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KR-102960770-B1 - VINYL ACETATE-SILICONE COPOLYMER RESIN AND METHOD FOR PRODUCING SAME

KR102960770B1KR 102960770 B1KR102960770 B1KR 102960770B1KR-102960770-B1

Abstract

The present invention provides a vinyl acetate-silicone copolymer resin, a method for manufacturing the same, and a vinyl acetate-silicone copolymer resin composition, characterized in that (A) an organopolysiloxane represented by a specified general formula is graft polymerized with (B) vinyl acetate, and the mass ratio of (A) organopolysiloxane and (B) vinyl acetate is (A):(B) = 10:90 to 95:5. The vinyl acetate-silicone copolymer resin of the present invention has sliding properties, adhesion to substrates, and solubility in organic solvents, and is suitablely used as a coating agent for various substrates, an adhesive, a paint for exterior and interior use in structures or building materials, a cosmetic, etc.

Inventors

  • 우치다, 고키
  • 와타나베, 겐타로

Assignees

  • 닛신 가가꾸 고교 가부시끼가이샤

Dates

Publication Date
20260507
Application Date
20220223
Priority Date
20210226

Claims (6)

  1. A vinyl acetate-silicone copolymer resin characterized by being formed by graft polymerizing (B) vinyl acetate into an organopolysiloxane represented by the following general formula (1), wherein the mass ratio of the organopolysiloxane (A) and the vinyl acetate (B) is (A):(B) = 10:90 to 95:5. (In the formula, R1 is an identical or heterogeneous substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R2 is a mercapto group, an acryloxy group, or a methacryloxy group-substituted alkyl group having 1 to 6 carbon atoms, or a vinyl group. X is an identical or heterogeneous 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, and Y is an identical or heterogeneous group represented by X or -[O-Si(X) 2 ] d -X, and 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 1,000, b is a positive number from 100 to 10,000, and c is 1 to 10 of Positive, d is a positive number from 1 to 1,000.)
  2. A vinyl acetate-silicone copolymer resin according to claim 1, which is an emulsion having a viscosity (25°C) of 1 to 500 mPa·s.
  3. A vinyl acetate-silicone copolymer resin according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the organopolysiloxane (A) component, determined by viscosity measurement, is 10,000 to 1,000,000.
  4. A vinyl acetate-silicone copolymer resin according to claim 1 or 2, wherein the organopolysiloxane represented by 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-ef) R 4 f Si(OR 5 ) e (2) (In the formula, R3 is a C1 to C6 alkyl group substituted with a mercapto group, an acryloxy group, or a methacryloxy group, R4 is a C1 to C4 alkyl group, R5 is a C1 to C4 alkyl group, e is 2 or 3, f is 0 or 1, and e+f is 2 or 3.)
  5. A method for manufacturing a vinyl acetate-silicone copolymer resin characterized by obtaining a vinyl acetate-silicone copolymer resin emulsion by emulsion polymerizing (A) an organopolysiloxane represented by the following general formula (1) and (B) vinyl acetate in a mass ratio of (A):(B) = 10:90 to 95:5. (In the formula, R1 is an identical or heterogeneous substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R2 is a mercapto group, an acryloxy group, or a methacryloxy group-substituted alkyl group having 1 to 6 carbon atoms, or a vinyl group. X is an identical or heterogeneous 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, and Y is an identical or heterogeneous group represented by X or -[O-Si(X) 2 ] d -X, and 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 1,000, b is a positive number from 100 to 10,000, and c is 1 to 10 of Positive, d is a positive number from 1 to 1,000.)
  6. A resin composition containing the vinyl acetate-silicone copolymer resin described in claim 1 or 2, characterized in that it is used as a product selected from the group consisting of coating agents, fiber treatment agents, adhesives, paints, and cosmetics.

Description

Vinyl Acetate-Silicone Copolymer Resin and Method for Producing Same The present invention relates to a resin copolymerized with vinyl acetate in an organopolysiloxane and a method for manufacturing the same. More specifically, it relates to a vinyl acetate-silicone copolymer resin having sliding properties, adhesion to a substrate, and solubility in organic solvents, and a method for manufacturing the same. Silicone resins have long been known as resins capable of imparting sliding properties to substrates. However, when silicone resins are used alone, there have been problems such as poor adhesion to the substrate. Therefore, methods are used to copolymerize other monomers, such as acrylic or urethane types, with silicone-based resins. For example, copolymers such as acrylic silicone copolymers or urethane silicone copolymers can impart advantages such as weather resistance, heat resistance, cold resistance, water repellency, gas permeability, and sliding properties to conventional acrylic or urethane emulsions. For example, Patent Document 1 (Japanese Patent Publication No. 2020-90563) discloses a silicone acrylic graft copolymer resin that imparts sliding properties and a method for manufacturing the same. Meanwhile, vinyl acetate resin is used in emulsion-based adhesives, photosensitive materials for screen printing, laundry starch, chewing gum bases, emulsifiers, and as a base for cosmetics, and is known as a resin with good adhesion properties. As a resin obtained by copolymerizing other monomers with vinyl acetate resin, for example, ethylene vinyl acetate copolymer obtained by copolymerizing ethylene. This copolymer is a synthetic resin having adhesiveness and flexibility due to vinyl acetate units, and is used as a coating material for paper containers such as food packaging paper and paper cups, as an adhesive for cloth and paper labels, as an emulsion adhesive, as a chewing gum base, as an artificial turf, as a sole for sandals, as a bathroom mat, as a bathroom cleaning boot, as a beat board, as a jump rope, etc. Silicone resin and vinyl acetate resin are resins with opposite properties, and while it is known that they can be copolymerized by reacting each with a separate monomer, no attempt has been made to copolymerize these two resins until now. Furthermore, it was not thought that a resin utilizing the respective properties could be obtained even if silicone and vinyl acetate were copolymerized. One could think of a method to obtain a coating agent by mixing a silicone resin emulsion and a vinyl acetate resin emulsion, but in the mixture, the silicone component bleed out, so the desired performance was not obtained, and there was room for improvement. The present invention is a vinyl acetate-silicone copolymer resin composed of (A) organopolysiloxane and (B) vinyl acetate polymer units. Here, (A) organopolysiloxane is represented by the following general formula (1). (In the formula, R1 is an identical or heterogeneous substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R2 is a mercapto group, an acryloxy group, or a methacryloxy group-substituted alkyl group having 1 to 6 carbon atoms, or a vinyl group. X is an identical or heterogeneous 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, and Y is an identical or heterogeneous group represented by X or -[O-Si(X) 2 ] d -X, and 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 1,000, b is a positive number from 100 to 10,000, and c is 1 to 10 of Positive, d is a positive number from 1 to 1,000.) Here, R1 is an identical or heterogeneous substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically, an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, alkyl group such as a cyclopentyl group, cyclohexyl group, cycloheptyl group, alkenyl group such as a vinyl group, allyl group, aryl group such as a phenyl group, tolyl group, naphthyl group, alkenylaryl group such as a vinylphenyl group, aralkyl group such as a benzyl group, phenylethyl group, phenylpropyl group, alkenylaralkyl group such as a vinylbenzyl group, vinylphenylpropyl group, etc., wherein some or all of the hydrogen atoms of these groups are halogen atoms such as fluorine, bromine, or chlorine, an acryloxy group, a methacrylatex group, etc. Examples include those substituted with a carboxyl group, an alkoxy group, an alkenyloxy group, an amino group, an alkyl or alkoxy or (meth)acryloxy substituted amino group, etc. As for R1 , it is preferably a methyl group. R2 is a carbon-1 to 6 alkyl group substit