# US 5,691,069 A · Acrylic emulsion coatings for rubber articles > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,691,069 A - Document ID: US5691069A - Status: Granted - Kind: A - Application number: 08/388,030 - Filed: 1995-02-14 - Granted: 1997-11-25 - Earliest claimed: 1995-02-14 - Assignees: Avery Dennison Corporation - Inventors: Ivan Lee - Web page: https://patentgrep.com/patent/US5691069A ## CPC - B29C 41/14: Dipping a core {(B29C41/10 takes precedence)} - C08J 7/0427: {with only one layer of a composition containing a polymer binder (with more layers C08J7/042)} - C08J 7/043: Improving the adhesiveness of the coatings per se, e.g. forming primers (adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50) - C08J 7/046: Forming abrasion-resistant coatings; Forming surface-hardening coatings - C09D 143/04: Homopolymers or copolymers of monomers containing silicon - C08J 2321/00: Characterised by the use of unspecified rubbers - C08J 2433/00: Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers - C08L 43/04: Homopolymers or copolymers of monomers containing silicon - C08L 2205/02: containing two or more polymers of the same C08L -group - Y10T 428/31663: As siloxane, silicone or silane - Y10T 428/31855: Of addition polymer from unsaturated monomers - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract There are provided powder-free polymer coated rubber articles in which at least one surface of the rubber article is coated with a non-tacky acrylic based emulsion copolymer formed by polymerization of at least one low surface energy monomer, at least one alkyl acrylate and at least one hard monomer. The copolymers are preferably formed by sequential polymerization. The polymer coatings can be stretched with the rubber without flaking. ## Claims ### Claim 1 A rubber article having a coating deposited on a surface thereof from an aqueous suspension of an emulsion copolymer of from about 0.7 to about 20% by weight of at least one copolymerizable low surface energy monomer selected from the group consisting of reactive silicones, reactive fluorocarbons and reactive fatty acids esters, said low surface energy monomer having a functionality selected from vinyl, acrylic and methacrylic, from about 30 to about 85% by weight of at least one alkyl acrylate containing from 1 to about 10 carbon atoms in the alkyl group, the balance of the monomers comprising hard monomers, said hard monomers, when homopolymerized having a glass transition temperature greater than about 25.degree. C. and present in an amount sufficient to provide non-tacky acrylic based emulsion. ### Claim 2 (depends on 1) A rubber article as claimed in claim 1 in which the low surface energy monomer is present in an amount of from about 1 to 15% by weight of the acrylic based copolymer. ### Claim 3 (depends on 1) A rubber article as claimed in claim 1 in which the alkyl acrylate is selected from the group consisting of methyl acrylate, butyl acrylate, and mixtures thereof. ### Claim 4 (depends on 2) A rubber article as claimed in claim 2 in which the alkyl acrylate is selected from the group consisting of methyl acrylate, butyl acrylate, and mixtures thereof. ### Claim 5 (depends on 1) A rubber article as claimed in claim 1 in which the hard monomer comprise monomers selected from the group consisting of styrenic monomers, alkyl methacrylates, unsaturated carboxylic acids containing from 3 to about 4 carbon atoms, amides and mixtures thereof. ### Claim 6 (depends on 2) A rubber article as claimed in claim 2 in which the hard monomer comprise monomers selected from the group consisting of styrenic monomers, alkyl methacrylates, unsaturated carboxylic acids containing from 3 to about 4 carbon atoms, amides and mixtures thereof. ### Claim 7 (depends on 3) A rubber article as claimed in claim 3 in which the hard monomer comprise monomers selected from the group consisting of styrenic monomers, alkyl methacrylates, unsaturated carboxylic acids containing from 3 to about 4 carbon atoms, amides and mixtures thereof. ### Claim 8 (depends on 1) A rubber article as claimed in claim 1 to which an acrylic based emulsion copolymer is comprised from about 0.7 to about 20% by weight of at least one copolymerizable low surface energy monomer, from about 40 to about 80% by weight of an alkyl acrylate selected from the group consisting of methyl acrylate, butyl acrylate, and mixtures thereof, the balance of the monomers selected from the group consisting of styrene, methacrylic acid, acrylic acid, methyl methacrylate, isobutoxymethacrylamide, isobutylmethacrylate, and mixtures thereof. ### Claim 9 (depends on 1) A rubber article as claimed in claim 1 in which the coatings comprises a first acrylic based emulsion copolymer and a second acrylic based emulsion copolymer, said first and second copolymers formed by emulsion polymerization of monomers comprised of from about 0.7 to about 20% by weight of at least one copolymerizable low surface energy monomer, from about 30 to about 85% by weight of at least one alkyl acrylate containing from 1 to about 10 carbon atoms in the alkyl group, the balance of the monomers comprising hard monomers, which when homopolymerized, have a glass transition temperature greater than 25.degree. C. and provided in an amount sufficient to form a mixture of first and second acrylic based emulsion copolymers which are non-tacky, said first acrylic based emulsion copolymer having a glass transition temperature from about -50.degree. C. to about 25.degree. C., said second acrylic based emulsion copolymer having a glass transition temperature from about 25.degree. C. to about 100.degree. C. ### Claim 10 (depends on 9) A rubber article as claimed in claim 9 in which the weight ratio of the first acrylic based emulsion copolymer to the second acrylic based emulsion copolymer is in the range of about 1:1 to about 1:3. ### Claim 11 (depends on 10) A rubber article as claimed in claim 10 in which the weight ratio of the first acrylic based emulsion copolymer to the second acrylic based emulsion copolymer is about 1 to 1.5. ### Claim 12 (depends on 11) A rubber article as claimed in claim 11 in which the weight ratio of the first acrylic based emulsion copolymer to the second acrylic based copolymer is in a range of about 3:1 to about 1:1. ### Claim 13 (depends on 12) A rubber article as claimed in claim 12 in which the weight ratio of first acrylic based emulsion copolymer to the second acrylic based emulsion copolymer is about 1.2 to 1. ### Claim 14 (depends on 9) A rubber article as claimed in claim 9 which comprises a first acrylic based emulsion copolymer which is the reaction product of a first monomer system comprising styrene, butyl acrylate, methyl acrylate, methacrylic acid, acrylic acid and at least one copolymerizable low surface energy monomer, said first emulsion copolymer having glass transition temperatures less than about 0.degree. C. and a second acrylic based emulsion copolymer which is the reaction product of a second monomer system sequentially polymerized in the presence of the first emulsion copolymer, said second monomer system comprised of styrene, butyl acrylate, methylacrylate, methacrylic acid, acrylic acid and at least one copolymerizable low surface energy monomer, said second copolymer having a glass transition temperature of from about 0.degree. C. to about 100.degree. C., said sequentially polymerized mixture of first and second acrylic based emulsion copolymers being non-tacky and formed in the presence of at least two anionic surfactants. ### Claim 15 (depends on 1) A rubber article as claimed in claim 1 in the shape of a glove. ### Claim 16 (depends on 14) A rubber article as claimed in claim 14 in the shape of a glove.