Low compression, resilient golf balls including an organosulfur catalyst and method for making same

• US 6,465,578 B1
• Filed: 12/16/1999
• Issued: 10/15/2002
• Est. Priority Date: 12/24/1998
• Status: Expired due to Term

• Current Assignee: Acushnet Company (FILA Holdings Corp.)
• Original Assignee: Acushnet Company (FILA Holdings Corp.)
• Inventors: Ladd, Derek, Bulpett, David A., Dalton, Jeffrey L., Bissonnette, Laurent C., Rajagopalan, Murali, Wrigley, Mark N., Gosetti, Steven M.
• Primary Examiner(s): Buttner, David J.
• Application Number:
  US09/461,736
• Time in Patent Office: 1,034 Days
• Field of Search: 525/261, 525/274, 473/354, 473/357, 473/371, 473/372, 473/373, 473/374, 473/377
• US Class Current: 525/261
• CPC Class Codes: A63B 37/0003 Golf balls
• CPC Class Codes: A63B 37/0021 Occupation ratio, i.e. percentage surface occupied by dimples
• CPC Class Codes: A63B 37/003 Coefficient of restitution
• CPC Class Codes: A63B 37/0031 Hardness
• CPC Class Codes: A63B 37/0034 Deflection or compression
• CPC Class Codes: A63B 37/0037 Flexural modulus; Bending stiffness
• CPC Class Codes: A63B 37/0039 characterised by the material
• CPC Class Codes: A63B 37/0092 Hardness distribution amongst different ball layers
• CPC Class Codes: A63B 37/02 Special cores balls with finger holes A63B37/0001, golf ball cores A63B37/005

Abstract

A low compression, resilient golf ball having a center and a cover, made from a polybutadiene reaction product having polybutadiene, a cis-to-trans catalyst including an organosulfur component, and a free radical source. The reaction product has a first dynamic stiffness measured at −50° C. that is less than about 130 percent of a second dynamic stiffness measured at 0° C. A multi-layer golf ball having a center, at least one intermediate layer disposed concentrically about the center, and a cover. At least a portion of at least one of the center, intermediate layer, or both, are made from a reaction product including polybutadiene having a cis-to-trans catalyst that includes at least one organosulfur component and a free radical source. The reaction product has a first dynamic stiffness measured at −50° C. that is less than about 130 percent of a second dynamic stiffness measured at 0° C. Addition of various combinations of polybutadiene, cis-to-trans catalyst including at least one organosulfur component, free radical source, filler, and crosslinker, produce golf balls and golf ball components that are resilient (fast) and have low compression (soft).

Claims

1. A golf ball having a cover disposed about a core, wherein the golf ball comprises a material formed from the conversion reaction of a sufficient amount of polybutadiene, a free radical source, and a cis-to-trans catalyst comprising at least one organosulfur component, wherein the reaction occurs at a sufficient temperature to form a polybutadiene reaction product, wherein the golf ball comprises:

at least about 32 percent trans-polybutadiene after the conversion reaction, wherein the amount of trans-polybutadiene after the conversion reaction is greater than the amount of trans-polybutadiene present before the conversion reaction; and

a cis-to-trans catalyst comprising at least one organosulfur component, wherein the reaction product comprises a sphere which has a midpoint having a first hardness and a surface having a second hardness such that the second hardness differs from the first hardness by greater than 10 percent of the first hardness.

2. The golf ball of claim 1, wherein the golf ball comprises a cover having at least one of a dimple coverage of greater than about 60 percent, a hardness from about 35 to 80 Shore D, or a flexural modulus of greater than about 500 psi, and wherein the golf ball has at least one of a compression from about 50 to 120 or a coefficient of restitution of greater than about 0.7.

3. The golf ball of claim 1, wherein the reaction product has a first dynamic stiffness measured at −

50°

C. that is less than about 130 percent of a second dynamic stiffness measured at 0°

C.

4. The golf ball of claim 1, wherein the organosulfur component comprises at least one of 4,4′

-diphenyl disulfide, 4,4′

-ditolyl disulfide, or 2,2′

-benzamido diphenyl disulfide.

5. The golf ball of claim 4, wherein the organosulfur component comprises 4,4′

-ditolyl disulfide.

6. The golf ball of claim 1, wherein the organosulfur component comprises at least one of 4,4′

-diphenyl disulfide, 4,4′

-ditolyl disulfide, or 2,2′

-benzamido diphenyl disulfide.

7. The golf ball of claim 1, wherein the cis-to-trans catalyst is present in an amount from about 0.1 to about 25 parts per hundred polybutadiene.

8. The golf ball of claim 7, wherein the cis-to-trans catalyst is present in an amount from about 0.1 to 12 parts per hundred of polybutadiene.

9. The golf ball of claim 1, wherein the cis-to-trans catalyst further comprises at least one of an inorganic sulfur compound, an aromatic organometallic compound, a metal-organosulfur compound, tellurium, selenium, elemental sulfur, a polymeric sulfur, or an aromatic organic compound.

10. The golf ball of claim 1, wherein the polybutadiene reaction product comprises less than about 7 percent vinyl isomer content based on the total polybutadiene.

11. The golf ball of claim 10, wherein the polybutadiene reaction product comprises less than about 4 percent vinyl isomer.

12. The golf ball of claim 11, wherein the polybutadiene reaction product comprises less than about 2 percent vinyl isomer.

13. The golf ball of claim 9, further comprising a vulcanization accelerator.

14. The golf ball of claim 13, wherein the vulcanization accelerator comprises at least one of sulfenamide, thiazole, dithiocarbamate, thiuram, xanthate, thiadiazine, thiourea, guanadine, or aldehyde-amine.

15. The golf ball of claim 13, wherein the accelerator is present in an amount from about 0.05 phr to 2 phr.

16. The golf ball of claim 15, wherein the accelerator is present in an amount from about 0.1 phr to 1 phr.

17. The golf ball of claim 1, wherein the reaction product is disposed in at least a portion of the core.

18. The golf ball of claim 1, wherein the golf ball comprises:

a core comprising a center and at least one intermediate layer; and

a cover disposed concentrically about the core, wherein the reaction product is disposed in a portion of the core.

19. The golf ball of claim 18, wherein the portion of the core having the reaction product is the center.

20. The golf ball of claim 18, wherein a portion of the center comprises a fluid.

21. The golf ball of claim 18 wherein the at least one intermediate layer comprises a wound layer of tensioned elastomeric material.

22. The golf ball of claim 21, wherein the tensioned elastomeric material comprises the reaction product.

23. The golf ball of claim 1, further comprising a density-modifying filler.

24. The golf ball of claim 1, wherein the material further comprises one or more metallic salts of unsaturated fatty acids or monocarboxylic acids.

25. The golf ball of claim 24, wherein the metallic salts are selected from the group consisting of zinc acrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate, and mixtures thereof.

26. A method for forming a golf ball having a cover disposed about a core, comprising the steps of;

combining (a) a cis-to-trans catalyst comprising at least one organosulfur component;

(b) a free radical source; and

(c) a first resilient polymer component comprising a cis-polybutadiene component present in an amount greater than about 70 percent of the total polymer component;

converting a portion of the first resilient polymer component to a second resilient polymer component in about 5 to 18 minutes at a sufficient temperature to convert at least a portion of the cis-polybutadiene component to a trans-polybutadiene component and wherein the polybutadiene in the second resilient polymer component is at least about 32 percent trans-polybutadiene and less than about 7 percent vinyl-polybutadiene; and

forming a mixture of the first resilient polymer component and the second resilient polymer component into at least a portion of the golf ball.

27. The method of claim 26, wherein the portion of the second resilient polymer component is formed into a solid sphere.

28. The method of claim 27, which further comprises forming at least one intermediate layer and the cover over the solid sphere.

29. The method of claim 26, which further comprises forming the portion of the second resilient polymer component into at least one layer disposed concentrically about a sphere.

30. The method of claim 26, wherein the portion of the second resilient polymer component is formed into the cover disposed concentrically about a sphere so as to form the golf ball.

31. The method of claim 26, wherein the polybutadiene component comprises a cis-polybutadiene present in an amount of at least about 80 percent of the total first resilient polymer component.

32. The method of claim 26, wherein the combining further comprises a density-modifying filler.

33. The method of claim 26, wherein the forming comprises forming a sphere having a midpoint having a first amount of trans-polybutadiene and a surface having a second amount of trans-polybutadiene, wherein the first amount is at least about 6 percent less than the second amount.

34. The method of claim 26, wherein the second amount of trans-polybutadiene component is selected to comprise a vinyl polybutadiene component present in an amount of less than about 4 percent of the total resilient polymer component.

35. The method of claim 26, wherein the organosulfur component comprises at least one of 4,4′

-diphenyl disulfide, 4,4′

-ditolyl disulfide, or 2,2′

-benzamido diphenyl disulfide.

36. The method of claim 35, wherein the at least one organosulfur component comprises 4,4′

-ditolyl disulfide.

37. The method of claim 26, wherein the cis-to-trans catalyst is present in an amount from about 0.1 to 25 parts per hundred of the total resilient polymer component.

38. The method of claim 37, wherein the cis-to-trans catalyst is present in an amount from about 0.1 to 12 parts per hundred of the total resilient polymer component.

39. The method of claim 38, wherein the cis-to-trans catalyst is present in an amount from about 0.1 to 8 parts per hundred of the total resilient polymer component.

40. The method of claim 26, wherein the cis-to-trans catalyst is selected to further comprise at least one of an inorganic sulfide, an aromatic organometallic compound, a metal-organosulfur compound, elemental sulfur, a polymeric sulfur, or an aromatic organic compound.

41. The method of claim 40, which further comprises providing an accelerator in an amount sufficient to facilitate cis-to-trans conversion.

42. The method of claim 41, wherein the accelerator is selected to comprise at least one of sulfenamide, thiazole, dithiocarbamate, thiuram, xanthate, thiadiazine, thiourea, guanadine, or aldehyde-amine.

43. The method of claim 41, wherein the accelerator is provided in an amount from about 0.05 to 2 phr of the total resilient polymer component.

44. The method of claim 43, wherein the accelerator is provided in an amount from about 0.1 to 1 phr of the total resilient polymer component.

45. The method of claim 29 wherein a portion of the sphere comprises a fluid.

46. The method of claim 29 wherein a tensioned elastomeric material is wound about the sphere.

47. The method of claim 46, wherein the tensioned elastomeric material comprises the reaction product.

48. The method of claim 26, wherein the forming comprises:

a single-step compression molding of the first resilient polymer component to convert the first resilient polymer component to the second resilient polymer in about 8 to 15 minutes; and

forming the second resilient polymer component into a solid sphere.

49. The method of claim 48, wherein the converting and forming are substantially simultaneous.

50. The golf ball of claim 26, further combining:

(d) one or more metallic salts of unsaturated fatty acids or monocarboxylic acids in an amount sufficient to crosslink a portion of the first resilient polymer component.

51. A golf ball having a core with at least two layers and a cover having at least two layers disposed about the core, wherein the golf ball comprises a material formed from the conversion reaction of a sufficient amount of polybutadiene, a free radical source, and a cis-to-trans catalyst comprising at least one organosulfur component, wherein the reaction occurs at a sufficient temperature to form a polybutadiene reaction product, wherein the golf ball comprises:

at least about 32 percent trans-polybutadiene after the conversion reaction, wherein the amount of trans-polybutadiene after the conversion reaction is greater than the amount of trans-polybutadiene present before the conversion reaction; and

a cis-to-trans catalyst comprising at least one organosulfur component, wherein the reaction product courses a sphere which has a midpoint having a first hardness and a surface having a second hardness such that the second hardness differs from the first hardness by greater than 10 percent of the first hardness.

52. The golf ball of claim 51, wherein the material further comprises one or more metallic salts of unsaturated fatty acids or monocarboxylic acids.

53. A golf ball having a cover disposed about a core, wherein the golf ball is prepared by a process which comprises:

combining (a) at least one of a cis-to-trans catalyst comprising at least one organosulfur component;

(b) a free radical source; and

(c) a first resilient polymer component comprising a cis-polybutadiene component present in an amount greater than about 70 percent of the total polymer component;

converting a portion of the first resilient polymer component to a second resilient polymer component in about 5 to 18 minutes, wherein at least a portion of the cis-isomer content is converted to a trans-isomer content and wherein the polybutadiene component in the second resilient polymer component is at least about 32 percent trans-polybutadiene and less than about 7 percent vinyl-polybutadiene; and

forming a mixture of the first resilient polymer component and the second resilient polymer component into at least a portion of the golf ball.

54. The golf ball of claim 53, further combining:

(d) one or more metallic salts of unsaturated fatty acids or monocarboxylic acids in an amount sufficient to crosslink a portion of the first resilient polymer component.

55. A golf ball having a cover disposed about a core, wherein the golf ball comprises a material formed from the conversion reaction of a sufficient amount of polybutadiene, a free radical source, and a cis-to-trans catalyst comprising at least one organosulfur component, wherein the reaction occurs at a sufficient temperature to form a polybutadiene reaction product, wherein the golf ball comprises:

at least about 32 percent trans-polybutadiene after the conversion reaction, wherein the amount of trans-polybutadiene after the conversion reaction is greater than the amount of trans-polybutadiene present before the conversion reaction; and

a cis-to-trans catalyst comprising at least one organosulfur component, wherein the reaction product has a fist dynamic stiffness measured at −

50°

C. that is less than about 130 percent of a second dynamic stiffness measured at 0°

C.

56. The golf ball of claim 55, wherein the material further comprises one or more metallic salts of unsaturated fatty acids or monocarboxylic acids.

57. A method for forming a golf ball having a cover disposed about a core, wherein the method comprises:

combining (a) a cis-to-trans catalyst comprising at least one organosulfur component;

(b) a free radical source; and

(c) a first resilient polymer component comprising a cis-polybutadiene component present in an amount greater than about 70 percent of the total polymer component;

converting a portion of the first resilient polymer component to a second resilient polymer component in about 5 to 18 minutes at a sufficient temperature to convert at least a portion of the cis-polybutadiene component to a trans-polybutadiene component and wherein the polybutadiene in the second resilient polymer component is at least about 32 percent trans-polybutadiene and less than about 7 percent vinyl-polybutadiene; and

forming a mixture of the first resilient polymer component and the second resilient polymer component into at least a portion of the golf ball, wherein the mixture comprises a sphere which has a midpoint having a first hardness and a surface having a second hardness such that the second hardness differs from the first hardness by greater than 10 percent of the first hardness.

58. The golf ball of claim 57, further combining:

(d) one or more metallic salts of unsaturated fatty acids or monocarboxylic acids in an amount sufficient to crosslink a portion of the first resilient polymer component.

59. A method for forming a golf ball having a cover disposed about a core, wherein the method comprises:

combining (a) a cis-to-trans catalyst comprising at least one organosulfur component;

(b) a free radical source; and

(c) a first resilient polymer component comprising a cis-polybutadiene component present in an amount greater than about 70 percent of the total polymer component;

converting a portion of the first resilient polymer component to a second resilient polymer component in about 5 to 18 minutes at a sufficient temperature to convert at least a portion of the cis-polybutadiene component to a trans-polybutadiene component and wherein the polybutadiene in the second resilient polymer component is at least about 32 percent trans-polybutadiene and less than about 7 percent vinyl-polybutadiene; and

forming a mixture of the first resilient polymer component and the second resilient polymer component into at least a portion of the golf ball, wherein the mixture has a first dynamic stiffness measured at −

50°

C. that is less than about 130 percent of a second dynamic stiffness measured at 0°

C.

60. The golf ball of claim 59, further combining:

(d) one or more metallic salts of unsaturated fatty acids or monocarboxylic acids in an amount sufficient to crosslink a portion of the first resilient polymer component.

61. A golf ball comprising a material formed from a conversion reaction of a sufficient amount of polybutadiene, a free radical source, and a cis-to-trans catalyst comprising at least one organosulfur component, wherein the reaction occurs at a sufficient temperature to form a polybutadiene reaction product, wherein the golf ball comprises:

at least about 32 percent trans-polybutadiene after the conversion reaction, wherein the amount of trans-polybutadiene after the conversion reaction is greater than the amount of trans-polybutadiene present before the conversion reaction; and

a cis-to-trans catalyst comprising at least one organosulfur component, wherein the reaction product comprises a sphere which has a midpoint having a dynamic stiffness of less than 30,000 N/m2 measured at 0°

C.

62. The golf ball of claim 61, wherein the material further comprises one or more metallic salts of unsaturated fatty acids or monocarboxylic acids.