# US 5,349,003 A · Aqueous fluorine-containing polymer dispersion and aqueous dispersion containing fluorine-containing polymer and water-soluble resin and/or water dispersible resin > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,349,003 A - Document ID: US5349003A - Status: Granted - Kind: A - Application number: 08/015,671 - Filed: 1993-02-09 - Granted: 1994-09-20 - Earliest claimed: 1988-09-20 - Assignees: Japan Synthetic Rubber Co., Ltd. - Inventors: Minoru Kato; Teruo Hiraharu; Koichi Nishiwaki; Hiroshi Tadenuma - Web page: https://patentgrep.com/patent/US5349003A ## CPC - C08F 259/08: on to polymers containing fluorine - C08L 51/003: {grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C08L51/04, C08L51/06 take precedence)} - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract An aqueous fluorine-containing polymer dispersion having particle diameters of 0.05-3 .mu.m, which is obtainable by emulsion-polymerizing 5-95 parts by weight of a monomer mixture consisting of at least one monomer selected from the group consisting of alkyl acrylates whose alkyl groups have 1-18 carbon atoms and alkyl methacrylates whose alkyl groups have 1-18 carbon atoms and optionally an ethylenically unsaturated compound copolymerizable with the alkyl acrylates and the alkyl methacrylates, in an aqueous medium in the presence of 100 parts by weight of particles of a vinylidene fluoride polymer; and an aqueous dispersion containing a fluorine-containing polymer which consists essentially of 95-30 parts by weight (in terms of solids content) of said aqueous fluorine-containing polymer dispersion and 5-70 parts by weight (in terms of solids content) of an aqueous dispersion of a water-soluble resin and/or a water-dispersible resin. The aqueous fluorine-containing polymer dispersion and the aqueous dispersion containing a fluorine-containing polymer have excellent heat resistance and weather resistance inherent in fluororesins and are significantly improved in film formability, transparency and adhesion to substrate. Therefore, these aqueous dispersions can be used as a coating composition for various applications, a fiber-treating compound, a paper-processing compound or a floor-coating compound. ## Claims ### Claim 1 An aqueous fluorine-containing polymer dispersion having average particle diameters of 0.05-3 .mu.m, which is obtained by emulsion-polymerizing 5-95 parts by weight of a monomer mixture of at least one monomer selected from the group consisting of alkyl acrylates whose alkyl groups have 1-8 carbon atoms and alkyl methacrylates whose alkyl groups have 1-8 carbon atoms in an aqueous medium in the presence of 100 parts by weight of particles of a vinylidene fluoride polymer, said monomer mixture being absorbed into the vinylidene fluoride polymer particles and the proportion of the alkyl acrylate in the monomer mixture being less than 80% by weight, wherein the vinylidene fluoride polymer is obtained by emulsion polymerization and is a vinylidene fluoride/tetrafluoroethylene copolymer or a vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer. ### Claim 2 (depends on 1) The aqueous fluorine-containing polymer dispersion according to claim 1, wherein the particle diameters of the vinylidene fluoride polymer are in the range of 0.04-2.9 .mu.m. ### Claim 3 (depends on 1) The aqueous fluorine-containing polymer dispersion according to claim 1, wherein the alkyl acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate, and the alkyl methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, amyl methacrylate, isoamyl methacrylate, hexyl methacrylate and lauryl methacrylate. ### Claim 4 (depends on 1) The aqueous fluorine-containing polymer dispersion according to claim 1, wherein the alkyl groups of the alkyl acrylates and the alkyl methacrylates have 1-5 carbon atoms. ### Claim 5 (depends on 1) The aqueous fluorine-containing polymer dispersion according to claim 1, wherein the ethylenically unsaturated compound is selected from the group consisting of a functional group-containing alkenyl compound and a functional group-free alkenyl compound. ### Claim 6 (depends on 5) The aqueous fluorine-containing polymer dispersion according to claim 5, wherein the functional group-containing alkenyl compound is selected from the group consisting of an .alpha.,.beta.-unsaturated carboxylic acid, a vinyl ester of a saturated carboxylic acid, an amide compound, an acrylic acid ester, a methacrylic acid ester and an alkenyl glycidyl ether. ### Claim 7 (depends on 6) The aqueous fluorine-containing polymer dispersion according to claim 6, wherein the .alpha.,.beta.-unsaturated carboxylic acid includes acrylic acid, methacrylic acid, fumaric acid, crotonic acid and itaconic acid; the vinyl ester of a saturated carboxylic acid includes vinyl acetate; the amide compound includes acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, an N-alkylacrylamide, an N-alkylmethacrylamide, an N,N-dialkylacrylamide and an N,N-dialkylmethacrylamide; the acrylic acid ester includes 2-hydroxyethyl acrylate, an N-dialkylaminoethyl acrylate, glycidyl acrylate and a fluoroalkyl acrylate; the methacrylic acid ester includes a dialkylaminoethyl methacrylate, a fluoroalkyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate and ethylene glycol dimethacrylate; and the alkenyl glycidyl ether includes allyl glycidyl ether. ### Claim 8 (depends on 5) The aqueous fluorine-containing polymer dispersion according to claim 5, wherein the functional group-containing alkenyl compound is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, N-methylolacrylamide, N-methylolmethacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and allyl glycidyl ether. ### Claim 9 (depends on 5) The aqueous fluorine-containing polymer dispersion according to claim 5, wherein the functional group-free alkenyl compound is selected from the group consisting of a conjugated diene, an aromatic alkenyl compound, a divinyl hydrocarbon compound and an alkenyl cyanide. ### Claim 10 (depends on 9) The aqueous fluorine-containing polymer dispersion according to claim 9, wherein the conjugated diene includes 1,3-butadiene and isoprene; the aromatic alkenyl compound includes styrene, .alpha.-methylstyrene and a styrene halide; the divinyl hydrocarbon compound includes divinylbenzene; and the alkenyl cyanide includes acrylonitrile and methacrylonitrile. ### Claim 11 (depends on 5) The aqueous fluorine-containing polymer dispersion according to claim 5, wherein the functional group-containing alkenyl compound is used in a proportion of less than 50% by weight based on the weight of the monomer mixture and the functional group-free alkenyl compound is used in a proportion of less than 30% by weight based on the weight of the monomer mixture. ### Claim 12 (depends on 1) The aqueous fluorine-containing polymer dispersion according to claim 1, wherein the proportion of the alkyl acrylate in the monomer mixture is less than 60% by weight. ### Claim 13 (depends on 1) The aqueous fluorine-containing polymer dispersion according to claim 1, wherein the amount of the monomer mixture is 20-90 parts by weight. ### Claim 14 (depends on 1) The aqueous fluorine-containing polymer dispersion according to claim 1, wherein the fluorine-containing polymer has a number-average particle diameter of 0.1-2 .mu.m. ### Claim 15 A process for producing an aqueous fluorine-containing polymer dispersion, which comprises emulsion-polymerizing 5-95 parts by weight of a monomer mixture consisting of at least one monomer selected from the group consisting of alkyl acrylates whose alkyl groups have 1-18 carbon atoms and alkyl methacrylates whose alkyl groups have 1-18 carbon atoms and optionally an ethylenically unsaturated compound copolymerizable with the alkyl acrylates and the alkyl methacrylates, in an aqueous medium in the presence of 100 parts by weight of particles of a vinylidene fluoride polymer, wherein the vinylidene fluoride polymer is obtained by emulsion polymerization and is a vinylidene fluoride/tetrafluoroethylene copolymer or a vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer. ### Claim 16 (depends on 15) The process according to claim 15, wherein the emulsion-polymerization is effected at a temperature of 30.degree.-100.degree. C. for 1-30 hours in the presence of an emulsifier and a polymerization initiator. ### Claim 17 (depends on 16) The process according to claim 16, wherein the emulsifier is an anionic emulsifier, a nonionic emulsifier, a combination of an anionic emulsifier and a nonionic emulsifier, a cationic emulsifier or an amphoteric emulsifier. ### Claim 18 (depends on 17) The process according to claim 17, wherein the emulsifier is an anionic emulsifier. ### Claim 19 (depends on 1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70) An aqueous dispersion containing a fluorine-containing polymer, which dispersion consists essentially of 95-30 parts by weight (in terms of solids content) of the aqueous fluorine-containing polymer dispersion of claim 1 and 5-70 parts by weight (in terms of solids content) of an aqueous dispersion of at least one resin selected from the group consisting of a water-soluble resin and a water-dispersible resin. ### Claim 20 (depends on 19) The aqueous dispersion according to claim 19, wherein both the water-soluble resin and the water-dispersible resin are contained at a weight proportion of 20/80-80/20. ### Claim 21 (depends on 19) The aqueous dispersion according to claim 19, wherein the water-soluble resin is an N-methylolmelamine resin, an alkylated N-methylolmelamine resin, a water-soluble acrylic resin, a urethane resin, an epoxy resin, a polyester resin, a water-soluble nylon resin, an alkyd resin, a urea resin, a maleinized polybutadiene or a maleinized oil. ### Claim 22 (depends on 21) The aqueous dispersion according to claim 21, wherein the water-dispersible resin is in the emulsion form and the emulsion is a (meth)acrylic emulsion, a vinyl acetate emulsion, an ethylene-vinyl acetate emulsion or a urethane emulsion. ### Claim 23 An aqueous fluorine-containing polymer dispersion having average particle diameters of 0.05-3 .mu.m, which is obtained by emulsion-polymerizing 5-95 parts by weight of a monomer mixture of at least one monomer selected from the group consisting of alkyl acrylates whose alkyl groups have 1-8 carbon atoms and alkyl methacrylates whose alkyl groups have 1-8 carbon atoms, and an ethylenically unsaturated compound copolymerizable with the alkyl acrylates and the alkyl methacrylates in an aqueous medium in the presence of 100 parts by weight of particles of a vinylidene fluoride polymer, said monomer mixture being absorbed into the vinylidene fluoride polymer particles and the proportion of the alkyl acrylate in the monomer mixture being less than 80% by weight, wherein the vinylidene fluoride polymer is obtained by emulsion polymerization and is a vinylidene fluoride/tetrafluoroethylene copolymer or a vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer. ### Claim 24 (depends on 1) The aqueous fluorine-containing polymer dispersion according to claim 1, wherein the vinylidene fluoride polymer is obtained by emulsion polymerization and is a vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer. ### Claim 25 (depends on 23) The aqueous fluorine-containing polymer dispersion according to claim 23, wherein the vinylidene fluoride polymer is obtained by emulsion polymerization and is a vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer.