Golf ball compositions comprising saponified polymer and polyamide blends

• US 6,486,250 B1
• Filed: 06/30/2000
• Issued: 11/26/2002
• Est. Priority Date: 11/21/1995
• Status: Expired due to Fees

• Current Assignee: Acushnet Company (FILA Holdings Corp.)
• Original Assignee: Acushnet Company (FILA Holdings Corp.)
• Inventors: Rajagopalan, Murali
• Primary Examiner(s): Buttner, David J.
• Application Number:
  US09/607,349
• Time in Patent Office: 879 Days
• Field of Search: 524/431, 524/440, 525/66, 525/179, 525/183, 473/354, 473/355, 473/365, 473/373, 473/374, 473/377, 473/378, 473/385
• US Class Current: 524/431
• CPC Class Codes: A63B 2037/085 liquid, jellylike
• CPC Class Codes: A63B 2037/087 Wound cores or layers
• CPC Class Codes: A63B 37/0003 Golf balls
• CPC Class Codes: A63B 37/0024 Materials other than ionomers or polyurethane
• CPC Class Codes: A63B 37/0031 Hardness
• CPC Class Codes: A63B 37/0033 Thickness
• CPC Class Codes: A63B 37/0037 Flexural modulus; Bending stiffness
• CPC Class Codes: A63B 37/0039 characterised by the material
• CPC Class Codes: A63B 37/0043 Hardness
• CPC Class Codes: A63B 37/0045 Thickness
• CPC Class Codes: A63B 37/0048 Melt flow rate [MFR]
• CPC Class Codes: A63B 37/0049 Flexural modulus; Bending stiffness
• CPC Class Codes: A63B 37/0051 Materials other than polybutadienes; Constructional details
• CPC Class Codes: A63B 37/0052 Liquid cores
• CPC Class Codes: A63B 37/0064 Diameter
• CPC Class Codes: A63B 37/0076 Multi-piece balls, i.e. having two or more intermediate layers
• CPC Class Codes: A63B 37/0078 Coefficient of restitution
• CPC Class Codes: A63B 37/0087 Deflection or compression
• CPC Class Codes: C08K 2003/2241 Titanium dioxide
• CPC Class Codes: C08L 33/06 of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• CPC Class Codes: C08L 77/00 : Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 77/02 : Polyamides derived from omega-amino carboxylic acids or from lactams thereof C08L77/10 takes precedence

Abstract

The present invention is directed to a golf ball and a to a process for forming a golf ball having least one layer, where the layer is formed of a saponified polymer/polyamide blend, having from about 1 to about 99 parts of at least one saponified polymer and from about 99 to 1 parts of at least one polyamide polymer, based on 100 parts by weight of the saponified polymer/polyamide blend. The layer may be foamed or unfoamed, and may form at least a portion of any of the cover, the core, or an intermediate layer situated between the cover and the core.

Claims

1. A golf ball having at least one layer, said layer comprising a saponified polymer/polyamide blend comprising at least one saponified polymer and at least one polyamide polymer, wherein the saponified polymer comprises:

a first olefinic, monomeric component having from 2 to 8 carbon atoms;

a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms and at least one ester group, wherein at least a portion of said at least one ester group has been saponified with an inorganic metal base; and

a third monomeric component selected from the group consisting of carbon monoxide, sulfur dioxide, an anhydride monomer, an unsaturated monocarboxylic acid, an olefin having from 2 to 8 carbon atoms and a vinyl ester or a vinyl ether of an alkyl acid having from 4 to 21 carbon atoms.

2. The golf ball of claim 1, wherein the golf ball has an Atti compression of at least 50 and a coefficient of restitution of at least 0.7.

3. The golf ball of claim 1, wherein the layer has a hardness of at least 15 Shore A, a flexural modulus of at least 500 psi and a specific gravity of at least 0.7.

4. The golf ball of claim 1, wherein said layer further comprises at least one density adjusting filler.

5. The golf ball of claim 4, wherein the density adjusting filler is a metallic powder.

6. The golf ball of claim 5, wherein the metallic powder is selected from the group consisting of titanium, tungsten and copper powder.

7. The golf ball of claim 4, wherein the density adjusting filler is a metallic oxide derivative.

8. The golf ball of claim 7, wherein the metallic oxide derivative is an oxide derivative selected from the group consisting of titanium, tungsten, copper and tin.

9. The golf ball of claim 1, wherein the layer has a foamed structure.

10. The golf ball according to claim 1, comprising a cover, wherein the layer forms at least a portion of the cover.

11. The golf ball of claim 10, wherein the cover layer has a hardness at least 40 Shore D to about 70 Shore D and a flexural modulus at least 10,000 to about 100,000 psi.

12. The golf ball according to claim 10, further comprising a core, wherein the layer forms at least a portion of the core.

13. The golf ball of claim 12, wherein the core layer has a hardness at least 40 Shore A to about 70 Shore D and a flexural modulus at least 500 to about 150,000 psi.

14. The golf ball of claim 12, wherein the cover has a thickness of at least 0.03 inch to about 0.125 inch and at least 60 percent dimple coverage, and a core, having a diameter of at least 0.5 to about 1.63 inches.

15. A golf ball according to claim 12, wherein the portion of the core is solid or fluid.

16. A golf ball according to claim 15, wherein the portion of the core is fluid further comprising a tensioned elastomeric material.

17. The golf ball according to claim 16, wherein the tensioned elastomeric material further comprises natural or synthetic elastomers or blends thereof.

18. The golf ball according to claim 8, further comprising at least one intermediate layer situated between the cover and the core.

19. The golf ball of claim 18, wherein the at least one intermediate layer has a hardness at least 20 Shore D to 70 Shore D and flexural modulus at least 500 to about 100,000 psi.

20. The golf ball of claim 18, wherein the intermediate layer has a thickness of at least 0.02 inches.

21. The golf ball according to claim 18, wherein the layer forms at least a portion of at least one intermediate layer.

22. The golf ball of claim 1, wherein the polyamide polymer is a copolymer selected from the group consisting of polyamide 6/6,6, polyamide 6,6/6,10, polyamide 6/6,T, polyamide 6/6,6/6,10 and mixtures thereof.

23. The golf ball of claim 1, wherein the polyamide polymer is a homopolymer selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 4,6, polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12 and mixtures thereof.

24. The golf ball of claim 23, wherein the polyamide homopolymer is selected from the group consisting of polyamide 11 and polyamide 12.

25. The golf ball of claim 1, wherein the saponified polymer of the saponified polymer/polyamide blend of said layer has a Shore D hardness of at least 15, a flexural modulus of at least 500 psi, a specific gravity of at least 0.7, a dynamic shear modulus at 23°

C. of at least 10⁴ dynes/cm² and a loss tangent of no more than about 1 at 23°

C.

26. The golf ball of claim 25, wherein the flexural modulus of the saponified polymer of the saponified polymer/polyamide blend is about 1000 psi to about 100,000 psi.

27. The golf ball of claim 25, wherein the specific gravity of the saponified polymer of the saponified polymer/polyamide blend is at least 0.75 to about 1.

28. The golf ball of claim 25, wherein the dynamic shear storage modulus of the saponified polymer of the saponified polymer/polyamide blend is about 10⁶ to about 10¹⁰ dynes/cm².

29. The golf ball of claim 25, wherein the loss tangent of the saponified polymer of the saponified polymer/polyamide blend is no more than 0.1 at 23°

C.

30. The golf ball according to claim 1, wherein the third monomeric component is present in an amount of about 49 percent or less by weight of the total polymer weight.

31. The golf ball according to claim 1, wherein the metal base comprises at least one metallic cation, selected from the group consisting of lithium, sodium, potassium, cesium, magnesium, calcium, barium, manganese, copper, zinc and aluminum and at least one anion, selected from the group consisting of hydroxide, alkoxide, acetate, carbonate, bicarbonate, oxide, formate and nitrate.

32. The golf ball according to claim 1, wherein the first monomeric component comprises an α

-olefin monomer having a terminal point of unsaturation.

33. The golf ball according to claim 1, wherein the first monomeric component has a formula:

wherein;

R₁ is hydrogen or an alkyl group; and

R₂ is hydrogen, lower alkyl including C₁-C₅, carbocyclic or aromatic.

34. The golf ball according to claim 32, wherein the first monomeric component is ethylene.

35. The golf ball according to claim 1, wherein the first monomeric component comprises from about 10 to about 95 percent by weight of the total polymer weight.

36. The golf ball according to claim 35, wherein the first monomeric component comprises from about 10 to about 70 percent by weight of the total polymer weight.

37. The golf ball according to claim 1, wherein the second monomeric component is an unsaturated acrylate class ester having a formula:

wherein;

R₃ is hydrogen or an alkyl group;

R₄ is hydrogen, lower alkyl including C₁-C₅, carbocyclic or aromatic; and

R₅ is selected from the group consisting of C_nH_2n+1, for n=1 to 18 and phenyl, in which from 0 to 5 H within R₅ can be replaced by substituents selected from the group consisting of COOH, SO₃H, NH₂, succinic anhydride and their salts, or R₅ can be replaced by substituents selected from the group consisting of F, Cl, Br, I, OH, SH, epoxy, silicone, lower alkyl esters, lower alkyl ethers and aromatic rings, wherein optionally R₄ and R₅ can be combined to form a bicyclic ring.

38. The golf ball according to claim 1, wherein the second monomeric component comprises from about 90 to about 5 percent by weight of the total polymer weight.

39. The golf ball according to claim 38, wherein the second monomeric component comprises from about 90 to about 30 percent by weight of the total polymer weight.

40. The golf ball according to claim 1, wherein a grafting agent has been added to at least one of the saponified polymer or the polyamide to form a grafted polymer.

41. The golf ball according to claim 40, wherein the grafting agent comprises an anhydride having a formula:

wherein;

R₁₄ and R₁₅ are the same or different and are selected from the group consisting of hydrogen, linear or branched chain alkyl and substituted or unsubstituted carboxylic groups.

42. The golf ball according to claim 40, wherein the grafting agent is added in an amount of between about 1 to about 50 percent by weight of the polymer.

43. The golf ball according to claim 42, wherein the grafting agent is added in an amount of between about 1 to about 15 percent by weight of the polymer.

44. The golf ball of claim 1, wherein the saponified polymer/polyamide blend further comprises at least one compatibilizer.

45. The golf ball of claim 44, wherein the compatibilizer is selected from the group consisting of olefinic block, random, and graft thermoplastic polymers and oligomers, which contain monomers and comonomers functionalized with groups selected from the group consisting of acids, esters, epoxies, isocyanates, hydroxys, anhydrides, amines, thiols;

polyester-polyether block copolymers;

polyamide-polyether block copolymers;

polysiloxanes;

silicones;

styrene-butadiene and hydrogenated styrene-butadiene block co-polymers; and

mixtures thereof.

46. The golf ball of claim 44, wherein the compatibilizer is up to about 20 parts, based on 100 parts by weight of the saponified polymer/polyamide blend.

47. A golf ball comprising a cover layer, a core layer and at least one intermediate layer situated between the cover layer and the core layer, wherein at least one of said layers comprises a blend of at least one saponified polymer and at least one polyamide polymer, wherein the polyamide polymer is selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 4,6, polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 6/6,6, polyamide 6,6/6,10 polyamide 6/6,T, polyamide 6/6,6/6,10, and mixtures thereof.

48. The golf ball of claim 47, wherein the cover layer comprises the blend.

49. The golf ball of claim 47, wherein the intermediate layer comprises the blend.

50. A golf ball having at least one layer, said layer comprising a saponified polymer/polyamide blend comprising from about 1 to about 99 parts of at least one saponified polymer and from about 99 to about 1 parts of at least one polyamide polymer, based on 100 parts by weight of the saponified polymer/polyamide blend, wherein the polyamide polymer is selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 4,6, polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 6/6,6, polyamide 6,6/6,10, polyamide 6/6,T, polyamide 6/6,6/6,10 and mixtures thereof.

51. The golf ball according to claim 50, wherein the saponified polymer/polyamide blend further comprises at least one compatibilizer selected from the group consisting of olefinic block, random, and graft thermoplastic polymers and oligomers, which contain monomers and comonomers functionalized with groups selected from the group consisting of acids, esters, epoxies, isocyanates, hydroxys, anhydrides, amines, thiols;

polyester-polyether block copolymers;

polyamide-polyether block copolymers;

polysiloxanes;

silicones;

styrene-butadiene and hydrogenated styrene-butadiene block co-polymers; and

mixtures thereof.

52. The golf ball of claim 50, wherein the golf ball has an Atti compression of at least 50 and a coefficient of restitution of at least 0.7.

53. The golf ball of claim 50, wherein said layer has a hardness of at least 15 Shore A, a flexural modulus of at least 500 psi and a specific gravity of at least 0.7.

54. The golf ball of claim 50, wherein said layer further comprises at least one density adjusting filler selected from the group consisting of titanium, tungsten and copper powder.

55. The golf ball of claim 50, wherein said layer has a foamed structure.

56. The golf ball of claim 50, wherein said saponified polymer of the saponified polymer/polyamide blend of said layer has a Shore D hardness of at least 15, a flexural modulus of at least 500 psi, a specific gravity of at least 0.7, a dynamic shear modulus at 23°

C. of at least 104 dynes/cm2 and a loss tangent of no more than about 1 at 23°

C.

57. The golf ball according to claim 50, wherein the saponified polymer comprises a first olefinic, monomeric component having from 2 to 8 carbon atoms and a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms and at least one ester group, wherein at least a portion of said at least one ester group has been saponified with an inorganic metal base.

58. The golf ball according to claim 50, further comprising a third monomeric component selected from the group consisting of carbon monoxide, sulfur dioxide, an anhydride monomer, an unsaturated monocarboxylic acid, an olefin having from 2 to 8 carbon atoms and a vinyl ester or a vinyl ether of an alkyl acid having from 4 to 21 carbon atoms.

59. The golf ball according to claim 50, wherein a grafting agent has been added to at least one of the saponified polymer or the polyamide to form a grafted polymer.