Aqueous coating compositions containing acetoacetyl-functional polymers, coatings, and methods

• US 20060135684A1
• Filed: 12/14/2005
• Published: 06/22/2006
• Est. Priority Date: 12/17/2004
• Status: Active Grant

• Current Assignee: Swimc, LLC (The Sherwin-Williams Company)
• Original Assignee: Valspar Sourcing, Inc. (Sherwin-Williams Company)
• Inventors: Killilea, T. Howard
• Granted Patent: US 9,803,045 B2
• Time in Patent Office: Days
• US Class Current: 524/556
• CPC Class Codes: C08G 18/0823 containing carboxylate salt groups or groups forming them
• CPC Class Codes: C08G 18/6659 with compounds of group C08G18/34
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C09D 133/14 of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C09D 175/16 having terminal carbon-to-carbon unsaturated bonds

Abstract

Aqueous coating compositions that include polymers having one or more of the following acetoacetyl-functional groups:
wherein R¹ is a C1 to C22 alkylene group and R² is a C1 to C22 alkyl group.

Claims

1. A coating composition comprising:

water;

a polymer comprising one or more acetoacetyl functional groups of the formula;

wherein R¹ is a C1 to C22 alkylene group and R² is a C1 to C22 alkyl group; and

a (meth)acrylate functional compound distinct from the polymer comprising acetoacetyl functionality.

2. The coating composition of claim 1 comprising no more than 10 wt-% volatile organic compounds, based on the total weight of the composition.

3. The coating composition of claim 1 wherein the (meth)acrylate functional compound is a monomer, oligomer, polymer, or mixture thereof.

4. The coating composition of claim 1 wherein the (meth)acrylate functional compound is a multifunctional monomer.

5. The coating composition of claim 4 wherein the (meth)acrylate-functional monomer selected from the group consisting of isobornyl (meth)acrylate, isodecyl (meth)acrylate, phenoxyethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, tripropylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, beta-carboxyethyl (meth)acrylate, bisphenol A ethoxylate di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, di-(trimethyolpropane tetra (meth)acrylate), pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and mixtures thereof.

6. The coating composition of claim 1 wherein the acetoacetyl-functional polymer comprises an acetoacetyl-functional polyurethane, epoxy, polyamide, chlorinated polyolefin, acrylic, oil-modified polymer, polyester, or mixtures or copolymers thereof.

7. The coating composition of claim 1 wherein the acetoacetyl-functional polymer comprises an acetoacetyl-functional latex polymer prepared from ethylenically unsaturated monomers.

8. The coating composition of claim 7 wherein the acetoacetyl-functional latex polymer comprises latex particles having an average particle size of less than 75 nm.

9. The coating composition of claim 7 wherein the ethylenically unsaturated monomers used in preparing the acetoacetyl-functional latex polymer are selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidylether, acrylamide, methylacrylamide, styrene, α

-methyl styrene, vinyl toluene, vinyl acetate, vinyl propionate, allyl methacrylate, and mixtures thereof.

10. The coating composition of claim 1 wherein the acetoacetyl-functional polymer is present in an amount of at least 30 wt-% and no more than 95 wt-%, based on the combined weight of the (meth)acrylate functional compound and the acetoacetyl-functional polymer.

11. The coating composition of claim 1 wherein the (meth)acrylate functional compound is present in an amount of at least 5 wt-% and no more than 70 wt-%, based on the combined weight of the (meth)acrylate functional compound and the acetoacetyl-functional polymer.

12. The coating composition of claim 1 wherein the acetoacetyl functional group is incorporated into the polymer using 2-(acetoacetoxy) ethyl methacrylate, t-butyl acetoacetate, diketene, or combinations thereof.

13. The coating composition of claim 1 further comprising a free-radical initiator.

14. The coating composition of claim 13 wherein the free-radical initiator comprises a photoinitiator, a thermal initiator, a catalyst for auto-oxidative cure, or combinations thereof.

15. The coating composition of claim 14 wherein the free radical initiator is a photoinitiator.

16. The coating composition of claim 15 wherein the photoinitiator comprises benzophenone, 4-methylbenzophenone, benzoyl benzoate, phenylacetophenones, 2,2-dimethoxy-2-phenylacetophenone, alpha,alpha-diethoxyacetophenone, hydroxycyclo-hexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, or combinations thereof.

17. The coating composition of claim 15 wherein the photoinitiator is a hydrogen abstraction-type photoinitiator.

18. The coating composition of claim 17 wherein the hydrogen abstraction-type photoinitiator is benzophenone or 4-methylbenzophenone.

19. The coating composition of claim 18 which is at least partially curable by ultraviolet or visible light.

20. A method of coating a substrate, the method comprising applying the coating composition of claim 1 to a substrate and allowing the coating composition to harden.

21. A coating on a substrate preparable by the method of claim 20.

22. A coating composition comprising:

water;

a polymer comprising one or more acetoacetyl functional groups of the formula;

wherein R¹ is a C1 to C22 alkylene group and R² is a C1 to C22 alkyl group;

an ethylenically unsaturated compound distinct from the polymer comprising acetoacetyl functionality; and

a photoinitiator.

23. The coating composition of claim 22 comprising no more than 10 wt-% volatile organic compounds, based on the total weight of the composition.

24. The coating composition of claim 22 wherein the ethylenically unsaturated compound is a monomer, oligomer, polymer, or mixture thereof and wherein the ethylenically unsaturated compound comprises (meth)acrylate functionality, vinyl ether functionality, vinyl functionality, (meth)allyl ether functionality, or mixtures thereof.

25. The coating composition of claim 24 wherein the ethylenically unsaturated compound comprises (meth)acrylate functionality, wherein the (meth)acrylate-functional compound is selected from the group consisting of isobornyl (meth)acrylate, isodecyl (meth)acrylate, phenoxyethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, tripropylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, beta-carboxyethyl (meth)acrylate, bisphenol A ethoxylate di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, di-(trimethyolpropane tetra (meth)acrylate), pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and mixtures thereof.

26. The coating composition of claim 22 wherein the acetoacetyl-functional polymer comprises an acetoacetyl-functional polyurethane, epoxy, polyamide, chlorinated polyolefin, acrylic, oil-modified polymer, polyester, or mixtures or copolymers thereof.

27. The coating composition of claim 22 wherein the acetoacetyl-functional polymer comprises an acetoacetyl-functional latex polymer.

28. The coating composition of claim 27 wherein the acetoacetyl-functional latex polymer comprises latex particles having an average particle size of less than 75 nm.

29. The coating composition of claim 22 wherein the acetoacetyl-functional polymer is present in an amount of at least 30 wt-% and no more than 95 wt-%, based on the combined weight of the ethylenically unsaturated compound and the acetoacetyl-functional polymer, and wherein the ethylenically unsaturated compound is present in an amount of at least 5 wt-% and no more than 70 wt-%, based on the combined weight of the ethylenically unsaturated compound and the acetoacetyl-functional polymer.

30. The coating composition of claim 22 wherein the acetoacetyl functionality is incorporated into the polymer using 2-(acetoacetoxy) ethylmethacrylate, t-butyl acetoacetate, or diketene.

31. The coating composition of claim 22 wherein the photoinitiator comprises benzophenone, 4-methylbenzophenone, benzoyl benzoate, phenylacetophenones, 2,2-dimethoxy-2-phenylacetophenone, alpha,alpha-diethoxyacetophenone, hydroxycyclo-hexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, or combinations thereof.

32. The coating composition of claim 22 wherein the photoinitiator initiator is a hydrogen abstraction-type photoinitiator.

33. The coating composition of claim 32 wherein the hydrogen abstraction-type photoinitiator is benzophenone or 4-methylbenzophenone.

34. A method of coating a substrate, the method comprising a applying the coating composition of claim 22 to a substrate and exposing the coating composition to ultraviolet or visible light.

35. A coating on a substrate preparable by the method of claim 34.

36. A method of coating a substrate surface, the method comprising:

providing a coating composition comprising;

water;

a polymer comprising one or more acetoacetyl-functional groups of the formula;

wherein R¹ is a C1 to C22 alkylene group and R² is a C1 to C22 alkyl group;

a (meth)acrylate functional compound distinct from the polymer comprising acetoacetyl functionality; and

optionally an initiator;

applying the coating composition to a substrate surface; and

at least partially curing the coating composition.

37. A method of coating a substrate surface, the method comprising:

providing a coating composition comprising;

water;

a polymer comprising one or more acetoacetyl-functional groups of the formula;

wherein R¹ is a C1 to C22 alkylene group and R² is a C1 to C22 alkyl group;

an ethylenically unsaturated compound distinct from the polymer comprising acetoacetyl functionality; and

a photoinitiator;

applying the coating composition to a substrate surface; and

applying ultraviolet or visible light to the coating composition to at least partially cure the coating composition.