Polyurethane resins in water-dilutable basecoats having low flash and quick-drying characteristics

Abstract

This invention, therefore, relates to the field of polyurethane coatings for use in automobile basecoat/clearcoat systems. In particular, this invention relates to the discovery that incorporating a long-chain carboxylic acid of at least 50% by weight of the carboxylic acid component used to make polyester resins which are further incorporated into polyurethane resins provides basecoat composition exhibiting low temperature flash characteristics. These low temperature flash characteristics are exhibited even where the basecoat is deposited at 50-90% relative humidity.

.[.1. A basecoat composition suitable for deposition onto metal or plastic comprising: 
     
        acid..]. 3. The basecoat composition according to claim .[.2.]. .Iadd.57 .Iaddend.wherein said long-chain carboxylic acid comprises about 50 to 80% of the carboxylic acid component used to synthesize said polyurethane principal resin. .[.4. The basecoat composition according to claim 3 wherein said long chain carboxylic acid used to synthesize said polyurethane resin is C 36  dimer fatty acid..]. .[.5. The basecoat composition according to claim 1 wherein said polyfunctional carboxylic 
     
     
        acid (d) is trimellitic anhydride..]. 6. The basecoat composition according to claim .[.1.]. .Iadd.60 .Iaddend.wherein said hectorite clay 
     
     
        is a purified sodium lithium magnesium silicate. 7. The basecoat composition according to claim .[.1.]. .Iadd.61 .Iaddend.wherein said fumed silica compound is Aerosil 972 ™. .[.8. The basecoat composition 
     
     
        according to claim 1 wherein said aminoplast is melamine..]. 9. A branched chain polyester resin for use in basecoat compositions comprising the reaction product of: (a) a polyester component comprised of the reaction product of (i) a carboxylic acid component comprised of at least about 50% by weight of a long-chain carboxylic acid having between 18 and 60 carbons, no more than about 50% by weight of a short-chain dicarboxylic acid; and   (ii) an alcohol component having an average functionality of at least 2; and     (b) between about 2 and 25% by weight of a polyfunctional carboxylic acid   
     
     
        or acid anhydride having at least 3 carboxylic acid groups. 10. The polyester resin according to claim 9 wherein said long-chain carboxylic 
     
     
        acid is C36 dimer fatty acid. 11. The polyester resin according to claim 9 
     
     
        wherein said short-chain dicarboxylic acid is isophthalic acid. 12. The polyester resin according to claim .[.11.]. .Iadd.65 .Iaddend.wherein said 
     
     
        polyfunctional carboxylic acid is trimellitic anhydride. 13. The polyester resin according to claim .[.12.]. .Iadd.66 .Iaddend.wherein said aliphatic 
     
     
        diol is 1,6 hexanediol. 14. A multi-layer paint composition comprising: (a) at least one waterborne basecoat composition comprising: (i) an anionic polyurethane composition comprised of the reaction product of: (1) a polyester resin component produced by the reaction of a carboxylic acid component comprised of at least 50% by weight of at least one long-chain carboxylic acid having between 18 and 60 carbon atoms, and at most about 50% by weight of a short-chain dicarboxylic acid and an alcohol having at least 2 hydroxyl groups; and   (2) a mixture of at least one multi-functional compound having at least 1 active hydrogen group and at least two active hydrogen groups, and a polyisocyanate, said carboxylic acid groups being neutralized with an amine;     (ii) a cross-linking agent;   (iii) a branched chain polyester resin comprised of the reaction product of: (1) (A) a polyester component comprised of the reaction product of a carboxylic acid component comprised of at least 50% by weight of a long-chain carboxylic acid having between 18 and 60 carbons, no more than about 50% by weight of a short-chain dicarboxylic acid; and   (B) an alcohol containing compound having an average alcohol functionality of at least 2; and   (2) between about 2 and 25% by weight of a poly-functional carboxylic acid or acid anhydride having at least 3 carboxylic acid groups;     (iv) a pigment; and     (b) a clear topcoat composition for overcoating said basecoat composition.   
     
     
        .[.15.  The composition according to claim 14 wherein said long-chain 
     
     
        carboxylic acid is C 36  dimer fatty acid..]. 16. The composition according to claim .[.15.]. .Iadd.67, 68, or 69 .Iaddend.wherein said cross-linking agent is melamine. .[.17. The composition according to claim 
     
     
        16 wherein said short chain dicarboxylic acid is isophthalic acid..]. 18. The composition according to claim 14 wherein said compound having at least two active .Iadd.hydrogen .Iaddend.groups .Iadd.of component (a) (i)(2) .Iaddend. is selected from the group consisting of diols, diamines, 
     
     
        and dithiols. 19. The composition according to claim .[.14.]. .Iadd.74 
     
     
        .Iaddend.wherein said aliphatic diol is 1,6 hexanediol. 20. The composition according to claim 14 wherein said polyfunctional carboxylic 
     
     
        acid is trimellitic anhydride. 21. The .[.method.]. .Iadd.composition .Iaddend.according to claim 20 wherein said long-chain carboxylic acid 
     
     
        .Iadd.of component (a)(i)(1) .Iaddend.is C 36  dimer acid. 22. The .[.method.]. .Iadd.composition .Iaddend.according to claim 21.Iadd., 75 or 76 .Iaddend.wherein said short-chain dicarboxylic acid is selected from 
     
     
        the group consisting of adipic acid and isophthalic acid. 23. The .[.method.]. .Iadd.composition .Iaddend.according to claim 22 wherein said 
     
     
        alcohol having at least 2 hydroxyl groups is 1,6-hexanediol. 24. The .[.method.]. .Iadd.composition .Iaddend.according to claim 23 wherein said 
     
     
        cross-linking agent is melamine. 25. The .[.method.]. .Iadd.composition .Iaddend.according to claim .[.24.]. .Iadd.79 .Iaddend.wherein said rheology control agent is selected form the group consisting of fumed 
     
     
        silica compounds, bentonite clays, and hectorite clays. 26. The .[.method.]. .Iadd.composition .Iaddend.according to claim 25 wherein said 
     
     
        hectorite clay is a purified sodium lithium magnesium silicate. 27. A method of coating an automobile substrate with a multilayer coating comprising: (a) applying to the primed substrate .[.old.]. at least one layer of a waterborne .[.coating.]. .Iadd.basecoat .Iaddend.composition comprised of: (i) a polyurethane resin obtained from the reaction product of: (1) a polyester resin component produced by the reaction of a carboxylic acid component comprised of at least 50% by weight of a long-chain carboxylic acid having between 18 and 60 carbon atoms and at most about 50% of a short chain dicarboxylic acid and an alcohol having at least 2 hydroxyl groups; and   (2) a mixture of a multi-functional compound having at least 1 active hydrogen functionality and at least one carboxylic acid functionality, at least one compound having at least two active hydrogen groups, and polyisocyanate, said carboxylic acid groups being neutralized with an amine;     (ii) a cross-linking agent;   (iii) a rheology control agent; and   (iv) a pre-formed branched chain polyester resin comprised of the reaction product of: (1) (A) a polyester component comprised of the reaction product of a carboxylic acid component comprised of at least 50% by weight of a long chain carboxylic acid having between 18 and 60 carbons, no more than about 50% by weight of a short-chain dicarboxylic acid and between about 2 and 25% by weight of a poly-functional carboxylic acid having at least 3 carboxylic acid groups; and   (B) an alcohol component having an average functionality of at least 2; and   (2) between about 2 and 25% by weight of a polyfunctional carboxylic acid having at least 3 carboxylic acid groups, (b) flash drying said basecoats; and   (c) applying at least one layer of a clear topcoat onto said basecoat; and         
     
     
       (d) curing said basecoats and topcoat to a hard, durable film. 28. The method according to claim 27 wherein said long-chain carboxylic acid is 
     
     
        C 36  dimer fatty acid .Iadd.of component (a)(i)(1).Iaddend.. 29. The method according to claim 28.Iadd., 81 or 82 .Iaddend.wherein said short-chain dicarboxylic acid .Iadd.of component (a)(i)(1) .Iaddend.is 
     
     
        isophthalic acid. 30. The method according to claim 29 wherein said 
     
     
        alcohol having at least 2 hydroxyl groups is 1,6 hexane diol. 31. A multi-coated metal or plastic substrate comprising: a substrate coated with at least one waterborne basecoat composition comprising:   (a) about 20 to 80% weight percent based on the final solids content of said basecoat composition of .[.a first.]. .Iadd.an .Iaddend.anionic polyurethane resin comprised of the reaction product of: (i) a polyester component with an alcohol having at least two hydroxyl groups .[.wherein said.]. .Iadd.and a .Iaddend.carboxylic acid component .[.is.]. comprised of at least about 50% by weight of a long-chain carboxylic acid having between 18 and 60 carbon atoms and at most about 50% of a short chain dicarboxylic acid:   (ii) a multi-functional compound having at least 1 active hydrogen functionality and at least one carboxylic acid functionality;   (iii) a compound having at least 2 active hydrogen groups;   (iv) a polyisocyanate; and   (v) an amine-containing compound for neutralizing the free carboxylic acid groups;     (b) about 5 to about 50 weight percent of an aminoplast cross-linking resin;   (c) about 0.1 to about 25 weight percent of a rheology control agent, selected from the group consisting of fumed silica compounds, bentonite clays, and hectorite clays;   (d) about 0 to about 35 weight percent of a branched chain polyester resin comprised of the reaction product of; (i) a carboxylic acid component comprised of at least 50% by weight of a long chain carboxylic acid having between 18 and 60 carbons, no more than about 48% by weight of a short-chain dicarboxylic acid and between 2 and 25% by weight of a polyfunctional carboxylic acid or acid anhydride, said polyfunctional carboxylic acid having at least 3 carboxylic acid groups; and   (ii) an alcohol component having an average functionality of about at least 2; and     (e) about 2 to about 75 weight percent of a pigment, each of said basecoat compositions being flash-dried before being coated with a clear topcoating, said basecoat composition and said topcoating being cured to a   
     
     
        hard, durable film. 32. The composition according to claim 31 wherein said long-chain carboxylic acid .Iadd.of component (a)(i)(1) .Iaddend.is 
     
     
        C 36  dimer acid. 33. The composition according to claim .[.1.]. .Iadd.31 .Iaddend.wherein said polyurethane resin is neutralized with an 
     
     
        amine. 34. The composition according to claim 33 wherein said amine is a 
     
     
        tertiary amine. 35. The composition according to claim 14 wherein said 
     
     
        amine is a tertiary amine. 36. The .[.method.]. .Iadd.composition .Iaddend.according to claim 21 wherein said amine is a tertiary amine. .[.37. The method according to claim 21 wherein said premixed slurry is 
     
     
        further comprised of pigment particles..]. 38. The .[.method.]. .Iadd.composition .Iaddend.according to claim .[.37.]. .Iadd.89 .Iaddend.wherein said pigment particles are selected from the group consisting of aluminum metal flakes and pigment coated mica particles 
     
     
        .[.in solvent.].. 39. The method according to claim 27 wherein said amine is a tertiary amine. .[.40. The method according to claim 27 wherein said first layer composition further comprises a composition selected from the 
     
     
        group consisting of aluminum, mica, and mixtures thereof..]. 41. The method according to claim .[.27.]. .Iadd.90 .Iaddend.wherein said first 
     
     
        layer .[.composition.]. further comprises a branched polyester resin. 42. The method according to claim .[.40.]. .Iadd.91 .Iaddend.wherein said 
     
     
        first layer further comprises a branched polyester resin. 43. The method according to claim 31 wherein said amine-containing compound is a tertiary amine-containing compound. .[.44. The basecoat composition of claim 1, wherein the rheology control agent is selected from the group consisting 
     
     
        of fumed silica compounds, bentonite clays, and hectorite clays..]. 45. The multi-layer paint composition of claim 14 wherein said topcoat composition is applied to the uncured basecoat compositions which have been flash dried at a time and temperature such that the topcoat can be 
     
     
        applied without an intervening cooldown period. 46. The multi-layer paint composition of claim 45 wherein the basecoat compositions are flash dried at a temperature between room temperature and about 145 degrees F. for 
     
     
        between about 30 seconds and about 10 minutes. 47. The multi-coated metal or plastic substrate of claim 31 wherein the basecoat compositions are flash dried at a time and temperature such that the topcoat can be applied 
     
     
        without an intervening cooldown period. 48. The multi-coated metal or plastic substrate of claim 47 wherein the basecoat .[.composition.]. .Iadd.compositions .Iaddend.are flash dried at a temperature between room temperature and about 145 degrees F. for between about 30 seconds and 
     
     
        about 10 minutes. 49. The basecoat composition of claim .[.1 additionally.]. .Iadd.59 .Iaddend.comprising from about 2 to about 25 
     
     
        weight percent of a rheology control agent. 50. The basecoat composition of claim 49 wherein the rheology control agent is selected from the group consisting of fumed silica compounds, bentonite clays and hectorite clays. 
     
     
        1. A method of making a waterborne basecoat composition for use in a multi-layer coating comprised of (A) an anionic polyurethane resin comprised of (1) a polyester resin component produced by the reaction of a carboxylic acid component comprised of at least 50% by weight of a long-chain acid having between 18 and 60 carbon atoms and at most about 50% of a short-chain dicarboxylic acid and an alcohol having at least 2 hydroxyl groups; and   (2) a mixture of at least one multi-functional compound having at least 1 active hydrogen functionality and at least one carboxylic acid functionality, at leat one compound having at least two active hydrogen groups, and a polyisocyanate, said carboxylic acid group being neutralized with an amine,     (B) a crosslinking agent, and   (C) a rheology control agent, comprising the sequential steps of: (a) adding the crosslinking agent in solution to the rheology control agent in solution and thoroughly mixing .Iadd.and.Iaddend.;   (b) adding an aqueous dispersion of the anionic polyurethane resin under     
     
     
        agitation and thoroughly mixing. 52. The method of claim 51 comprising the additional sequential step of (c) adding under agitation and with thourough mixing a premixed slurry comprised of: (i) a slurry of mica particles and, optionally, aluminum metal flakes and (ii) a pre-formed branched chain polyester resin dispersions, said polyester resin comprised of the reaction product of: (1) (A) a polyester component compound of the reaction product of a carboxylic acid component comprised of at least 50% by weight of a long chain carboxylic acid having between 18 and 60 carbons, no more than about 50% by weight of a short-chain dicarboxylic acid and between about 2 and 25% by weight of a polyfunctional carboxylic acid having at least 3 carboxylic acid groups; and   (B) an alcohol component having an average functionality of at least 2; and   (2) between about 2 and 25% by weight of a polyfunctional carboxylic acid     
     
     
        having at least 3 carboxylic acid groups. 53. The method of claim 52 comprising the additional sequential steps of (d) adding under agitation and with thorough mixing a pigment-containing grind resin, and (e) 
     
     
        adjusting the pH and viscosity of the mixture so obtained. 54. The method of claim 27 wherein the basecoat compositions are flash dried at a time and temperature such that the topcoat can be applied without an 
     
     
        intervening cooldown period. 55. The method of claim 54 wherein the basecoat compositions are flash dried at a temperature between room temperature and about 145 degrees F. for between about 30 seconds and 
     
     
        about 10 minutes. .Iadd.56.  A basecoat composition for deposition onto metal or plastic comprising: (a) about 20 to 80% weight percent based on the final solids content of said basecoat composition of an anionic polyurethane resin comprised of the reaction product of: (i) a polyester component comprised of the reaction product of a carboxylic acid component with an alcohol having at least two hydroxyl groups wherein said carboxylic acid component is comprised of at least about 50% by weight of at least one long-chain carboxylic acid having between 18 and 60 carbon atoms and at most about 50% of at least one short-chain dicarboxylic acid;   (ii) a multifunctional compound having at least one active hydrogen and at least one carboxylic acid functionality;   (iii) a compound having at least 2 active hydrogen groups selected from the group consisting of hydroxyl, sulfhydryl, primary amine and secondary amine, one of said primary amines accounting for one active hydrogen and   (v) a polyisocyanate;     (b) about 5 to about 50% by weight of an aminoplast cross-linking resin;   (c) 5 to about 35 weight percent of a branched chain polyester resin comprised of the reaction product of: (i) a polyester component comprised of the reaction product of: (1) a carboxylic acid component comprised of at least 50% by weight of at least one long chain carboxylic acid containing compound having between 18 and 60 carbons and not more than 50% by weight of at least one short-chain dicarboxylic acid, and   (2) an alcohol component having an average functionality of at least 2; and     (ii) 2 to 25% by weight of a polyfunctional carboxylic acid or acid anhydride, said polyfunctional carboxylic acid or acid anhydride having at least 3 carboxylic acid groups; and     (d) about 2 to 75 weight percent of pigment-containing grind resin comprising: (i) about 6 to about 60% by weight of said pigment-containing grind resin of a pigment;   (ii) about 20 to about 75% by weight of said pigment-containing grind resin of a polyurethane resin produced by the reaction product of: (1) a polyester resin component produced by the reaction of a carboxylic acid component comprised of at least 50% by weight of a long-chain carboxylic acid having between 18 and 60 carbon atoms, and at most about 50% of a short-chain dicarboxylic acid, and an alcohol having at least 2 hydroxyl groups; and   (2) a mixture of a multifunctional compound having at least 1 active hydrogen and at least one carboxylic acid functionality, and at least one compound having at least two active hydrogen groups, and a polyisocyanate, said at least one carboxylic acid functionality being neutralized with amine; and     (iii) about 20% to about 60% by weight of said pigment-containing grind     
     
     
        resin of an aminoplast cross-linking agent. .Iaddend. .Iadd.57.  The basecoat according to claim 56, wherein the long-chain carboxylic acid contained in the polyurethane resin of component (a) is comprised of C 36  dimer fatty acid. .Iaddend. .Iadd.58. The basecoat composition according to claim 56 wherein the multifunctional compound of component (d)(ii)(2) is trimellitic anhydride. .Iaddend. .Iadd.59. The basecoat composition according to claim 56 further comprising a rheology control 
     
     
        agent. .Iaddend. .Iadd.60.  The basecoat composition according to claim 59 wherein the rheology control agent is hectorite clay. .Iaddend. .Iadd.61. The basecoat composition according to claim 59 wherein the rheology control agent is a fumed silica compound. .Iaddend. .Iadd.62. The basecoat composition of claim 57 wherein the aminoplast cross-linking agent of component (b) is an aldehyde condensation product of melamine. .Iaddend. .Iadd.63. The basecoat composition of claim 57 wherein the aminoplast cross-linking agent of component (d)(iii) is an aldehyde condensation product of melamine. .Iaddend. .Iadd.64. The basecoat composition of claim 57 wherein the aminoplast cross-linking resin of components (b) and (d)(iii) is an aldehyde condensation product melamine. .Iaddend. .Iadd.65. The polyester resin of claim 9 wherein component (b) is a polyfunctional carboxylic acid. .Iaddend. .Iadd.66. The polyester resin of claim 9 wherein the alcohol component is an aliphatic diol. .Iaddend. .Iadd.67. The composition of claim 14 wherein the long-chain carboxylic acid of component (a)(i)(1) is C 36  dimeter acid. .Iaddend. .Iadd.68. The composition of claim 14 wherein the long-chain carboxylic acid of component (a)(iii)(1)(A) is C 36  dimer acid. .Iaddend. .Iadd.69. The composition of claim 14 wherein the long-chain carboxylic acid of component (a)(i)(1) and of component (a)(iii)(1)(A) is C 36  dimer acid. .Iaddend. .Iadd.70. The composition of claim 67, 68, or 69 wherein the short-chain dicarboxylic acid of component (a)(i)(1) is isophthalic acid. .Iaddend. .Iadd.71. The composition of claim 67, 68, or 69 wherein the short-chain dicarboxylic acid of component (a) (iii)(1)(A) is isophthalic acid. .Iaddend. .Iadd.72. The composition of claim 67, 68 or 69 wherein the short-chain dicarboxylic acid of component (a)(i)(1) and of component (a)(iii)(1)(A) is isophthalic acid. .Iaddend. .Iadd.73. The composition of claim 14 wherein the alcohol containing compound of 
     
     
        component (a)(iii)(1)(B) is an aliphatic diol. .Iaddend. .Iadd.74.  The composition according to claim 20 wherein said long-chain carboxylic acid of component (a)(iii)(1)(A) is C 36  dimer acid. .Iaddend. .Iadd.75. The composition of claim 20 wherein the long-chain carboxylic acid of components (a)(i)(1) and (a)(iii)(1)(A) is C 36  dimer acid. .Iaddend. .Iadd.76. The composition according to claim 21, 74 or 75 wherein said short-chain dicarboxylic acid of component (a)(iii)(1)(A) is selected from adipic acid and isophthalic acid. .Iaddend. .Iadd.77. The composition according to claim 21, 74 or 75 wherein said short-chain dicarboxylic acid of components (a)(i)(1) and (a)(iii)(1)(A) is selected from adipic acid isophthalic acid. .Iaddend. .Iadd.78. The composition of claim 24 further comprising a rheology control agent. .Iaddend. .Iadd.79. The method of claim 27 wherein said long-chain carboxylic acid of component (a)(iv)(1)(A) is C 36  dimer acid. .Iaddend. .Iadd.80. The method of claim 27 wherein the long-chain carboxylic acid of components (a)(i)(1) and (a)(iv)(1)(A) is C 36  dimer acid. .Iaddend. .Iadd.81. The method of claim 28, 79 or 80 wherein said short-chain dicarboxylic acid of component (a)(iv)(1)(A) is isophthalic acid. .Iaddend. .Iadd.82. The method of claim 28, 79 or 80 wherein the short-chain dicarboxylic acid of components (a)(i)(1) and (a)(iv)(1)(A) is isophthalic acid. .Iaddend. .Iadd.83. The method according to claim 81 wherein the alcohol having at least 2 hydroxyl groups is 1,6-hexanediol. .Iaddend. .Iadd.84. The method according to claim 82 wherein the alcohol having at least 2 hydroxyl groups is 1,6-hexanediol. .Iaddend. .Iadd.85. The composition according to claim 31 wherein said long-chain carboxylic acid of component (d)(i) is 
     
     
        C 36  dimer acid. .Iaddend. .Iadd.86.  The composition according to claim 31 wherein said long-chain carboxylic acid of components (a)(i)(1) and (d)(i) is C 36  dimer acid. .Iaddend. .Iadd.87. The composition according to claim 21 wherein the pigment particles are in the form of a premixed slurry. .Iaddend. .Iadd.88. The method of claim 27 wherein the at least one layer of a waterborne basecoat composition is further comprised of a first layer and at least one other layer. .Iaddend. .Iadd.89. The method of claim 88 wherein the first layer of the at least one layer of a waterborne coating composition further comprises aluminum, mica or a mixture thereof. .Iaddend.