Amide-modified urethane acrylate radiation curable compounds and coating compositions and methods of making same

Abstract

Radiation curable compounds are disclosed comprising an amide moiety, a urethane moiety and an ethylenically unsaturated functional group, typically an acrylate functional group. The compounds comprise the reaction products of an amide-containing compound having at least one hydroxy functional group, a polyisocyanate and a polyfunctional compound having a hydroxy functional group reactive with an isocyanato group of the polyisocyanate, which polyfunctional compound provides an ethylenic functional group in the reaction product. Coating compositions containing these radiation curable reaction products cure at relatively high rates to form films having high abrasion resistance and improved tensile strength and elongation properties as compared to conventional urethane acrylate coating compositions.

What is claimed: 
     
       1. Addition polymerizable compound having .[.at least.]. one .Iadd.or two .Iaddend.amide .[.group.]. .Iadd.groups.Iaddend., at least .[.one.]. .Iadd.three .Iaddend.urethane .[.group.]. .Iadd.groups .Iaddend.and at least one .[.ethylenically unsaturated functional.]. .Iadd.acrylate or methacrylate .Iaddend.group comprising the reaction product of .[.the.]. components .[.of.]. .Iadd.comprising: .Iaddend. (a) an amide-containing compound .[.having.]. .Iadd.which contains one or two amide groups and .Iaddend.at least one NCO-reactive hydroxy functional group;   (b) a polyisocyanate .Iadd.which is a diisocyanate or a triisocyanate.Iaddend.; .[.and.].   (c) a polyfunctional compound .[.containing at least one functional group reactive with an isocyanato group of said polyisocyanate and.]. which .[.polyfunctional compound.]. provides at least one .[.ethylenically unsaturated functional.]. .Iadd.acrylate or methacrylate .Iaddend.group in said reaction product.Iadd., said polyfunctional compound being a hydroxy-containing ester of acrylic acid or a hydroxy-containing ester of methacrylic acid; and .Iaddend.   .Iadd.(d) polyol selected from the group consisting of polyester polyol and polyether polyol.Iaddend..   
     
     
       2. The addition polymerizable compound of claim 1, wherein said amide-containing compound .[.having at least one hydroxy functional group.]. is selected from the group consisting of (a) a reaction product of a monocarboxylic acid and an aminoalcohol;   (b) a reaction product of an ester of a carboxylic acid and an aminoalcohol;   (c) a reaction product of a hydroxy carboxylic acid and a compound containing .[.at least.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens.Iaddend.;   (d) a reaction product of a lactone and ammonia or a compound containing .[.at least.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens.Iaddend.; and   (e) a reaction product of a lactide and ammonia or a compound containing .[.at least.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens.Iaddend..  .[.   
     
     
       3.  The addition polymerizable compound of claim 1, wherein said amide-containing compound having at least one hydroxy functional group is a polyamide polyol..]. 
     
     
       4. The addition polymerizable compound of claim .[.2.]. .Iadd.1.Iaddend., wherein said .Iadd.amide-containing compound is a reaction product of (a) a .Iaddend.monocarboxylic acid .[.is.]. selected from the group consisting of formic acid, acetic acid, propionic acid and benzoic acid .Iadd.and (b) an aminoalcohol. .Iaddend. 
     
     
       5. The addition polymerizable compound of claim .[.2.]. .Iadd.1.Iaddend., wherein said .Iadd.amide-containing compound is a reaction product of (a) an .Iaddend.ester of a carboxylic acid .[.is.]. selected from the group consisting of methyl formate, ethyl acetate, dimethyl adipate and .[.methyl-2-ethyl hexanoate.]. .Iadd.methyl 2-ethylhexanoate and (b) an aminoalcohol. .Iaddend. 
     
     
       6. The addition polymerizable compound of claim .[.2.]. .Iadd.1.Iaddend., wherein said .Iadd.amide-containing compound is a reaction product of (a) a .Iaddend.hydroxy carboxylic acid .[.is.]. .Iadd.selected from the group consisting of .Iaddend.hydroxyacetic acid, 2,2-bis(hydroxymethyl)propionic acid .[.or.]. .Iadd.and .Iaddend.an aromatic hydroxy acid prepared from the reaction of phthalic anhydride and diethylene glycol .Iadd.and (b) a compound containing one or two amino nitrogens. .Iaddend. 
     
     
       7. The addition polymerizable compound of claim .[.2.]. .Iadd.1.Iaddend., wherein said .Iadd.amide-containing compound is a reaction product of (a) a .Iaddend.lactone .[.is.]. selected from the group consisting of γ-butyrolactone, γ-valerolactone, δ-valerolactone and ε-caprolactone .Iadd.and (b) a compound containing one or two amino nitrogens. .Iaddend. 
     
     
       8. The addition polymerizable compound of claim .[.2.]. .Iadd.6 or 7.Iaddend., wherein said compound containing .[.at least.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens .Iaddend.is selected from the group consisting of aminoalcohol, aliphatic mono- or .[.polyamine.]. .Iadd.diamine.Iaddend., aromatic mono- or .[.polyamine.]. .Iadd.diamine .Iaddend.and cyclic mono- or .[.polyamine.]. .Iadd.diamine. .Iaddend. 
     
     
       9. The addition polymerizable compound of claim .[.8.]. .Iadd.4 or 5.Iaddend., wherein said aminoalcohol .[.that is reactable with one of said carboxylic acid, carboxylic acid ester, hydroxy carboxylic acid, lactone and lactide.]. is selected from the group consisting of ethanolamine, diethanolamine, N-methylethanolamine and aminobenzyl alcohol. 
     
     
       10. The addition polymerizable compound of claim .[.8.]. .Iadd.6 or 7.Iaddend., wherein said .Iadd.compound containing one or two amino nitrogens is an .Iaddend.aliphatic .[.mono- or polyamine is.]. .Iadd.diamine .Iaddend.selected from the group consisting of ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N,N-dimethylpropylenediamine, hexamethylenediamine and .[.poly(alkyleneoxide diamines).]. .Iadd.poly(alkyleneoxide) diamine. .Iaddend. 
     
     
       11. The addition polymerizable compound of claim .[.8.]. .Iadd.6 or 7.Iaddend., wherein said .[.aromatic mono- or polyamine.]. .Iadd.compound containing one or two amino nitrogens .Iaddend.is benzylamine. 
     
     
       12. The addition polymerizable compound of claim .[.8.]. .Iadd.6 or 7.Iaddend., wherein said .Iadd.compound containing one or two amino nitrogens is a .Iaddend.cyclic mono- or .[.polyamine is.]. .Iadd.diamine .Iaddend.selected from the group consisting of piperazine, piperidine and morpholine.  .[.13. The addition polymerizable compound of claim 1, wherein said reaction product further comprises a moiety derived from the 
     
     
        reaction of said polyisocyanate and a polyol..]. 14. The addition polymerizable compound of claim .[.13,.]. .Iadd.1 .Iaddend.wherein said polyol is .[.selected from the group consisting of a polyester polyol, 
     
     
        alkyl diol, alkyl triol and.]. polyoxyalkylene polyol. 15. The addition polymerizable compound of claim .[.13,.]. .Iadd.1 .Iaddend.wherein said 
     
     
        polyol is a poly(caprolactone) polyol. 16. The addition polymerizable compound of claim .[.13 or.]. 1 wherein said polyisocyanate is selected from the group consisting of 1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane, toluene diisocyanate and bis(4-isocyanatocyclohexyl)methane.  .[.17. The addition polymerizable compound of claim 1, wherein said polyfunctional compound is selected from the group consisting of acrylic acid and hydroxy-containing 
     
     
        acrylic ester..]. 18. The addition polymerizable compound of claim .[.17.]. .Iadd.1.Iaddend., wherein said .[.hydroxy-containing acrylic ester.]. .Iadd.polyfunctional compound .Iaddend.is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 
     
     
        2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. 19. A coating composition containing addition polymerizable compound as defined 
     
     
        in claim 1. 20. An article of manufacture having a cured film thereon made 
     
     
        from the coating composition of claim 19. 21. The addition polymerizable compound of claim .[.2.]. .Iadd.1 .Iaddend.wherein said amide-containing compound .[.having at least one hydroxy functional group.]. is a reaction product of γ-butyrolactone and ethanolamine, and wherein said reaction product of said γ-butyrolactone and ethanolamine comprises 
     
     
        N-(2-hydroxyethyl)pyrrolidone. 22. A blend of the reaction product of claim 1 and the additional reaction product of (a) a polyol;   (b) a polyisocyanate; and   (c) a polyfunctional compound containing at least one functional group reactive with an isocyanato group of said polyisocyanate and which polyfunctional compound provides at least one ethylenically unsaturated   
     
     
        functional group in said additional reaction product. 23. A method for preparing .Iadd.a reaction product comprising .Iaddend.an addition polymerizable compound .[.comprising a reaction product.]. .Iadd.having one or two amide groups, at least three urethane groups and at least one acrylate or methacrylate group.Iaddend., said method comprising reacting together .[.the.]. components .[.of.]. .Iadd.comprising: .Iaddend. (a) an amide-containing compound .[.having.]. .Iadd.which contains one or two amide groups and .Iaddend.at least one NCO-reactive hydroxy functional group;   (b) a polyisocyanate .Iadd.which is a diisocyanate or a triisocyanate.Iaddend.; .[.and.].   (c) a polyfunctional compound .[.containing at least one functional group reactive with an isocyanato group of said polyisocyanate and.]. which .[.polyfunctional compound.]. provides at least one .[.ethylenically unsaturated functional.]. .Iadd.acrylate or methacrylate .Iaddend.group in said reaction product.[...]..Iadd., said polyfunctional compound being a hydroxy-containing ester of acrylic acid or a hydroxy-containing ester of methacrylic acid; and .Iaddend.   (d) polyol selected from the group consisting of polyester polyol and polyether polyol.  .[.24. The method of claim 23, wherein said components and a polyol are reacted to provide in said reaction product a urethane moiety derived from the reaction of said polyisocyanate with said   
     
     
        polyol..]. 25. The method of claim 23, wherein said reaction product is made by (a) forming a blend comprising (1) an NCO-terminated intermediate having at least one urethane group prepared from the reaction of said polyisocyanate and said amide-containing compound .[.having at least one NCO-reactive hydroxy functional group.].; and   (2) an NCO-terminated intermediate having at least one urethane group prepared from the reaction of .[.a.]. .Iadd.said .Iaddend.polyol and said polyisocyanate;     (b) reacting said blend of NCO-terminated intermediates with said polyfunctional compound, to provide .[.in.]. said reaction product .[.at least one amide group, at least one urethane group and at least one ethylenically unsaturated     
     
     
        functional group.].. 26. The method of claim 25, wherein said reaction product is made by the steps of (a) adding a mixture of said amide-containing compound and said polyol to said polyisocyanate to form said blend comprising NCO-terminated intermediates; and   (b) adding said polyfunctional compound to said blend of NCO-terminated   
     
     
        intermediates. 27. The method of claim 26, wherein (a) said mixture is added gradually to said polyisocyanate; and   
     
     
       (b) said polyfunctional compound is added gradually to said blend. 28. The method of claim .[.24.]. .Iadd.23 .Iaddend.or 25, wherein said polyol is .[.selected from the group consisting of polyester polyol, alkyl diol, 
     
     
        alkyl triol and.]. polyoxyalkylene polyol. 29. The method of claim .[.28.]. .Iadd.23 or 25.Iaddend., wherein said .[.polyester.]. polyol is a 
     
     
        poly(caprolactone) polyol. 30. The method of claim 23, wherein said amide-containing compound .[.having at least one hydroxy functional group.]. is selected from the group consisting of (a) a reaction product of a monocarboxylic acid and an aminoalcohol;   (b) a reaction product of an ester of a carboxylic acid and an aminoalcohol;   (c) a reaction product of a hydroxy carboxylic acid and a compound containing .[.at least.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens.Iaddend.;   (d) a reaction product of a lactone and ammonia or a compound containing .[.at least.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens.Iaddend.; and   (e) a reaction product of a lactide and ammonia or a compound containing .[.at least.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens. .Iaddend. .[.31. The method of claim 23, wherein said amide-containing compound having at least one hydroxy functional group is   
     
     
        a polyamide polyol..]. 32. The method of claim .[.30.]. .Iadd.23.Iaddend., wherein said .[.carboxylic.]. .Iadd.amide-containing compound is a reaction product of (a) a monocarboxylic .Iaddend.acid .[.is.]. selected from the group consisting of formic acid, acetic acid, propionic acid and 
     
     
        benzoic acid .Iadd.and (b) an aminoalcohol.Iaddend.. 33. The method of claim .[.30.]. .Iadd.23.Iaddend., wherein said .Iadd.amide-containing compound is a reaction product of (a) an .Iaddend.ester of a carboxylic acid .[.is.]. selected from the group consisting of methyl formate, ethyl acetate, .[.methyl-2-ethyl hexanoate.]. .Iadd.methyl 2-ethylhexanoate .Iaddend.and dimethyl adipate .Iadd.and (b) an aminoalcohol. .Iaddend. 
     
     
            The method of claim .[.30.]. .Iadd.23.Iaddend., wherein said .Iadd.amide-containing compound is a reaction product of (a) a .Iaddend.hydroxy carboxylic acid .[.is.]. .Iadd.selected from the group consisting of .Iaddend.hydroxyacetic acid, 2,2-bis(hydroxymethyl)propionic acid .[.or.]. .Iadd.and .Iaddend.an aromatic hydroxy acid prepared from the reaction of phthalic anhydride and diethylene glycol .Iadd.and (b) a 
     
     
        compound containing one or two amino nitrogens. .Iaddend. 35. The method of claim .[.30.]. .Iadd.23.Iaddend., wherein said .Iadd.amide-containing compound is a reaction product of (a) a .Iaddend.lactone .[.is.]. selected from the group consisting of γ-butyrolactone, γ-valerolactone, δ-valerolactone and ε-caprolactone .Iadd.and (b) a compound 
     
     
        containing one or two amino nitrogens. .Iaddend. 36. The method of claim .[.30.]. .Iadd.34 or 35.Iaddend., wherein said compound containing .[.at least.]. one .Iadd.or two .Iaddend.amino .[.nitrogen.]. .Iadd.nitrogens .Iaddend.is selected from the group consisting of aminoalcohol, aliphatic mono- or .[.polyamine.]. .Iadd.diamine.Iaddend., aromatic mono- or .[.polyamine.]. .Iadd.diamine .Iaddend.and cyclic mono- or .[.polyamine.]. 
     
     
        .Iadd.diamine. .Iaddend. 37. The method of claim .[.36.]. .Iadd.32 or 33.Iaddend., wherein said aminoalcohol .[.that is reactable with one of said carboxylic acid, carboxylic acid ester, hydroxy carboxylic acid, lactone and lactide,.]. is selected from the group consisting of ethanolamine, diethanolamine, N-methylethanolamine and aminobenzyl 
     
     
        alcohol. 38. The method of claim .[.36.]. .Iadd.34 or 35.Iaddend., wherein said .Iadd.compound containing one or two amino nitrogens is an .Iaddend.aliphatic .[.mono- or polyamine is.]. .Iadd.diamine .Iaddend.selected from the group consisting of ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N,N-dimethylpropylenediamine, hexamethylenediamine and .[.poly(alkyleneoxide diamines).]. 
     
     
        .Iadd.poly(alkyleneoxide) diamine. .Iaddend. 39. The method of claim .[.36.]. .Iadd.34 or 35.Iaddend., wherein said .[.aromatic mono- or polyamine.]. .Iadd.compound containing one or two amino nitrogens 
     
     
        .Iaddend.is benzylamine. 40. The method of claim .[.36.]. .Iadd.34 or 35.Iaddend., wherein said .Iadd.compound containing one or two amino nitrogens is a .Iaddend.cyclic mono- or .[.polyamine is.]. .Iadd.diamine .Iaddend.selected from the group consisting of piperazine, piperidine and 
     
     
        morpholine. 41. The method of claim 23.[., 24.]. or 25, wherein said polyisocyanate is selected from the group consisting of 1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane, toluene diisocyanate and bis(4-isocyanatocyclohexyl)methane.  .[.42. The method of claim 23 or 25, wherein said polyfunctional compound is selected from the group consisting of acrylic acid and hydroxy-containing acrylic ester..]. 
     
     
         3. The method of claim .[.42.]. .Iadd.23.Iaddend., wherein said .[.hydroxy-containing acrylic ester.]. .Iadd.polyfunctional compound .Iaddend.is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl 
     
     
        methacrylate. 44. The method of claim .[.30.]. .Iadd.23 .Iaddend.wherein said amide-containing compound .[.having at least one hydroxy functional group.]. is a reaction product of γ-butyrolactone and ethanolamine, and wherein said reaction product of said γ-butyrolactone and ethanolamine comprises N-(2-hydroxyethyl)pyrrolidone. .Iadd. 45. The addition polymerizable compound of claim 6 or 7 wherein said compound containing one or two amino nitrogens is an aminoalcohol selected from the group consisting of ethanolamine, diethanolamine, N-methylethanolamine and aminobenzyl alcohol. .Iaddend..Iadd. 46. The method of claim 34 or 35 wherein said compound containing one or two amino nitrogens is an aminoalcohol selected from the group consisting of ethanolamine, diethanolamine, N-methylethanolamine and aminobenzyl alcohol. .Iaddend.