AQUEOUS CROSS-LINKING COMPOSITIONS AND METHODS

• US 20120142847A1
• Filed: 06/03/2011
• Published: 06/07/2012
• Est. Priority Date: 06/04/2010
• Status: Active Grant

• Current Assignee: Benjamin Moore & Company (Berkshire Hathaway Incorporated)
• Original Assignee: Columbia Insurance Company (Berkshire Hathaway Incorporated)
• Inventors: Yang, Yong, Chen, Yue, Tilara, Navin, Sheerin, Robert J., Mauck, Jean Fredrick, Garcia de Visicaro, Johanna
• Granted Patent: US 9,790,374 B2
• Time in Patent Office: Days
• US Class Current: 524/556
• CPC Class Codes: C08G 59/4014 Nitrogen containing compounds
• CPC Class Codes: C08K 5/30 Hydrazones; Semicarbazones
• CPC Class Codes: C08L 2201/56 Non-aqueous solutions or dispersions
• CPC Class Codes: C09D 133/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• CPC Class Codes: C09D 133/068 containing glycidyl groups
• CPC Class Codes: C09D 163/00 Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• CPC Class Codes: C09D 5/024 characterised by the additives

Abstract

Water-borne cross-linking polymeric compositions and related embodiments, such as methods of making and using the compositions, as well as products formed with said compositions are described. For example, the water-borne composition may comprise polymers incorporating cross-linking functionality such as, but not limited to, carbonyl or epoxy functionality, and a blocked cross-linking agent, for example, a hydrazone. The cross-linking functionality does not react with the blocked cross-linking agent; however, the blocked cross-linking agent is capable of reacting with the alternative form cross-linking agent such as, but not limited to, a hydrazide, to yield a cross-linked polymer. The alternative form cross-linking agent may be formed in an equilibrium reaction including the blocked cross-linking agent.

Claims

1. A water-borne polymeric composition, which comprises water;

at least one polymer comprising one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups; and

a blocked cross-linking agent having at least one hydrazone group incorporated therein.

2. The water-borne polymeric composition of claim 1, which comprises different chain polymers comprising one or more reactive carbonyl groups, one or more reactive epoxy groups, or both one or more reactive carbonyl groups and one or more reactive epoxy groups.

3. The water-borne polymeric composition of claim 2, wherein the polymers are present in the composition in a range of 3% to 60% by weight.

4. The water-borne polymeric composition of claim 3, wherein a ratio of the moles of blocked cross-linking agent to the number of said reactive groups from 0.1:

1 to 2;

1.

5. The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent comprises at least two hydrazone groups.

6. The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent further comprises a hydrazine group.

7. The water-borne polymeric composition of claim 1, wherein the pH of the composition is from 6.5 to 10.3.

8. The water-borne polymeric composition of claim 7, wherein the pH of the composition is from 8.0 to 9.8.

9. The water-borne polymeric composition of claim 8, wherein the pH of the composition is from 8.5 to 9.5.

10. The water-borne polymeric composition of claim 1, which comprises the blocked cross-linking agent of formula:

11. The water-borne polymeric composition of claim 10, wherein each of R1, R2, R3, and R4 is selected to be, independently of the others:

C1 to C12 linear alkyl, alkenyl, or alkynyl;

or a branched alkyl, alkenyl, or alkynyl having a C1 to C 12 primary chain;

or R1 and R2 or R3 and R4 are joined together to form a cyclic organic group or said linear or branched alkyl, alkenyl, or alkynyl being substituted with an hydroxyl, amino, phenyl, benzyl, or halogen.

12. The water-borne polymeric composition of claim 11, wherein each of R1, R2, R3, and R4 is selected to be independently of the others methyl, ethyl, n-propyl, n-butyl, iso-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

14. The water-borne polymeric composition of claim 1, wherein the carbonyl is incorporated within a ketone, aldehyde, or anhydride group.

15. The water-borne polymeric composition of claim 1, wherein the polymeric composition functions as a paint, primer, other coating, ink, or adhesive.

16. The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent comprises two or more hydrazone groups.

17. The water-borne polymeric composition of claim 16, wherein the blocked cross-linking agent has the following formula:

18. The water-borne polymeric composition of claim 17, wherein R is oxalic, malonic, succinic, glutaric, adipic or sebacic.

19. The water-borne polymeric composition of claim 16, wherein the blocked cross-linking agent has the following formula:

20. The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent is adipic di(2-butylidene hydrazide).

13. The water-borne polymeric composition of claim 13, wherein the cyclic group is cyclopentyl or cyclohexyl.

21. A cross-linked polymeric material, which comprises

a first polymer moiety and a second polymer moiety;

and

cross-linkage formed by reaction of a cross-linking agent with each of the first and second polymer moieties, which agent is derived from a blocked cross-linking agent having at least one hydrazone group incorporated therein, said cross-linkage being between a plurality of sites on the first polymer moiety and their respective corresponding sites on the second polymer moiety via a cross-linking moiety attached at one of said sites on the first polymer moiety and also at the corresponding site on the second polymer moiety;

each of the sites on the first and second polymer moieties being one at which there was a carbonyl group or epoxy group prior to cross-linking.

22. A method of preparing a water-borne composition, comprising:

combining a blocked cross-linking agent comprising at least one hydrazone group and an aqueous dispersion of one or more cross-linkable polymers, wherein at least one polymer in the dispersion comprises one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups.

23. A method of making a cross-linked polymeric material, which comprises combining

an aqueous dispersion containing a first polymer moiety having incorporated therein one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups, and a second polymer moiety having incorporated therein one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups;

and

a blocked cross-linking agent having at last one hydrazone group incorporated therein.

24. A method of coating a surface, comprising:

applying an water-borne polymeric dispersion on a surface, wherein the aqueous polymeric dispersion comprises water, one or more polymers, and a blocked cross-linking agent comprising at least one hydrazone group, wherein at least one of the polymers comprises one or more carbonyl groups, one or more epoxy groups or a combination of one or more carbonyl groups and one or more epoxy groups.

50. A material adherent to a surface which is formed in accordance with the method defined in claim 24.

25. A water-borne composition, comprising:

water;

at least one polymer having functionality capable of reacting with a cross-linking agent; and

a blocked cross-linking agent comprising at least one functional group that is not capable of reacting with said functionality of the polymer but is convertible via an equilibrium reaction to an alternate functional group to provide the cross-linking agent which is capable of reacting with said functionality.

26. The water-borne composition of claim 25, wherein the equilibrium reaction produces a byproduct and the equilibrium is shifted to the second functional group by evaporation of byproduct.

27. A water-borne primer latex, comprising:

water;

a plurality of polymers comprising a number average molecular weight less than 100,000 Daltons, a glass transition temperature less than 10°

C., and one or more carbonyl groups, one or more epoxy groups, or a combination of one or more carbonyl groups and one or more epoxy groups; and

a blocked cross-linking agent having at least one hydrazone group incorporated therein.

28. The water-borne primer latex of claim 27, wherein the glass transition temperature is less than 6°

C.

29. The water-borne primer latex of claim 27, wherein the glass transition temperature is less than 4°

C.

30. The water-borne primer latex of claim 27, wherein polymers comprise a number average molecular weight less than 50,000 Daltons.

31. The water-borne primer latex of claim 27, wherein polymers comprise a number average molecular weight less than 25,000 Daltons,

32. The water-borne primer latex of claim 27, wherein the polymers are present in the composition in a range of 3% to 60% by weight.

33. The water-borne primer latex of claim 27, wherein a ratio of the moles of blocked cross-linking agent and the number of reactive carbonyl and epoxy groups on the polymer chains is from 0.1:

1 to 2;

1.

34. The water-borne primer latex of claim 27, wherein the blocked cross-linking agent comprises at least two hydrazone groups.

35. The water-borne primer latex of claim 27, wherein the blocked cross-linking agent further comprises a hydrazine group.

36. The water-borne primer latex of claim 27, wherein the pH of the composition is from 6.5 to 10.3.

37. The water-borne primer latex of claim 27, wherein the blocked cross-linking agent is of the formula:

38. The water-borne primer latex of claim 37, wherein each of R1, R2, R3, and R4 is selected to be independently of the others:

C1 to C12 linear alkyl, alkenyl, or alkynyl group;

a branched alkyl, alkenyl, or alkynyl group having a C1 to C12 primary chain;

or R1 and R2 or R3 and R4 joined together to form a cyclic organic group or said linear or branched alkyl, alkenyl, or alkynyl group substituted with an hydroxyl, amino, phenyl, benzyl, or halogen.

39. The water-borne primer latex of claim 38, wherein each of R1, R2, R3, and R4 is selected to be independently of the others methyl, ethyl, n-propyl, n-butyl, iso-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

40. The water-borne primer latex of claim 38, wherein the cyclic group is cyclopentyl or cyclohexyl.

41. The water-borne primer latex of claim 27, wherein the carbonyl is incorporated within ketone, aldehyde, or anhydride group.

42. The water-borne primer latex of claim 35, wherein the blocked cross-linking agent has the following formula:

43. The water-borne primer latex of claim 42, wherein R is oxalic, malonic, succinic, glutaric, adipic or seberic.

44. The water-borne primer latex of claim 27, wherein the blocked cross-linking agent has the following formula:

45. The water-borne primer latex of claim 27, wherein the blocked cross-linking agent is adipic di(2-butylidene hydrazide).

51. A material adherent to a surface which is formed in accordance with the method defined in claim 30.

46. A cross-linked polymeric material, which comprises

a first polymer moiety and a second polymer moiety;

and

cross-linkage formed by reaction of a cross-linking agent with each of the first and second polymer moieties, which cross-linking agent is derived from a blocked cross-linking agent having at least one functional group that is not capable of reacting with any functionality of said first or second polymer moiety but is convertible via an equilibrium reaction to an alternative functional group to provide the cross-linking agent, said cross-linkage being between a plurality of sites on the first polymer moiety and their respective corresponding sites on the second polymer moiety via a cross-linking moiety attached at one of said sites on the first polymer moiety and also at the corresponding site on the second polymer moiety;

each of the sites on the first and second polymer moieties being one at which there was a functionality capable of reacting with the cross-linking agent.

47. A method of preparing a water-borne composition, comprising:

combining an aqueous dispersion of one or more cross-linkable polymers, wherein at least one polymer in the dispersion has functionality capable of interacting with a cross-linking agent, and a blocked cross-linking agent that is not capable of reacting with said functionality but is convertible via an equilibrium reaction to said cross-linking agent.

48. A method of making a cross-linked polymeric material, which comprises combining

an aqueous dispersion of a first polymer moiety and a second polymer moiety, each of said polymer moieties comprising functionality capable of reacting with a cross-linking agent;

and

a blocked cross-linking agent that is not capable of reacting with said functionality but is convertible via an equilibrium reaction to said cross-linking agent.

49. A method of depositing adherent material on a surface, comprising:

applying an water-borne polymeric dispersion on a surface, wherein the water-borne polymeric dispersion comprises water, one or more polymers which include functionality capable of reacting with a cross-linking agent, and a blocked cross-linking agent that is not capable of reacting with said functionality but is convertible via an equilibrium reaction to said cross-linking agent.