In-mold appearance coatings for nylon and nylon based thermoplastic substrates

1. An in-mold coating for in-mold coating a nylon based plastic substrate, the coating comprising by weight a coreactive polymerizable composition of:

at least about 10% of a urethane-acrylate oligomer having at least one terminal acrylate and/or methacrylate group and a number average molecular weight from about 500 to about 8000;

at least about 0.2% of an alkylsulfonic acid functional acrylate having a terminal acrylate or methacrylate group;

at least about 0.2% of acrylic acid and/or methacrylic acid; and the balance including at least one other coreactive polymerizable diacrylate and/or mono-ethylenically unsaturated monomer.

2. The in-mold coating composition of claim 1 , wherein the urethane-acrylate oligomer has a molecular weight from about 500 to about 4000.

3. The in-mold coating composition of claim 1 , wherein the alkylsulfonic acid functional acrylate is an alkylsulfonic acid amido acrylate and comprises from about 0.2% to about 5% of the coreactive polymerizable composition.

4. The in-mold coating composition of claim 3 , wherein the alkylsulfonic acid monomer comprises from about 0.5% to about 2% of the coreactive polymerizable composition.

5. The in-mold coating composition of claim 3 , wherein the alkylsulfonic acid amido acrylate is terminated with an acrylate group.

6. The in-mold coating composition of claim 3 , wherein the alkylsulfonic acid amido acrylate is terminated with a methacrylate group.

7. The in-mold coating composition of claim 3 , wherein the alkylsulfonic acid functional acrylate comprises 2-acrylamido-2-methyl propane sulfonic acid.

8. The in-mold coating composition of claim 1 , containing from about 0.2% to about 5% acrylic acid.

9. The in-mold coating composition of claim 8 , wherein the polymerizable composition contains from about 0.5% to about 2% acrylic acid.

10. The in-mold coating composition of claim 1 , containing from about 0.2% to about 5% of methacrylic acid.

11. The in-mold coating composition of claim 10 , wherein the polymerizable composition contains from about 0.5% to about 2% methacrylic acid.

12. The in-mold coating composition of claim 1 , containing from about 10 to about 40 weight parts of a coreactive polymerizable acrylate diester Of a diol per 100 weight parts of urethane-acrylate oligomer.

13. The in-mold coating composition of claim 12 , wherein the acrylate diester of a diol comprises a diacrylate terminated with acrylate end groups.

14. The in-mold coating composition of claim 12 , wherein the acrylate diester of a diol comprises a dimethacrylate terminated with methacrylate end 25 groups.

15. The in-mold coating composition of claim 1 , containing from about 5 to about 25 weight parts of a coreactive polymerizable hydroxyl functional acrylate or methacrylate per 100 weight parts of urethane-acrylate oligomer.

16. The in-mold coating composition of claim 1 , containing from about 30 to about 80 weight parts of a coreactive polymerizable isobornyl acrylate or methacrylate per 100 weight parts of urethane-acrylate oligomer.

17. The in-mold coating composition of claim 1 , containing from about 20 weight parts to about 80 weight parts of a coreactive polymerizable vinyl aromatic monomer per 100 weight parts of urethane-acrylate oligomer.

18. The in-mold coating composition of claim 17 , wherein the vinyl aromatic monomer comprises styrene.

19. The in-mold coating composition of claim 1 , wherein the coreactive polymerizable diacrylate is an acrylate diester of a diol and comprises from about 5% to about 20% of the polymerizable in-mold coating composition.

20. The in-mold coating composition of claim 19 , wherein the acrylate diester is an ester of acrylic acid and comprises from about 5% to about 15% of the polymerizable in-mold coating composition.

21. The in-mold coating composition of claim 19 , wherein the acrylate diester is an ester of methacrylic acid and comprises from about 5% to about 15% of the polymerizable in-mold coating composition.

22. The in-mold coating composition of claim 1 , wherein the mono-ethylenically unsaturated monomer is an hydroxyl acrylate or methacrylate and comprises from about 1% to about 15% of the polymerizable in-mold coating composition.

23. The in-mold coating composition of claim 22 , wherein the hydroxyl acrylate or methacrylate is hydroxyl-alky acrylate and comprises from about 2% at about 10% of the polymerizable in-mold coating composition.

24. The in-mold coating composition of claim 22 , wherein the hydroxyl acrylate or methacrylate is hydroxy-alkyl methacrylate and comprises from about 2% to about 10% of the polymerizable in-mold coating composition.

25. The in-mold coating composition of claim 1 , wherein the mono-ethylenically unsaturated monomer is isobornyl acrylate or methacrylate and comprises from about 10% to about 40% of the polymerizable in-mold coating composition.

26. The in-mold coating composition of claim 25 , wherein the isobornyl acrylate or methacrylate is isobornyl acrylate and comprises from about 20% to about 30% of the polymerizable in-mold coating composition.

27. The in-mold coating composition of claim 25 , wherein the isobornyl acrylate or methacrylate is isobornyl methacrylate and comprises from about 20% to about 30% of the polymerizable in-mold coating compositions.

28. The in-mold coating composition of claim 1 , wherein the mono-ethylenically unsaturated monomer is vinyl aromatic monomer and comprises from about 1% to about 30% of the polymerizable in-mold coating composition.

29. The in-mold coating composition of claim 28 , wherein the vinyl aromatic monomer comprises from about 10% to about 20% of the polymerizable in-mold coating composition.

30. The in-mold coating composition of claim 28 , wherein the vinyl aromatic monomer comprises styrene.

31. The in-mold coating composition of claim 1 , wherein the coreactive polymerizable composition comprises by weight:

from about 10% to about 50% urethane-acrylate oligomer;

from about 0.2% to about 5% alkylsulfonic acid amido acrylate and/or methacrylate;

from about 0.2% to about 5% of acrylic acid and/or methacrylate acid;

from about 5% to about 20% of an acrylate and/or methacrylate diester of a diol;

from about 1% to about 15% of an hydroxyl-alkyl acrylate or methacrylate;

from about 10% to about 40% of an isobornyl acrylate and/or methacrylate;

from about 1% to about 30% of a vinyl aromatic monomer.

32. The in-mold coating composition of claim 31 , containing from about 20% to 40% urethane-acrylate oligomer.

33. The in-mold coating composition of claim 31 , containing from about 5 to about 15% of the acrylate and/or methacrylate diester of a diol.

34. The in-mold coating of claim 31 , containing from about 20% to about 30% of the isobornyl acrylate and/or methacrylate.

35. The in-mold coating composition of claim 31 , containing from about 10% to about 20% of the vinyl aromatic monomer.

36. The in-mold coating composition of claim 31 , wherein the vinyl aromatic monomer comprises styrene.

37. An in-mold coating for a thermoplastic substrate, the in-mold coating comprising:

a urethane-acrylate oligomer having at least one terminal acrylate and/or methacrylate group and a number average molecular weight of from about 500 to about 8000;

from about 0.25 to about 6 parts by weight of a sulfonic acid functional acrylate and/or methacrylate monomer; and

from about 1 to about 8 parts by weight of an acrylic acid and/or methacrylic acid; and

wherein said parts by weight are based upon 100 parts by weight of said urethane-acrylate oligomer.

38. The in-mold coating composition of claim 37 , wherein the amount of said sulfonic acid functional monomer is from about 0.5 to about 4 parts by weight, and wherein the amount of said acrylic acid and/or methacrylic acid is from about 1.5 to about 6 parts by weight.

39. The in-mold coating composition of claim 37 , further comprising from about 10 to about 40 parts by weight of an acrylate and/or methacrylate diester of a diol, from about 5 to about 25 parts by weight of a hydroxyl functional acrylate or methacrylate, from about 30 to about 80 parts by weight isobornyl acrylate and/or methacrylate, and from about 20 to about 80 parts by weight of a vinyl substituted aromatic, and wherein said parts by weight are based upon 100 parts by weight of said urethane-acrylate oligomer.

40. The in-mold coating composition of claim 38 , comprising from about 15 to about 30 parts by weight of the acrylate and/or methacrylate diester of a diol, from about 5 to about 15 parts by weight of the hydroxyl functional acrylate and/or methacrylate, from about 30 to about 50 parts by weight isobornyl acrylate and/or methacrylate, and from about 30 to about 50 parts by weight of said vinyl substituted aromatic, and wherein said parts by weight are based upon 100 parts by weight of said urethane-acrylate oligomer.

41. The in-mold coating composition of claim 39 , wherein said urethane-acrylate oligomer has a number average molecular weight of from about 500 to about 4000 and is derived from a polyester urethane and has 2 terminal acrylate groups, wherein said sulfonic acid functional acrylate is alkylsulfonic acid amido acrylate, wherein said acid is methacrylic acid, wherein said acrylic diester of a diol is hexamethylene diacrylate, wherein said hydroxy functional methacrylate is hydroxypropyl methacrylate, wherein said vinyl substituted aromatic is styrene, and wherein said isobornyl compound is isobornyl acrylate.

42. The in-mold coating composition of claim 40 , wherein said urethane-acrylate oligomer has a number average molecular weight of from about 500 to about 4000 and is derived from a polyester urethane and has 2 terminal acrylate groups, wherein said sulfonic acid functional acrylate is alkylsulfonic acid amido acrylate, wherein said acid is methacrylic acid, wherein said acrylic diester of a diol is hexamethylene diacrylate, wherein sdaid hydroxy functional methacrylate is hydroxypropyl methacrylate, wherein said vinyl substituted aromatic is styrene, and wherein said isobornyl compound is isobornyl acrylate.

43. The in-mold coating composition of claim 37 , wherein the thermoplastic substrate is nylon, or a nylon alloy blended with a thermoplastic resin, or a nylon blended with a thermoplastic resin, or combinations thereof.

44. The in-molded coating composition of claim 42 , wherein the thermoplastic substrate is nylon, or a nylon alloy blended with a thermoplastic resin, or a nylon blended with a thermoplastic resin, or combinations thereof, and wherein said coating is heat cured on said substrate.

45. A molded thermoplastic laminate, comprising:

an injection molded thermoplastic substrate, a cured in-mold coating located upon at least a portion of said substrate, said in-mold coating derived from:

a urethane-acrylate oligomer having a number average molecular weight from about 500 to about 8000;

from about 0.25 to about 6 parts by weight of a sulfonic acid amido acrylate or methacrylate monomer;

from about 1 to about 8 parts by weight of an acrylic acid or methacrylic monomer;

from about 10 to about 40 parts by weight of an acrylic and/or methacrylic diester of diol;

from about 5 to about 25 parts by weight of an hydroxyl functional acrylate or methacrylate;

from about 30 to about 80 parts by weight of isobornyl acrylate and/or methacrylate; and

from about 20 to about 80 parts by weight of a vinyl substitued aromatic monomer,

wherein said parts by weight are based upon 100 parts by weight of said urethane-acrylate oligomer, and

wherein said thermoplastic substrate is a nylon polymer or copolymer.

46. The laminate according to claim 45 , wherein the urethane-acrylate oligomer has a molecular weight of from about 500 to about 4000.

47. The laminate according to claim 46 , wherein the amount of said sulfonic acid amido acrylate or methacrylate monomer is from about 0.5 to about 4 parts by weight,

wherein the amount of said acrylic acid or methacrylic monomer is from about 1.5 to about 6 parts by weight,

wherein the amount of said acrylic and/or methacrylic diester of diol is from about 15 to about 30 parts by weight,

wherein the amount of said hydroxyl functional acrylate or methacrylate is from about 5 to about 15 parts by weight,

wherein the amount of said isobornyl acrylate and/or methacrylate is from about 30 to about 50 parts by weight, and

wherein the amount of said vinyl substituted aromatic monomer is from about 30 about 50 parts by weight.

48. The laminate according to claim 46 , wherein said urethane-acrylate is derived from a polyester urethane and has 2 terminal acrylate groups, wherein said sulfonic acid functional acrylate is alkylsulfonic acid amido acrylate, wherein said acid is methacrylic acid, wherein said acrylic diester of a diol is hexamethylene diacrylate, wherein said hydroxy functional methacrylate is hydroxypropyl methacrylate, wherein said vinyl substituted aromatic is styrene, and wherein said isobornyl compound is isobornyl acrylate.

49. The laminate according to claim 47 , wherein said urethane-acrylate is derived from a polyester urethane and has 2 terminal acrylate groups; wherein said sulfonic acid functional acrylate is alkylsulfonic acid amido acrylate, wherein said acid is methacrylic acid, wherein said acrylic diester of a diol is hexamethylene diacrylate, wherein said hydroxy functional methacrylate is hydroxypropyl methacrylate, wherein said vinyl substituted aromatic is styrene, and wherein said isobornyl compound is isobornyl acrylate.

50. The laminate according to claim 45 , wherein said substrate is nylon, modified nylon, a nylon alloy, or a blend of a nylon and a thermoplastic.

51. The laminate according to claim 47 , wherein said substrate is a nylon, or a nylon blended with a thermoplastic.

52. The laminate according to claim 49 , wherein said substrate is nylon, or nylon blended with polycarbonate or blended with polyester.

53. An in-mold coating process, comprising the steps of:

injection molding a thermoplastic substrate,

applying in-mold coating on said thermoplastic substrate, said in-mold coating comprising:

about 100 parts by weight of a urethane-acrylate oligomer having a number average molecular weight from about 500 to about 8000,

from about 0.25 to about 6 parts by weight of an alkylsulfonic acid functional amido acrylate or methacrylate,

from about 1 to about 8 parts by weight of an acrylic acid monomer,

from about 10 to about 40 parts by weight of an acrylate or methacrylate diester of a diol,

from about 5 to about 25 parts by weight of an hydroxyl functional alkyl acrylate or methacrylate,

from about 30 to about 80 parts by weight of isobornyl acrylate or methacrylate, and

from about 20 to about 80 parts by weight of a vinyl aromatic monomer;

wherein said parts by weight are based upon 100 parts by weight of said urethane-acrylate oligomer, and

polymerizing the in-mold coating to form a thermoset coating on said thermoplastic substrate.

54. The in-mold coating process of claim 53 , wherein the amount of said acrylic acid and/or methacrylic acid is from about 2 to about 8 parts by weight, and wherein the amount of said alkylsulfonic acid function amido acrylate or methacrylate is from about 0.5 to about 4 parts by weight.

55. The in-mold coating process of claim 54 , wherein the substrate comprises a nylon, or a nylon blended with a thermoplastic.