# US 4,393,094 A · Stabilization of electron beam curable compositions for improved exterior durability > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,393,094 A - Document ID: US4393094A - Status: Granted - Kind: A - Application number: 06/369,946 - Filed: 1982-04-19 - Granted: 1983-07-12 - Earliest claimed: 1982-04-19 - Assignees: Ford Motor Company - Inventors: David L. Garrett, Jr.; Joseph C. Cassatta - Web page: https://patentgrep.com/patent/US4393094A ## CPC - C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16} - 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) ## Abstract A low dosage electron beam radiation polymerizable protective and decorative coating composition or paint with improved weatherability, coated articles bearing such a protective coating and processes for preparing such articles. The radiation polymerizable coating composition comprises an organic resin/monomer mixture of: (A) between about 97 and about 3 weight percent alpha-beta olefinically unsaturated organic resin containing between about 0.5 and about 5 vinyl unsaturation units per 1000 molecular weight of said resin; and (B) between about 3 and about 97 weight percent vinyl monomers polymerizable with said resin upon exposure to radiation, characterized in that said vinyl monomers include N-vinyl-2-pyrrolidone in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B); and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR1## where R.sub.1 or R.sub.2 =H or an alkyl group of C.sub.1 -C.sub.25, preferably C.sub.3 -C.sub.9 ; and (ii) hindered amine selected from the group consisting of amines having the formula: ##STR2## wherein R=H methyl, preferably H. The flexible coating exhibits excellent physical qualities including improved weatherability and good adhesion to a variety of substrates being particularly suitable for use on polyvinyl chloride fabric, wherein it is discoloration resistant after heat aging. ## Claims ### Claim 1 A coating composition polymerizable by low dosage ionizing radiation, which comprises an organic resin/monomer mixture of: (A) between about 97 and about 3 weight percent alpha-beta olefinically unsaturated organic resin containing between about 0.5 and about 5 vinyl unsaturation units per 1000 units molecular weight of said resin; and (B) between about 3 and about 97 weight percent vinyl monomers polymerizable with said resin upon exposure to radiation, said vinyl monomers including N-vinyl-2-pyrrolidone in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B); and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR11## wherein R.sub.1 or R.sub.2 =H or an alkyl group of C.sub.1 -C.sub.25 ; and (ii) hindered amine selected from the group consisting of amine having the formula: ##STR12## wherein R=H or methyl. ### Claim 2 (depends on 1) A coating composition according to claim 1, wherein said R.sub.1 or R.sub.2 of said benzotriazole is an alkyl group of C.sub.3 -C.sub.9. ### Claim 3 (depends on 1, 2) A coating composition according to claims 1 or 2, wherein said R of said hindered amine is hydrogen. ### Claim 4 (depends on 1) A coating composition according to claim 1, wherein said benzotriazole is a mixture of benzotriazoles. ### Claim 5 (depends on 1, 4) A coating composition according to claims 1 or 4, wherein said hindered amine is a mixture of hindered amines. ### Claim 6 (depends on 1) A coating composition according to claim 1, wherein said benzotriazole is present in said composition in a weight amount (i) in excess of said hindered amine, or (ii) about equal to said hindered amine. ### Claim 7 (depends on 1) A coating composition according to claim 1, wherein said composition further comprises between 5 and about 12 parts by weight per 100 parts of the total of said (A) and (B) of micronized polyethylene. ### Claim 8 (depends on 1) A coating composition according to claim 1, wherein said resin contains between about 0.5 and about 3 vinyl unsaturation units per 1000 units molecular weight of said resin. ### Claim 9 (depends on 1) A coating composition according to claim 1, wherein said resin comprises a urethane acrylic oligomer having the formula: ##STR13## wherein R' is hydrogen or methyl and Y is a divalent urethane residue. ### Claim 10 (depends on 1) A coating composition according to claim 1, wherein said N-vinyl-2-pyrrolidone is included in an amount of between about 3 and about 10 weight percent based on the total weight of (A) and (B). ### Claim 11 (depends on 9) A coating composition according to claim 9, wherein said vinyl monomers other than said N-vinyl-2-pyrrolidone consist essentially of acrylic ester monomers. ### Claim 12 (depends on 9, 11) A coating composition according to claim 9 or 11, wherein said R' of said oligomer is hydrogen. ### Claim 13 (depends on 9) A coating composition according to claim 9, wherein said oligomer has a molecular weight between about 400 and about 10,000. ### Claim 14 (depends on 11) A coating composition according to claim 11, wherein said acrylic ester monomers comprise at least 70 weight percent of monovinyl acrylic ester monomers. ### Claim 15 (depends on 14) A coating composition according to claim 14, wherein said acrylic ester monomers comprise greater than 80 weight percent of monovinyl acrylic ester monomers. ### Claim 16 (depends on 14) A coating composition according to claim 14, wherein said monovinyl acrylic ester monomers are selected from the group consisting essentially of ethoxyethyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, ethoxyethoxyethyl acrylate, glycidyl acrylate and mixtures thereof. ### Claim 17 (depends on 14, 16) A coating composition according to claim 14 or 16, wherein said acrylic ester monomer, other than said monovinyl acrylic ester monomer, is selected from the group consisting of 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, trimethylol propane triacrylate and mixtures thereof. ### Claim 18 A 100% solids coating composition polymerizable by low dosage ionizing radiation adapted to coat flexible substrates, which exclusive of pigments, initiators and other non-reactive components, consists essentially of an oligomer/monomer mixture of: (A) between about 90 and about 10 weight percent oligomer having the formula: ##STR14## wherein R' is hydrogen or methyl; and Y is a divalent urethane residue; and said oligomer has between about 0.5 and about 5 vinyl unsaturation units per 1000 units molecular weight of said oligomer; and (B) between about 10 and about 90 weight percent vinyl monomers polymerizable with said oligomer upon exposure to radiation, said vinyl monomers consisting essentially of (i) acrylic ester monomers and (ii) N-vinyl-2-pyrrolidone, wherein said N-vinyl-2-pyrrolidone is included in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B), and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR15## where R.sub.1 or R.sub.2 =H or an alkyl group of C.sub.1 -C.sub.25 ; and (ii) hindered amine selected from the group consisting of amines having the formula: ##STR16## wherein R=H or methyl. ### Claim 19 (depends on 18) A 100% solids coating composition according to claim 18, wherein said R.sub.1 or R.sub.2 of said benzotriazole is an alkyl group of C.sub.3 -C.sub.9. ### Claim 20 (depends on 18, 19) A 100% solids coating composition according to claims 18 or 19, wherein said R of said hindered amine is hydrogen. ### Claim 21 (depends on 18) A 100% solids coating composition according to claim 18, wherein said benzotriazole is a mixture of benzotriazoles. ### Claim 22 (depends on 18, 21) A 100% solids coating composition according to claims 18 or 21, wherein said hindered amine is a mixture of hindered amines. ### Claim 23 (depends on 18) A 100% solids coating composition according to claim 18, wherein said benzotriazole is present in said composition in a weight amount (i) in excess of said hindered amine, or (ii) about equal to said hindered amine. ### Claim 24 (depends on 18) A 100% solids coating composition according to claim 18, wherein said composition further comprises between 5 and about 12 parts by weight per 100 parts of the total of said (A) and (B) of micronized polyethylene. ### Claim 25 (depends on 24) A 100% solids coating composition according to claim 24, wherein said N-vinyl-2-pyrrolidone is included in an amount of between about 3 and about 10 weight percent based on the total weight of (A) and (B). ### Claim 26 (depends on 24) A 100% solids coating composition according to claim 24, wherein said R' of said oligomer is hydrogen. ### Claim 27 (depends on 16, 24) A 100% solids coating composition according to claim 24 or 16, wherein said oligomer has a molecular weight of between about 400 and about 5000. ### Claim 28 (depends on 24) A 100% solids coating composition according to claim 24, wherein said acrylic ester monomers comprise at least 70 weight percent monovinyl acrylic ester monomers. ### Claim 29 (depends on 28) A 100% solids coating composition according to claim 28, wherein said acrylic ester monomers comprise greater than 80 weight percent monovinyl acrylic ester monomers. ### Claim 30 (depends on 28) A 100% solids coating composition according to claim 28, wherein said monovinyl acrylic ester monomers are selected from the group consisting essentially of ethoxyethyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, ethoxyethoxyethyl acrylate, glycidyl acrylate and mixtures thereof. ### Claim 31 (depends on 24, 30) A 100% solids coating composition according to claim 24 or 30, wherein said acrylic ester monomers, other than said monovinyl acrylic ester monomers, are selected from the group consisting of 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate and mixtures thereof. ### Claim 32 A method for coating a substrate, the coating composition polymerizable by low dosage ionizing radiation, which comprises: (A) applying a first coating composition comprising up to about 60 weight percent pigment to the surface of a prepared substrate; (B) curing said first coating composition by exposure to an electron beam until an adherent dry coating is formed; (C) applying a second coating composition comprising 0-10 weight percent pigment to the coated surface of said substrate; and (D) curing said second coating composition by exposure to an electron beam until an adherent dry coating is formed; wherein said first coating composition and said second coating composition comprises an organic resin/monomer mixture of: (A) between about 97 and about 3 weight percent alpha-beta olefinically unsaturated organic resin containing between about 0.5 and about 5 vinyl unsaturation units per 1000 units molecular weight of said resin; and (B) between about 3 and about 97 weight percent vinyl monomers polymerizable with said resin upon exposure to radiation, said vinyl monomers comprising N-vinyl-2-pyrrolidone which is included in said composition in an amount of between about 3 and about 20 weight percent based on the total weight of (A) and (B); and (C) about 0.5 to about 5.0 parts each per 100 parts of the total of said organic resin and said monomer of: (i) benzotriazole selected from the group consisting of compounds having the formula: ##STR17## where R.sub.1 or R.sub.2 =H or an alkyl group of C.sub.1 -C.sub.25 ; and (ii) hindered amine selected from the group consisting of amines having the formula: ##STR18## wherein R=H or methyl. ### Claim 33 (depends on 32) A method for coating a substrate according to claim 32, wherein said R.sub.1 or R.sub.2 of said benzotriazole is an alkyl group of C.sub.3 -C.sub.9. ### Claim 34 (depends on 32, 33) A method for coating a substrate according to claim 32 or 33, wherein said R of said hindered amine is hydrogen. ### Claim 35 (depends on 32) A method for coating a substrate according to claim 32, wherein said benzotriazole is a mixture of benzotriazoles. ### Claim 36 (depends on 32, 35) A method for coating a substrate according to claim 32 or 35, wherein said hindered amine is a mixture of hindered amines. ### Claim 37 (depends on 32) A method for coating a substrate according to claim 32, wherein said benzotriazole is present in said composition in a weight amount (i) in excess of said hindered amine, or (ii) about equal to said hindered amine. ### Claim 38 (depends on 32) A coating composition according to claim 32, wherein said composition further comprises between 5 and about 12 parts by weight per 100 parts of the total of said (A) and (B) of micronized polyethylene. ### Claim 39 (depends on 32) A method for coating a substrate according to claim 32, wherein said resin comprises a urethane acrylic oligomer having the formula: ##STR19## wherein R' is hydrogen or methyl and Y is a divalent urethane residue. ### Claim 40 (depends on 32, 39) A method for coating a substrate according to claim 32 or 39, wherein said N-vinyl-2-pyrrolidone is included in an amount of between about 3 and about 10 weight percent based on the total weight of (A) and (B). ### Claim 41 (depends on 39) A method for coating a substrate according to claim 39, wherein said R' of said oligomer is hydrogen. ### Claim 42 (depends on 39) A method for coating a substrate according to claim 39, wherein said oligomer has a molecular weight of between about 400 and about 10,000. ### Claim 43 (depends on 39) A method for coating a substrate according to claim 39, wherein said vinyl monomers other than said N-vinyl-2-pyrrolidone consist essentially of acrylic ester monomers. ### Claim 44 (depends on 43) A method for coating a substrate according to claim 43, wherein said acrylic ester monomers comprise at least 70 weight percent of a monovinyl acrylic ester. ### Claim 45 (depends on 44) A method for coating a substrate according to claim 44, wherein said monovinyl acrylic ester monomers are selected from the group consisting of ethoxyethyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, ethoxyethoxyethyl acrylate, glycidyl acrylate, ethoxyethyl methacrylate, glycidyl methacrylate and mixtures thereof. ### Claim 46 (depends on 45) A method for coating a substrate according to claim 45, wherein said acrylic ester monomers other than said monovinyl acrylic ester monomers, are selected from the group consisting of 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate and mixtures thereof. ### Claim 47 (depends on 32) A method for coating a substrate according to claim 32, wherein said substrate is comprised of polyvinyl chloride. ### Claim 48 (depends on 45) A method for coating a substrate according to claim 45, wherein said substrate is flexible polyvinyl chloride fabric. ### Claim 49 (depends on 47) A method for coating a substrate according to claim 47, wherein said first coating composition and said second coating composition are 100% solids.