 60° C. overnight. This was made into a toluene solution of the organopolysiloxane with a concentration of 1 g / 100 ml, and measured using an Ubbelohde viscometer at 25° C. The molecular weight can be obtained by substituting the viscosity into the above formula (references: Nakamuta, Nichika, 77 858

[1956] , Doklady Akad. Nauk. USSR8965

[1953] ).

[0066] The organosilicon-vinyl acetate copolymer resin of the present invention can be obtained by adding (C) a water-soluble polymer during emulsification graft polymerization of (B-1) vinyl acetate to the organopolysiloxane (A-1) obtained as described above.

[0067] The mass ratio of the organopolysiloxane of the formula (1) to vinyl acetate during graft polymerization (mass ratio of the organopolysiloxane of the formula (1) to the vinyl acetate unit) is 10:90 to 95:5, preferably 20:80 to 85:15. If the ratio of the polysiloxane component of the formula (1) is less than 10, there is a disadvantage that the sliding effect cannot be exerted.

[0068] Examples of the water-soluble polymer (C) include natural polymers such as protein, starch, gelatin, and casein, modified natural polymers such as dextrin, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose, and synthetic polymers such as polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyvinyl pyrrolidone, polyacrylamide, polyvinylamide, polyamine, and polyethylene oxide. Polyvinyl alcohol having surface activation energy is preferred.

[0069] The content of the water-soluble polymer (C) in the silicone-vinyl acetate copolymer resin of the present invention is prepared so that the mass ratio of the vinyl acetate unit (B) to the water-soluble polymer (C) is 100:5 to 50. Therefore, the amount of the water-soluble polymer (C) used in the emulsion graft polymerization is preferably adjusted so that the solid content of the water-soluble polymer (C) is 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the vinyl acetate (B-1) used. If the amount of the component (C) is less than 5 parts by mass, the solvent resistance effect cannot be exerted, and if it exceeds 50 parts by mass, there is a disadvantage that the sliding effect cannot be exerted.

[0070] The (C) water-soluble polymer can be added at any time before, during, or after the emulsification graft polymerization of (B-1) vinyl acetate and (A-1) organopolysiloxane. For example, after adding the (C) water-soluble polymer to the (A-1) organopolysiloxane, the (B-1) vinyl acetate can be added to start the polymerization. Alternatively, the (C) water-soluble polymer can be added after the polymerization of (A-1) organopolysiloxane and (B-1) vinyl acetate starts. When the (C) water-soluble polymer is added after the polymerization starts, the (C) water-soluble polymer is preferably added when the polymerization rate of (A-1) and (B-1) is between 0.1% and 80%, and more preferably between 1% and 60%.

[0071] As free radical initiators used when emulsifying and graft-polymerizing (A-1) organopolysiloxane (B-1) vinyl acetate, persulfates such as potassium persulfate and ammonium persulfate, hydrogen persulfate, tert-butyl hydroperoxide, and hydrogen peroxide can be listed. If necessary, a redox system using a reducing agent such as acidic sodium sulfite, Rongalite, L-ascorbic acid, tartaric acid, sugars, and amines can be used. The amount of the free radical initiator used is preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of (B-1) vinyl acetate.

[0072] The surface activation energy of the surfactant and (C) water-soluble polymer already contained in the organopolysiloxane emulsion can be fully grafted and polymerized. However, in order to improve the stability, sodium lauryl sulfate, sodium lauryl alcohol ether sulfate, N-acyl amino acid salt, N-acyl taurate, fatty soap, alkyl phosphate, 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 amount of the surfactant used when added is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of vinyl acetate (B-1).

[0073] The graft polymerization temperature of the component (B) and the component (A) is preferably 25 to 85° C., more preferably 75 to 85° C. The polymerization time is preferably 2 to 8 hours, more preferably 3 to 6 hours.

[0074] Furthermore, a chain transfer agent may be added to adjust the molecular weight and grafting ratio of the graft polymer, for example, halogenated hydrocarbons such as chloroform and carbon tetrachloride; and mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan.

[0075] The resin composition containing the silicone-vinyl acetate copolymer resin thus obtained is a polymer to which vinyl acetate is randomly grafted. The obtained resin composition is in a form in which a water-soluble polymer is dispersed around the silicone-vinyl acetate copolymer resin.

[0076] In addition, the resin composition containing the above-obtained silicone-vinyl acetate copolymer resin preferably has a solid content of 25 to 40% by mass. In addition, the viscosity (25°C) of the emulsion is preferably 1 to 500 mPa·s, more preferably 1 to 200 mPa·s. The viscosity can be measured using a rotational viscometer. The average particle size is preferably 0.1 μm (100 nm) to 0.5 μm (500 nm). Furthermore, the average particle size can be measured using a laser diffraction / scattering particle size distribution measuring device.

[0077] In addition, in 100% by mass of the above-mentioned emulsion (solid content), the total content of the copolymer resin of (A) organopolysiloxane units and (B) vinyl acetate units and (C) water-soluble polymer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

[0078] The resin composition containing the silicone-vinyl acetate copolymer resin of the present invention can be granulated and powdered by the methods listed below. That is, freeze grinding, spray drying, airflow drying, etc. can be listed. From the viewpoint of productivity, freeze grinding is preferably used. The above-mentioned freeze grinding is carried out by a known freeze grinding method. That is, it can be carried out by immersing the above-mentioned resin in liquid nitrogen, freezing it, putting the frozen resin into a freeze grinder, and crushing it into powder. The above-mentioned freeze grinder can use a known freeze grinder. The average particle size of the obtained powder particles is as small as possible, preferably less than 50μm, and more preferably 1 to 30μm. In addition, the particle size of the above-mentioned emulsion and powder can be measured as the cumulative mass average value D50 in a laser diffraction type particle size measuring instrument.

[0079] The resin composition containing the organosilicon-vinyl acetate copolymer resin of the present invention is compounded with other resins, pigments, fillers, matting agents, antioxidants, ultraviolet absorbers, antifreeze agents, pH adjusters, preservatives, defoamers, antibacterial agents, mildewproof agents, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, surfactants, film-forming aids and other organic solvents, other resins, etc., so that it can be used as a resin composition for coating agents, adhesives, exterior / interior coating adhesives for structures, building materials, etc., paper processing agents, fiber treatment agents, cosmetics, etc. for various substrates such as synthetic resins, metals, glass, ceramics, gypsum, paper, wood, leather, and lightweight concrete, lightweight air concrete, mortar, calcium silicate board, stone board, gypsum board, etc.

[0080] The resin composition containing the organosilicon-vinyl acetate copolymer resin of the present invention and the dispersion containing the resin composition can be used as a coating agent. In this case, the coating composition is obtained by mixing and dissolving the organosilicon-vinyl acetate copolymer resin and other components using a known mixing preparation method such as a propeller stirrer, a homogenizer, a ball mill, a bead mill, etc. When the coating composition is used as a coating agent, it is applied or impregnated on one or both sides of a substrate such as glass or resin, and dried, and then the coating composition can be given sliding properties and substrate adhesion.

[0081] Example

[0082] The following examples and comparative examples are shown to specifically illustrate the present invention, but the present invention is not limited to the following preparation examples and examples. In addition, the molecular weight described below is the weight average molecular weight (Mw) obtained by viscosity measurement from the specific viscosity of a toluene solution of an organopolysiloxane having a concentration of 1 g / 100 ml.

[0083] [Example 1]

[0084] A solution of 500 g of octamethylcyclotetrasiloxane, 2.5 g of γ-methacryloxypropylmethyldimethoxysilane, 5 g of sodium dodecyl sulfate dissolved in 45 g of pure water, and a solution of 5 g of dodecylbenzenesulfonic acid dissolved in 45 g of pure water were placed in a 2 L polyethylene beaker, and after being uniformly emulsified with a homomixer, 400 g of water was slowly added to dilute, and the mixture was stirred at a pressure of 300 kgf / cm 2 After passing through a high-pressure homogenizer twice, a uniform white emulsion was obtained. The emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, and a polymerization reaction was carried out at 55°C for 24 hours. After aging at 20°C for 24 hours, it was neutralized to pH 7 with a 10% sodium carbonate aqueous solution. The non-volatile component (solid content) of the emulsion after drying at 105°C for 3 hours was 45%, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel. The organosilicone composition has a molecular weight of about 250,000 as measured by the viscosity of the toluene solution and has a structure represented by formula (1). The structure of the organopolysiloxane obtained by the above polymerization reaction adopts 1 H-NMR (frequency 600 MHz, room temperature, accumulation times 128 times) and 29 Si-NMR (frequency 600 MHz, room temperature, accumulation number 5000 times) (apparatus name: JNM-ECA600, measurement solvent: CDCl 3 ) was used for confirmation.

[0085] 1580 g of a 10% aqueous solution of polyvinyl alcohol (98.5 mol% saponification degree, 500 degree of polymerization) was added thereto, and 1053 g of vinyl acetate was added dropwise over 3 to 5 hours while reacting at 80°C using an initiator, thereby grafting the vinyl acetate onto the silicone composition to obtain a silicone-vinyl acetate copolymer resin emulsion containing 30% of non-volatile components. The presence of polyvinyl alcohol in the obtained resin emulsion was confirmed by FT-IR (ATR method) [device name: IR Affinity-1s (Shimadzu Corporation)] and GCMS [device name: GCMS-QP2010 Ultra (Shimadzu Corporation)].

[0086] [Examples 2 to 4]

[0087] A silicone-vinyl acetate copolymer resin emulsion having a nonvolatile content of 30% was obtained in the same manner as in Example 1 except that the blending amounts of (A) to (C) were changed to those shown in Table 1.

[0088] [Comparative Example 1]

[0089] A solution of 500 g of octamethylcyclotetrasiloxane, 2.5 g of γ-methacryloxypropylmethyldimethoxysilane, 5 g of sodium dodecyl sulfate dissolved in 45 g of pure water, and a solution of 5 g of dodecylbenzenesulfonic acid dissolved in 45 g of pure water were placed in a 2 L polyethylene beaker, and after being uniformly emulsified with a homomixer, 400 g of water was slowly added to dilute, and the mixture was stirred at a pressure of 300 kgf / cm 2 After passing through a high-pressure homogenizer twice, a uniform white emulsion was obtained. The emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, and a polymerization reaction was carried out at 55°C for 24 hours. After aging at 20°C for 24 hours, it was neutralized to pH 7 with a 10% sodium carbonate aqueous solution. The non-volatile component (solid content) of the emulsion after drying at 105°C for 3 hours was 45%, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel. The organosilicon composition has a molecular weight of about 250,000 as measured by the viscosity of the toluene solution and is represented by the structure represented by formula (1).

[0090] 26 g of polyoxyethylene alkyl ether was added thereto, and 1053 g of vinyl acetate was added dropwise over a period of 3 to 5 hours while reacting at 80°C using an initiator, thereby graft copolymerizing vinyl acetate onto the above-mentioned silicone composition to obtain a silicone-vinyl acetate copolymer resin emulsion with a non-volatile component content of 30%.

[0091] [Comparative Example 2]

[0092] A solution of 500 g of octamethylcyclotetrasiloxane, 46 g of vinylmethyldimethoxysilane, 5 g of sodium dodecyl sulfate dissolved in 45 g of pure water, and a solution of 5 g of dodecylbenzenesulfonic acid dissolved in 45 g of pure water were placed in a 2 L polyethylene beaker, and after being uniformly emulsified with a homomixer, 450 g of water was slowly added to dilute, and the mixture was stirred at a pressure of 300 kgf / cm 2 After passing through a high-pressure homogenizer twice, a uniform white emulsion was obtained. The emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, and a polymerization reaction was carried out at 55°C for 24 hours. After aging at 10°C for 24 hours, it was neutralized to pH 7 with a 10% sodium carbonate aqueous solution. The non-volatile component (solid content) of the emulsion after drying at 105°C for 3 hours was 45%, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel. The organosilicon composition has a molecular weight of about 400,000 as measured by the viscosity of the toluene solution and is represented by the structure represented by formula (1).

[0093] 23 g of polyoxyethylene alkyl ether was added thereto, and 1151 g of vinyl acetate was added dropwise over a period of 3 to 5 hours while reacting at 80°C using an initiator, thereby graft copolymerizing vinyl acetate onto the above-mentioned silicone composition to obtain a silicone-vinyl acetate copolymer resin emulsion with a non-volatile component content of 30%.

[0094] [Comparative Example 3]

[0095] A solution of 500 g of octamethylcyclotetrasiloxane, 1.1 g of vinylmethyldimethoxysilane, 5 g of sodium dodecyl sulfate dissolved in 45 g of pure water, and a solution of 5 g of dodecylbenzenesulfonic acid dissolved in 45 g of pure water were placed in a 2 L polyethylene beaker, and after being uniformly emulsified with a homomixer, 400 g of water was slowly added to dilute, and the mixture was stirred at a pressure of 300 kgf / cm 2 After passing through a high-pressure homogenizer twice, a uniform white emulsion was obtained. The emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, and a polymerization reaction was carried out at 55°C for 24 hours. After aging at 10°C for 24 hours, it was neutralized to pH 7 with a 10% sodium carbonate aqueous solution. The non-volatile component (solid content) of the emulsion after drying at 105°C for 3 hours was 45%, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel. The organosilicon composition has a molecular weight of about 400,000 as measured by the viscosity of the toluene solution and is represented by the structure represented by formula (1).

[0096] 21 g of polyoxyethylene alkyl ether was added thereto, and 1051 g of vinyl acetate was added dropwise over 3 to 5 hours while reacting at 80°C using an initiator, thereby graft copolymerizing vinyl acetate onto the above-mentioned silicone composition to obtain a silicone-vinyl acetate copolymer resin emulsion with a non-volatile component content of 30%.

[0097] The emulsions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated by the following methods.

[0098] <Grafting point>

[0099] The grafting point was calculated using the following calculation formula.

[0100] ·Mass of silane coupling agent / molecular weight of silane coupling agent = A

[0101] · Mass of siloxane / calculated molecular weight of organopolysiloxane = B

[0102] The value of "A / B" is defined as the number of branching points.

[0103] For example, in the silicone-vinyl acetate copolymer resin emulsion shown in Production Example 1,

[0104] A = 2.5 / 232 = 0.0108 mol

[0105] ·B=(500+2.5) / 250000=0.00201mol

[0106] "A / B ≒ 5", the number of branching points is "5".

[0107] The number of grafting points can be adjusted by adjusting the amount of the silane coupling agent.

[0108] <Solid content measurement method>

[0109] About 1 g of the sample is accurately weighed in an aluminum foil dish, placed in a desiccator maintained at about 105°C, and heated for 1 hour. Then, the sample is taken out of the desiccator and allowed to cool in a desiccator. The sample is weighed after drying and the evaporation residue is calculated using the following formula.

[0110] [Number 1]

[0111]

[0112] R: Evaporation residue (%)

[0113] W: The mass of the aluminum foil dish containing the sample before drying (g)

[0114] L: The mass of the aluminum foil dish (g)

[0115] T: The mass of the aluminum foil dish containing the dried sample (g)

[0116] Aluminum foil dish size: 65φ×23h(mm)

[0117] <Viscosity measurement method>

[0118] The liquid temperature of the sample was maintained at 23±0.5°C and measured using a BM type viscometer (No. 1 rotor, 6 rpm).

[0119] <Static and dynamic friction coefficients, dynamic friction coefficients measurement>

[0120] The emulsion composition of each example and comparative example was applied to a PET film using a bar coater and dried at 105° C. for 3 minutes to form a coating film having a thickness of about 10 μm.

[0121] HEIDON TYPE-38 (manufactured by Shinto Science Co., Ltd.) was used to bring a 30 g metal indenter into vertical contact with the coating film, and the friction force when moving at 3 cm / min was measured, and the friction coefficient was calculated from the friction force. In addition, the preferred ranges of the static friction coefficient and the dynamic friction coefficient under the above conditions were that the static friction coefficient was 0.3 or less, and the dynamic friction coefficient was 0.20 or less.

[0122] <Water resistance and chemical resistance>

[0123] The emulsion composition of each example and comparative example was cast on a PP tray and dried at 40°C for 24 hours to form a coating film of about 1 mm. The formed coating film was molded into 1 inch × 1 inch to obtain a test piece for evaluation.

[0124] 100 g of each solvent (water, methanol, DMF) was weighed in a glass bottle, and the above test piece whose mass was measured was placed therein, and stirred for 1 hour with a stirrer. After 1 hour, it was filtered with 300 mesh, dried at 40°C for 24 hours, and the mass was measured again. The insoluble rate (%) was calculated from the mass reduction.

[0125] <Adhesion to substrate>

[0126] The emulsion composition of each example and comparative example was applied to a PET film using a bar coater and dried at 105° C. for 3 minutes to form a coating film having a thickness of about 10 μm.

[0127] The coating film was scratched with a knife, and the scratched portion was rubbed back and forth 10 times with a finger, and the adhesion was evaluated visually.

[0128] ○: No peeling from the substrate

[0129] ×: There is peeling from the base material

[0130] <Scratch resistance>

[0131] The emulsion composition of each example and comparative example was applied to a PET film using a bar coater and dried at 105° C. for 3 minutes to form a coating film having a thickness of about 10 μm.

[0132] The scratch resistance of the PET film formed with the coating was measured by applying a load of 98 N, attaching a cotton cloth to a metal contact object, and using a Gakushin friction tester (manufactured by Yasuda Seiki Co., Ltd.) The test was repeated up to 1,000 times, and the number of times the coating was damaged was visually confirmed.

[0133] <Exudation>

[0134] The emulsion composition of each example and comparative example was cast on a PP tray and dried at 40° C. for 24 hours to form a coating film having a thickness of about 1 mm.

[0135] The state of silicone bleeding out of the film surface over time was visually observed.

[0136] ○: No bleeding was observed.

[0137] △: A small amount of bleeding was observed.

[0138] ×: Remarkable bleeding was confirmed.

[0139] [Table 1]

[0140]

[0141] * The brackets in the table for (C) polyvinyl alcohol indicate the mass parts of the (C) component relative to 100 mass parts of (B) vinyl acetate.

[0142] As shown in Table 1, the emulsion compositions containing silicone-acrylic copolymer resins of Comparative Examples 1 to 3 have poor solvent resistance. However, the silicone-vinyl acetate copolymer resin emulsion compositions of Example 1 all have excellent sliding properties and adhesion, and can form coating films with solvent resistance and scratch resistance.

Claims

1. A resin composition comprising (A) a copolymer resin of an organopolysiloxane unit represented by the following general formula (1) and (B) a vinyl acetate unit, and (C) a water-soluble polymer, wherein: The mass ratio of the (A) organopolysiloxane unit to the (B) vinyl acetate unit is (A):(B)=10:90-95:5, and the mass ratio of the (B) vinyl acetate unit to the (C) water-soluble polymer is 100:5-50. [Chemistry 1] In the formula, R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R 2 is an alkyl group having 1 to 6 carbon atoms, or a vinyl group substituted with a mercapto group, an acryloyloxy group, or a methacryloyloxy group; X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group; Y is X or -[O-Si(X)2] d -X represents the same or different groups, at least two of X and Y are hydroxyl groups, Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, a is a positive number from 0 to 1000, b is a positive number from 100 to 10000, c is a positive number from 1 to 10, and d is a positive number from 1 to 1000. 2 . The resin composition according to claim 1 , which is in the form of an emulsion having a viscosity (25° C.) of 1 to 500 mPa·s.

3. The resin composition according to claim 1 or 2, wherein The weight average molecular weight (Mw) of the organopolysiloxane represented by the formula (1) is 10,000 to 1,000,000, as measured by viscosity.

4. The resin composition according to claim 1 or 2, wherein The organopolysiloxane represented by the formula (1) is a polymer of a cyclic organosiloxane, an α,ω-dihydroxysiloxane oligomer, an α,ω-dialkoxysiloxane oligomer or an alkoxysilane and a silane coupling agent represented by the following general formula (2), R 3 (4-e-f) R 4 f Si(OR 5 ) e (2) In the formula, R 3 is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, an acryloyloxy group or a methacryloyloxy group, R 4 is an alkyl group having 1 to 4 carbon atoms, R 5 is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, and e+f is 2 or 3.

5. The resin composition according to claim 1 or 2, which is used as a product selected from the group consisting of a coating agent, a fiber treatment agent, an adhesive, a paint and a cosmetic.

6. A dispersion, characterized in that The invention comprises the resin composition according to claim 1 or 2.

7. A method for producing a resin composition, characterized in that: (A-1) an organopolysiloxane represented by the following general formula (1) and (B-1) vinyl acetate are subjected to emulsion polymerization at a mass ratio of (A-1):(B-1)=10:90 to 95:5, and further, during the emulsion polymerization, 5 to 50 parts by mass of a water-soluble polymer are co-polymerized with respect to 100 parts by mass of the vinyl acetate (B-1) to obtain a resin emulsion. [Chemistry 2] In the formula, R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R 2 is an alkyl group having 1 to 6 carbon atoms, or a vinyl group substituted with a mercapto group, an acryloyloxy group, or a methacryloyloxy group; X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group; Y is X or -[O-Si(X)2] d -X represents the same or different groups, at least two of X and Y are hydroxyl groups, Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, a is a positive number from 0 to 1000, b is a positive number from 100 to 10000, c is a positive number from 1 to 10, and d is a positive number from 1 to 1000.

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