# US 4,394,486 A · High solids coatings with enhanced flexibility and impact strength > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,394,486 A - Document ID: US4394486A - Status: Granted - Kind: A - Application number: 06/334,684 - Filed: 1981-12-28 - Granted: 1983-07-19 - Earliest claimed: 1981-12-28 - Assignees: Ford Motor Company - Inventors: Mohinder S. Chattha; Ares N. Theodore - Web page: https://patentgrep.com/patent/US4394486A ## CPC - C09D 133/068: {containing glycidyl groups} - C08L 61/20: Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen (with aminophenols C08L61/04) - Y10T 428/31681: Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.] - Y10T 428/31688: Next to aldehyde or ketone condensation product - 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 A thermosetting coating composition with enhanced flexibility and impact strength and excellent weatherability adapted for use as an automotive topcoat which upon curing forms a hard, glossy, durable coating. The coating composition comprises: (A) a modified hydroxy acrylic copolymer which is the stepwise reaction product of: (i) a copolymer bearing pendant hydroxyl groups and having a number average molecular (M.sub.n) of between about 1000-5000, (ii) a dicarboxylic acid anhydride comprising at least about 50 percent by weight of an alkyl hexahydrophthalic anhydride, and (iii) a monoepoxide functional monomer comprising at least about 90 percent by weight of a C.sub.2 -C.sub.10 monoepoxide functional monomer; (B) an amine-aldehyde crosslinking agent; (C) optionally a hydroxy functional additive; and (D) solvent. The anhydride is reacted in an amount sufficient to esterify at least about 30 percent of the pendant hydroxyl groups of copolymer (i) thereby generating carboxyl functionality, substantially all of which is thereafter reacted with the monoepoxide functional monomer. The amine-aldehyde crosslinking agent is included in the composition in an amount sufficient to provide at least about 0.60 equivalent of nitrogen crosslinking functionality per equivalent of hydroxy functionality included in the composition either as a hydroxyl group of the modified hydroxy acrylic copolymer or as a hydroxyl group of the optional hydroxy-functional additive. ## Claims ### Claim 1 A thermosetting coating composition exhibiting improved flexibility and impact strength and having excellent weatherability and comprising: (A) a modified hydroxy acrylic copolymer which is the stepwise reaction product of: (i) a copolymer bearing pendant hydroxyl groups and having a number average molecular weight (M.sub.n) of between about 1000-5000, said copolymer being prepared from (a) between about 5 and about 40 weight percent of monoethylenically unsaturated hydroxy alkyl ester of the formula CH.sub.2 .dbd.CR.sub.1 --COOR.sub.2 wherein R.sub.1 is H or an alkyl group and R.sub.2 is a hydroxy alkyl group and (b) between about 95-60 weight percent of other monoethylenically unsaturated monomers; (ii) dicarboxylic acid anhydride comprising at least about 50 percent by weight of an alkyl hexahydrophthalic anhydride, wherein (i) and (ii) are reacted in an amount sufficient to esterify between about 30 and about 100 percent of said pendant hydroxyl groups of said copolymer thereby generating pendant carboxyl groups; and (iii) a monoepoxide functional monomer comprising at least about 90 percent by weight C.sub.2 -C.sub.10 monoepoxide functional monomers, wherein said monomer is reacted with said pendant carboxyl groups of the polymer reaction product of (i) and (ii) in an amount so as to provide at least about 1.0 equivalent of epoxide groups per equivalent of said pendant carboxyl groups to generate pendant hydroxyl groups; (B) an amine-aldehyde crosslinking agent; (C) 0-50 weight percent based on the total weight of (A), (B) (C) and (D) of a hydroxy functional additive having a number average molecular weight (M.sub.n) of between about 150 and about 6000; and (D) solvent said amine-aldehyde crosslinking agent being included in said composition in an amount sufficient to provide at least about 0.60 equivalents of nitrogen crosslinking functionality for each equivalent of hydroxyl functionality included in said composition either as a hydroxyl group on said modified hydroxy acrylic copolymer or as a hydroxyl group on said hydroxy functional additive. ### Claim 2 (depends on 1) A coating composition according to claim 1, wherein said monoethylenically unsaturated hydroxy alkyl ester comprises C.sub.5 -C.sub.7 hydroxy alkyl acrylates, C.sub.6 -C.sub.8 hydroxy alkyl methacrylates, or mixtures thereof. ### Claim 3 (depends on 2) A coating composition according to claim 2, wherein said other monoethylenically unsaturated monomers comprise acrylates, other vinyl monomer, or mixtures of said acrylates and other vinyl monomers. ### Claim 4 (depends on 1) A coating composition according to claim 1, wherein said alkyl group of said alkyl hexahydrophthalic anhydride comprises a lower alkyl group having up to about seven carbons. ### Claim 5 (depends on 1) A coating composition according to claim 1, wherein said dicarboxylic acid anhydride comprises at least 80 percent by weight of an alkyl hexahydrophthalic anhydride. ### Claim 6 (depends on 4, 5) A coating composition according to claims 4 or 5, wherein said alkyl hexahydrophthalic anhydride is methyl hexahydrophthalic anhydride. ### Claim 7 (depends on 1) A coating composition according to claim 1, wherein up to 50 percent by weight of said dicarboxylic acid anhydride employed in the preparation of said copolymer comprises an anhydride selected from the group consisting of hexahydrophthalic anhydride, 2-dodecene-1-ylsuccinic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, camphoric anhydride, and mixtures of the above. ### Claim 8 (depends on 1) A coating composition according to claim 1, wherein said C.sub.2 -C.sub.10 monoepoxide functional monomers comprises a monomer selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, glycidol, 1,2-epoxy butane, 1,2 epoxy-1 butene, 1,2-epoxyethyl benzene, 1,2 epoxy-3-phenoxy propane, and mixtures of the above. ### Claim 9 (depends on 8) A coating composition according to claim 8, wherein said C.sub.2 -C.sub.10 monoepoxide functional monomer is a C.sub.3 -C.sub.7 monomer. ### Claim 10 (depends on 9) A coating composition according to claim 9, wherein said C.sub.3 -C.sub.7 monomer contains terminal epoxide functionality. ### Claim 11 (depends on 1) A coating composition according to claim 1, wherein said monoepoxide functional monomer other than said C.sub.2 -C.sub.10 monoepoxide monomer comprises a monomer selected from the group consisting of epoxidized fatty esters, 2,3-epoxypropyl octyl ether, 1,2-epoxy-3,3,3-trichloropropane, 1,2-epoxytetradecane, 1,2-epoxycyclodecane, exo-2,3-epoxynorbornane, 1,4-epoxy-cyclohexane, 1,2-epoxy-3-floropropane, and mixtures of the above. ### Claim 12 (depends on 1) A coating composition according to claim 1, wherein said amine-aldehyde crosslinking agent is selected from the group consisting of condensation products of formaldehyde with melamine, substituted melamine, urea, benzoquanamine and substituted benzoguanamine and mixtures of said condensation products and is included in an amount sufficient to provide between about 0.75 and about 3.75 equivalent of nitrogen crosslinking functionality for each equivalent of hydroxy functionality included in said composition, either as a hydroxyl group on said modified hydroxy acrylic copolymer or as a hydroxyl group on said hydroxy functional additive. ### Claim 13 (depends on 1) A coating composition according to claim 1, wherein said hydroxy functional additive is a polyol selected from the group consisting of (i) hydroxy functional polyesters, (ii) hydroxy functional polyethers, (iii) hydroxy functional oligoesters, (iv) monomeric polyols, (v) hydroxy functional copolymers formed from monoethylenically unsaturated monomers, one or more of which bears hydroxy functionality and which is included in said copolymer in amounts ranging from about 10 to about 50 weight percent of said copolymer, and (vi) mixtures of (i)-(v). ### Claim 14 (depends on 1) A coating composition according to claim 1, which further comprises up to 15 weight percent based on the total weight of the composition of a flow control additive. ### Claim 15 (depends on 1) A coating composition according to claim 1, wherein said dicarboxylic acid anhydride consists of methyl hexahydrophthalic anhydride and said monoepoxide functional monomer consists of a C.sub.2 -C.sub.10 monoepoxide functional monomer. ### Claim 16 A modified hydroxy acrylic copolymer which is the stepwise reaction product of: (i) a copolymer bearing pendant hydroxyl groups having a number average molecular weight (M.sub.n) of between about 1000-5000, said copolymer being prepared from (a) between about 5 and about 40 weight percent of monoethylenically unsaturated hydroxy alkyl ester having formula CH.sub.2 .dbd.CR.sub.1 --COOR.sub.2 wherein R.sub.1 is H or an alkyl group and R.sub.2 is a hydroxy alkyl group and (b) between about 95-60 weight percent of other monoethylenically unsaturated monomers; (ii) dicarboxylic acid anhydride comprising at least about 50 percent by weight of an alkyl hexahydrophthalic anhydride, wherein (i) and (ii) are reacted in an amount sufficient to esterify between about 30 and about 100 percent of said pendant hydroxyl groups of said copolymer thereby generating pendant carboxyl groups; and (iii) a monoepoxide functional monomer comprising at least about 90 percent by weight C.sub.2 -C.sub.10 monoepoxide functional monomers, wherein said monomer is reacted with said pendant carboxyl groups of the polymer reaction product of (i) and (ii) in an amount so as to provide at least about 1.0 equivalent of epoxide groups per equivalent of said pendant carboxyl groups to generate pendant hydroxyl groups. ### Claim 17 (depends on 16) A modified hydroxy acrylic copolymer according to claim 16, wherein said monoethylenically unsaturated hydroxy alkyl ester comprises C.sub.5 -C.sub.7 hydroxy alkyl acrylates, C.sub.6 -C.sub.8 hydroxy alkyl methacrylates, or mixtures thereof. ### Claim 18 (depends on 16) A modified hydroxy acrylic copolymer according to claim 16, wherein said other monoethylenically unsaturated monomers comprise acrylates, other vinyl monomer, or mixtures of said acrylates and other vinyl monomers. ### Claim 19 (depends on 16) A modified hydroxy acrylic copolymer according to claim 16, wherein said alkyl group of said alkyl hexahydraphthalic anhydride comprises a lower alkyl group having up to about seven carbons. ### Claim 20 (depends on 16) A modified hydroxy acrylic copolymer according to claim 16, wherein said dicarboxylic acid anhydride comprises at least 80 percent by weight of an alkyl hexahydrophthalic anhydride. ### Claim 21 (depends on 19, 20) A modified hydroxy acrylic copolymer according to claims 19 or 20, wherein said alkyl hexahydrophthalic anhydride is methyl hexahydrophthalic anhydride. ### Claim 22 (depends on 16) A modified hydroxy acrylic copolymer according to claim 16, wherein up to about 50 percent by weight of said dicarboxylic acid anhydride employed in the preparation of said copolymer comprises an anhydride selected from the group consisting of hexahydrophthalic anhydride, 2-dodecene-1-ylsuccinic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, camphoric anhydride, and mixtures of the above. ### Claim 23 (depends on 16) A modified hydroxy acrylic copolymer according to claim 16, wherein said C.sub.2 -C.sub.10 monoepoxide functional monomers comprises a monomer selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, glycidol, 1,2-epoxy butane, 1,2 epoxy-1-butene, 1,2-epoxyethyl benzene, 1,2-epoxy-3-phenoxy propane, and mixtures of the above. ### Claim 24 (depends on 23) A modified hydroxy acrylic copolymer according to claim 23, wherein said C.sub.2 -C.sub.10 nonoepoxide functional monomer is a C.sub.3 -C.sub.7 monomer. ### Claim 25 (depends on 24) A modified hydroxy acrylic copolymer according to claim 24, wherein said C.sub.3 -C.sub.7 monomer contains terminal epoxide functionality. ### Claim 26 (depends on 16) A modified hydroxy acrylic copolymer according to claim 16, wherein said monoepoxide functional monomer other than said C.sub.2 -C.sub.10 monoepoxide monomer comprises a monomer selected from the group consisting of epoxidized fatty esters, 2,3-epoxypropyloctyl ether, 1,2-epoxy-3,3,3-trichloropropane, 1,2-epoxytetradecane, 1,2-epoxycyclodecane, exo-2,3-epoxynorbornane, 1,4-epoxycyclohexane, 1,2-epoxy-3-fluoropropane and mixtures of the above. ### Claim 27 A high solids thermosetting coating composition which contains greater than about 60 percent by weight of nonvolatile solids and which except for pigments and other nonreactive components, consists essentially of: (A) a modified hydroxy acrylic copolymer which is the stepwise reaction product of: (i) a copolymer bearing pendant hydroxyl groups and having a number average molecular weight (M.sub.n) of between about 1000-5000, said copolymer being prepared from (a) between about 5 and about 40 weight percent of monoethylenically unsaturated hydroxy alkyl ester having the formula CH.sub.2 .dbd.CR.sub.1 --COOR.sub.2 wherein R.sub.1 is H or an alkyl group and R.sub.2 is a hydroxy alkyl group and (b) between about 95-60 weight percent of other monoethylenically unsaturated monomers; (ii) dicarboxylic acid anhydride comprising at least about 50 percent by weight of an alkyl hexahydrophthalic anhydride, wherein (i) and (ii) are reacted in an amount sufficient to esterify between about 30 and about 100 percent of said pendant hydroxyl groups of said copolymer thereby generating pendant carboxyl groups; and (iii) a monoepoxide functional monomer comprising at least about 90 percent by weight C.sub.2 -C.sub.10 monoepoxide functional monomers, wherein said monomer is reacted with said pendant carboxyl groups of the polymer reaction product of (i) and (ii) in an amount so as to provide at least about 1.0 equivalent of epoxide groups per equivalent of said pendant carboxyl groups to generate pendant hydroxyl groups; (B) an amine-aldehyde crosslinking agent; (C) 0-50 weight percent based on the total weight of (A), (B), (C), (D) and (E) of a hydroxy functional additive having a number average molecular weight (M.sub.n) of between about 150 and about 6000, (D) solvent; and (E) up to 15 weight percent based on the total weight of (A), (B), (C), (D) and (E) of a flow control additive, said amine-aldehyde crosslinking agent being included in said composition in an amount sufficient to provide at least about 0.60 equivalents of nitrogen cross-linking functionality for each equivalent of hydroxyl functionality included in said composition either as a hydroxyl group on said modified hydroxy acrylic copolymer or as a hydroxyl group on said hydroxy functional additive. ### Claim 28 (depends on 27) A high solids coating composition according to claim 27, wherein said other monoethylenically unsaturated hydroxy alkyl ester is selected from the group consisting of C.sub.5 -C.sub.7 hydroxy alkyl acrylates, C.sub.6 -C.sub.8 hydroxy alkyl methacrylates, and mixtures thereof. ### Claim 29 (depends on 28) A high solids coating composition according to claim 28, wherein said other monoethylenically unsaturated monomers are selected from the group consisting of acrylates, other vinyl monomer, and mixtures of said acrylates and other vinyl monomers. ### Claim 30 (depends on 27) A high solids coating composition according to claim 27, wherein said alkyl group of said alkyl hexahydrophthalic anhydride comprises a lower alkyl group having up to about seven carbons. ### Claim 31 (depends on 27) A high solids coating composition according to claim 27, wherein said dicarboxylic acid anhydride comprises at least 80 percent by weight of an alkyl hexahydrophthalic anhydride. ### Claim 32 (depends on 30, 31) A high solids coating composition according to claims 30 or 31, wherein said alkyl hexahydrophathalic anhydride is methyl hexahydrophthalic anhydride. ### Claim 33 (depends on 27) A high solids coating composition according to claim 27, wherein up to 50 percent by weight of said dicarboxylic acid anhydride employed in the preparation of said copolymer is selected from the group consisting of hexahydrophthalic anhydride, 2-dodecene-1-ylsuccinic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, camphoric anhydride, and mixtures of the above. ### Claim 34 (depends on 27) A high solids coating composition according to claim 27, wherein said C.sub.2 -C.sub.10 monoepoxide functional monomers are selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, glycidol, 1-2-epoxy butane, 1,2 epoxy-1 butene, 1,2-epoxyethyl benzene, 1,2 epoxy-3-phenoxy propane, or mixtures of the above. ### Claim 35 (depends on 34) A high solids coating composition according to claim 34, wherein said C.sub.2 -C.sub.10 monoepoxide functional monomer is a C.sub.3 -C.sub.7 monomer. ### Claim 36 (depends on 35) A high solids coating composition according to claim 35, wherein said C.sub.3 -C.sub.7 monomer contains terminal epoxide functionality. ### Claim 37 (depends on 27) A high solids coating composition according to claim 27 wherein said monoepoxide functional monomer other than said C.sub.2 -C.sub.10 monoepoxide monomer is selected from the group consisting of epoxidized fatty esters, 2,3-epoxypropyl octyl ether, 1,2-epoxy 3,3,3-trichloropropane, 1,2-epoxytetradecane, 1,2-epoxycyclodecane, exo-2,3-epoxynorbornane, 1,4-epoxycyclohexane, 1,2 epoxy-3-fluoropropane, or mixtures of the above. ### Claim 38 (depends on 27) A high solids coating composition according to claim 27, wherein said amine-aldehyde crosslinking agent is selected from the group consisting of condensation products of formaldehyde with melamine, substituted melamine, urea, benzoquanamine and substituted benzoguanamine and mixtures of said condensation products and is included in an amount sufficient to provide between about 0.75 and about 3.75 equivalent of nitrogen crosslinking functionality for each equivalent of hydroxy functionality included in said composition either as a hydroxyl group on said modified hydroxy acrylic copolymer or as a hydroxyl group on said hydroxy functional additive. ### Claim 39 (depends on 27) A high solids coating composition according to claim 27, wherein said hydroxy functional additive is a polyol selected from the group consisting of (i) hydroxy functional polyesters, (ii) hydroxy functional polyethers, (iii) hydroxy functional oligoesters, (iv) monomeric polyols, (v) hydroxy functional copolymers formed from monoethylenically unsaturated monomers, one or more of which bears hydroxy functionality and which is included in said copolymer in amounts ranging from about 10 to about 50 weight percent of said copolymer, and (vi) mixtures of (i)-(v). ### Claim 40 (depends on 27) A high solids coating composition according to claim 27, wherein said dicarboxylic acid anhydride consists of methyl hexahydrophthalic anhydride and said monoepoxide functional monomer consists of a C.sub.2 -C.sub.10 monoepoxide functional monomer.