Thermoplastic polyurethane golf ball with improved resiliency

• US 6,645,091 B2
• Filed: 01/10/2001
• Issued: 11/11/2003
• Est. Priority Date: 05/14/1999
• Status: Expired due to Term

• Current Assignee: Acushnet Company (FILA Holdings Corp.)
• Original Assignee: Acushnet Company (FILA Holdings Corp.)
• Inventors: Wu, Shenshen, Rajagopalan, Murali
• Primary Examiner(s): Vo, Peter
• Assistant Examiner(s): Kim, Paul D
• Application Number:
  US09/756,761
• Publication Number:
  US 20020098918A1
• Time in Patent Office: 1,035 Days
• Field of Search: 473/372, 473/377, 473/378, 473/385, 525/129, 525/207, 525/208, 524/839, 524/847, 528/66, 528/79
• US Class Current: 473/377
• CPC Class Codes: A63B 37/0003 Golf balls
• CPC Class Codes: A63B 37/0066 Density; Specific gravity
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/3215 containing aromatic groups or benzoquinone groups
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C09D 175/04 Polyurethanes

Abstract

A golf ball comprising a center, a cover, and optionally, at least one intermediate layer disposed between the center and the cover, wherein at least one of the cover and the at least one intermediate layer is formed with a thermoplastic polyurethane composition comprising a reaction product of at least one polyol and at least one diisocyanate, and a curing agent consisting essentially of at least one diol having the formula:

HOH₂CH₂C(OH₂CH₂C)_nO—X—O(CH₂CH₂O)_mCH₂CH₂OH;

wherein n and m, each separately have a value of 0, 1, 2, or 3, X is o-phenylene, m-phenylene, p-phenylene, 1,2-cyclohexyl, 1,3-cyclohexyl, 1,4-cyclohexyl; and mixtures a thereof.

Claims

1. A golf ball comprising a center and a cover, wherein the cover is formed with a thermoplastic polyurethane composition comprising a reaction product of at least one polyol and at least one diisocyanate, and a curing agent consisting essentially of at least one diol having the formula:

2. The golf ball of claim 1, wherein n and m each separately have a value of 1 or 2.

3. The golf ball of claim 1, wherein the thermoplastic polyurethane composition further comprises at least one diol curing agent selected from the group consisting of ethylene glycol;

diethylene glycol;

polyethylene glycol;

propylene glycol;

1,4-butanediol;

1,5-pentanediol;

1,4-cydohexane-dimethanol;

1,6-hexanediol; and

polytetramethylene ether glycol having molecular weight less than 2000.

4. The golf ball of claim 1, wherein the thermoplastic polyurethane composition comprises at least two curing agents.

5. The golf ball of claim 1, wherein the curing agent has a molecular weight of about 50 or greater.

6. The golf ball of claim 1, wherein the at least one diisocyanate is selected from the group consisting of 4,4′

-diphenylmethane diisocyanate;

polymeric 4,4′

-diphenylmethane diisocyanate;

liquid 4,4′

-diphenylmethane diisocyanate;

toluene diisocyanate;

3,3′

-dimethyl-4,4′

-biphenylene diisocyanate;

p-phenylene diisocyanate;

hexamethylene diisocyanate;

p-tetramethylxylene diisocyanate;

m-tetramethylxylene diisocyanate;

naphthalene diisocyanate;

4,4′

-dicyclohexylmethane diisocyanate;

isophorone diisocyanate;

m-phenylene diisocyanate;

low free isocyanate monomers; and

mixtures thereof.

7. The golf ball of claim 6, wherein the at least one diisocyanate is liquid 4,4′

-diphenylmethane diisocyanate.

8. The golf ball of claim 1, wherein the at least one polyol is selected from the group consisting of polytetramethylene ether glycol;

polyoxypropylene glycol;

polyethylene adipate glycol;

polyethylene propylene adipate glycol; and

polybutylene adipate glycol;

ortho-phthalate-1,6-hexanediol polyester polyol;

diethylene glycol initiated polycaprolactone;

trimethylol propane initiated polycaprolactone;

neopentyl glycol initiated polycaprolactone;

1,4-butanediol-initiated polycaprolactone;

16-hexanediol-initiated polycaprolactone;

saturated and unsaturated hydrocarbon polyols;

hydroxy-terminated liquid isoprene rubber;

hydroxy-terminated polybutadiene polyol;

copolymers of the above mentioned polyols; and

mixtures thereof.

9. The golf ball of claim 8, wherein the at least one polyol has a molecular weight from about 200 to 4000.

10. The golf ball of claim 1, wherein the at least one polyol is selected from the group consisting of polytetramethylene ether glycol;

polyethylene adipate glycol;

polybutylene adipate glycol;

diethylene glycol initiated polycaprolactone; and

mixtures thereof.

11. The golf ball of claim 1, wherein the at least one polyol is present in an amount of about 70 to 98 percent by weight of the at least one diisocyanate and the at least one polyol;

the at least one diisocyanate is present in an amount of about 2 to 30 percent by weight of the at least one diisocyanate and the at least one polyol; and

the outing agent is present in an amount of about 10 to 110 weight percent of the at least one diisocyanate and the at least one polyol.

12. The golf ball of claim 11, wherein the at least one diisocyanate is present in an amount of about 2.5 to 12 percent by weight of the at least one diisocyanate and the at least one polyol.

13. The golf ball of claim 1, wherein the thermoplastic polyurethane composition further comprises at least one secondary diamine curing agent.

14. The golf ball of claim 13, wherein the at least one secondary diamine curing agent is selected from the group consisting of 4,4′

-bis-sec-butylamino-diphenylmethane;

1,4-bis-sec-butylamino-benzene;

1,2-bis-sec-butylamino-benzene;

derivatives of 4,4′

-bis-sec-butylamino-diphenylmethane;

1,4-bis-sec-butylamino-cyclohexane;

1,2-bis-sec-butylamino-cyclohexane;

4,4′

-bis-sec-butylamino-diclohexylmethane;

derivatives of 4,4′

-bis-sec-butylamino-dicyclohexylmethane; and

mixtures thereof.

15. The golf ball of claim 1, wherein the thermoplastic polyurethane composition comprises a reaction product of 4,4′

-diphenylmethane diisocyanate;

polytetramethylene ether glycol; and

mixtures of 1,3-bis-(2-hydroxyethoxy) benzene and 1,3-[bis-(2-hydroxyethoxy)]-diethoxy benzene.

16. The golf ball of claim 1, wherein the golf ball further comprises an intermediate layer disposed between the center and the cover.

17. The golf ball of claim 16, wherein the intermediate layer comprises a thermoplastic polyurethane composition.

18. The golf ball of claim 1, wherein the center is a fluid-filled center, a solid center, a gel center, or a hollow center.

19. The golf ball of claim 1, wherein the thermoplastic polyurethane composition further comprises a density-modifying filler.

20. A golf ball comprising a center and a cover, wherein the cover is formed with a thermoplastic polyurethane composition comprising a reaction product of at least one polyol and at least one diisocyanate, and a secondary diamine curing selected from the group consisting of 1,4-bis-(sec-butylamino)-cyclohexane:

1,2-bis-(sec-butylamino)-cyclohexane;

4,4′

-bis-(sec-butylamino)-dicyclohexylmethane;

derivatives of 4,4′

-bis-(sec-butylamino)-dicyclohexylmethane; and

mixtures thereof.

21. The golf ball of claim 20, wherein the thermoplastic polyurethane composition comprises at least two secondary diamine curing agents.

22. The golf ball of claim 20, wherein the at least one diisocyanate is selected from the group consisting of 4,4′

-diphenylmethane diisocyanate;

polymeric 4,4-diphenylmethane diisocyanate;

liquid 4,4′

-diphenylmethane diisocyanate;

toluene diisocyanate;

3,3′

-dimethyl-4,4′

-biphenylene diisocyanate;

p-phenylene diisocyanate;

hexamethylene diisocyanate;

p-tetramethylxylene diisocyanate;

m-tetramethylxylene diisocyanate;

naphthalate diisocyanate;

4,4′

-dicyclohexylmethane diisocyanate;

isophorone diisocyanate;

m-phenylene diisocyanate;

low free isocyanate monomers; and

mixtures thereof.

23. The golf ball of claim 20, wherein the at least one polyol is selected from the group consisting of polytetramethylene ether glycol;

polyoxypropylene glycol;

polyethylene adipate glycol;

polyethylene propylene adipate glycol; and

polybutylene adipate glycol;

ortho-phthalate-1,6-hexanediol polyester polyol;

diethylene glycol initiated polycaprolactone;

trimethylol propane initiated polycaprolactone;

neopentyl glycol initiated polycaprolactone;

1,4-butanediol-initiated polycaprolactone;

1,6-hexanediol-initiated polycaprolactone;

saturated and unsaturated hydrocarbon polyols;

hydroxy-terminated liquid isoprene rubber;

hydroxy-terminated polybutadiene polyol;

copolymers of the above mentioned polyols; and

mixtures thereof.

24. The golf ball of claim 23, wherein the at least one polyol has a molecular weight from about 200 to 4000.

25. The golf ball of claim 23, wherein the at least one polyol is present in an amount of about 70 to 98 percent by weight of the at least one diisocyanate and the at least one polyol;

the at least one diisocyanate is present in an amount of about 2 to 30 percent by weight of the at least one diisocyanate and the at least one polyol; and

the secondary diamine curing agent is present in an amount of about 10 to 110 weight percent of the at least one diisocyanate and the at least one polyol.

26. The golf ball of claim 25, wherein the at least one diisocyanate is present in an amount of about 2.5 to 12 percent by weight of the at least one diisocyanate and the at least one polyol.

27. The golf ball of claim 20, wherein the at least one polyol is selected from the group consisting of polytetramethylene ether glycol;

polyethylene adipate glycol;

polybutylene adipate glycol;

diethylene glycol initiated polycaprolactone; and

mixtures thereof.

28. The golf ball of claim 20, wherein the thermoplastic polyurethane composition comprises a reaction product of 4,4′

-dicyclohexylmethane diisocyanate, copolymer of polytetramethylene ether glycol and polycaprolactone, and 4,4′

-bis-(sec-butylamino)-dicyclohexylmethane.

29. The golf ball of claim 20, wherein the golf ball further comprises an intermediate layer disposed between the center and the cover.

30. The golf ball of claim 20, wherein the intermediate layer is formed of tensioned elastomeric material.

31. The golf ball of claim 20, wherein the center is a fluid-filled center, a solid center, a gel center, or a hollow center.

32. The golf ball of claim 20, wherein the thermoplastic polyurethane composition futher comprises a density-modifying filler.

33. A golf ball comprising a center and a cover, wherein the cover is formed from a thermoplastic polyurethane composition comprising:

a prepolymer comprising at least one polyol and liquid 4,4-diphenylmethane diisocyanate; and

a curing agent.

34. The golf ball of claim 33, wherein the at least one polyol is selected from the group consisting of polytetramethylene ether glycol;

polyoxypropylene glycol;

polyethylene adipate glycol;

polyethylene propylene adipate glycol; and

polybutylene adipate glycol;

ortho-phthalate-1,6-hexanediol polyester polyol;

diethylene glycol initiated polycaprolactone;

trimethylol propane initiated polycaprolactone;

neopentyl glycol initiated polycaprolactone;

1,4-butanediol-initiated polycaprolactone;

1,6-hexanediol-initiated polycaprolactone;

saturated and unsaturated hydrocarbon polyols;

hydroxy-terminated liquid isoprene rubber;

hydroxy-terminated polybutadiene polyol;

copolymers of the above mentioned polyols; and

mixtures thereof.

35. The golf ball of claim 33, wherein the at least one polyol is present in an amount of about 70 to 98 percent by weight of the prepolymer;

the liquid 4,4′

-diphenylmethane diisocyanate is present in an amount of about 2 to 30 percent by weight of the prepolymer; and

the curing agent is present in an amount of about 10 to 110 weight percent of the prepolymer.

36. The golf ball of claim 33, wherein the liquid 4,4′

-diphenylmethane diisocyanate is present in an amount of about 2.5 to 12 percent by weight of the prepolymer.

37. The golf ball of claim 33, wherein the curing agent comprises at least one secondary diamine curing agent, at least one diol curing agent, or mixtures thereof.

38. The golf ball of claim 37, wherein the at least one secondary diamine curing agent is selected from the group consisting of 4,4′

-bis-sec-butylamino-diphenylmethane;

1,4-bis-sec-butylamino-benzene;

1,2-bis-sec-butylamino-benzene;

derivatives of 4,4′

-bis-sec-butylamino-diphenylmethane;

1,4-bis-sec-butylamino-cyclohexane;

1,2-bis-sec-butylamino-cyclohexane;

4,4′

-bis-sec-butylamino-diclohexylmethane;

derivatives of 4,4-bis-sec-butylamino-dicyclohexylmethane; and

mixtures thereof.

39. The golf ball of claim 37, wherein the at least one diol curing agent is selected from the group consisting of ethylene glycol;

diethylene glycol;

polyethylene glycol;

propylene glycol;

1,4-butanediol;

1,5-pentanediol;

1,4-cydohexane-dimethanol;

1,6-hexanediol;

polytetramethylene ether glycol having molecular weight less than 2000; and

mixtures thereof.

40. The golf ball of claim 33, wherein the curing agent comprises at least one diol having the formula:

41. The golf ball of claim 40, wherein the cover has a hardness of about 30 Shore D to about 60 Shore D.