Golf ball compositions containing oxa esters

• US 6,391,955 B1
• Filed: 06/30/2000
• Issued: 05/21/2002
• Est. Priority Date: 06/07/1995
• Status: Expired due to Fees

• Current Assignee: Acushnet Company (FILA Holdings Corp.)
• Original Assignee: Acushnet Company (FILA Holdings Corp.)
• Inventors: Rajagopalan, Murali, Harris, Kevin
• Primary Examiner(s): Buttner, David J.
• Application Number:
  US09/608,566
• Time in Patent Office: 690 Days
• Field of Search: 525/175, 525/176, 525/190, 524/308, 524/317, 473/354, 473/365, 473/371, 473/372, 473/373, 473/374, 473/377, 473/378, 473/385
• US Class Current: 524/308
• CPC Class Codes: A63B 37/0003 Golf balls
• CPC Class Codes: A63B 37/0031 Hardness
• 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 37/0047 Density; Specific gravity
• CPC Class Codes: A63B 37/0054 Substantially rigid, e.g. metal
• CPC Class Codes: A63B 37/0062 Hardness
• CPC Class Codes: A63B 37/0069 Flexural modulus; Bending stiffness
• CPC Class Codes: A63B 37/0074 Two piece balls, i.e. cover and core
• CPC Class Codes: A63B 37/0075 Three piece balls, i.e. cover, intermediate layer and core
• CPC Class Codes: A63B 37/0078 Coefficient of restitution
• CPC Class Codes: A63B 37/0087 Deflection or compression
• CPC Class Codes: A63B 37/12 Special coverings , i.e. outer layer material balls with finger holes A63B37/0001, golf ball covers A63B37/0023
• CPC Class Codes: A63B 45/00 Apparatus or methods for manufacturing balls working of plastics or substances in a plastic state B29
• CPC Class Codes: C08K 5/09 Carboxylic acids; Metal salts thereof; Anhydrides thereof
• CPC Class Codes: C08K 5/11 of acyclic polycarboxylic acids
• CPC Class Codes: C08L 23/0869 Acids or derivatives thereof
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 33/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Abstract

The present invention is directed to a golf ball and to a process for forming a golf ball having at least one layer, where the layer is formed of a polymer blend comprising an oxa ester or a saponified polymer/oxa ester blend, having from about 65 to about 99 parts of at least one saponified polymer and from about 35 to 1 parts of at least one oxa ester, based on 100 parts by weight of the saponified polymer/oxa ester blend. The layer may be foamed or unfoamed, and may form at least a portion of any of the cover, the core, or a mantle layer situated between the cover and the core.

Claims

1. A golf ball having least one layer, the layer formed of a polymer blend comprising at least one oxa ester.

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 titanium, tungsten, tin or 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 said 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 13, wherein the core further comprises cis-polybutadiene.

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 12, 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 according to claim 18, wherein the layer forms at least a portion of at least one intermediate layer.

21. The golf ball according to claim 1, wherein the at least one oxa ester is selected from the group consisting of

monoesters of the formula:

diesters of formula;

wherein n is an integer greater than or equal to 1, R₁ and R₃ are any organic moiety selected from the group consisting of a linear or branch chained alkyl, a substituted or unsubstituted carbocyclic or heterocyclic groups, and R₂ is H or an organic moiety selected from the group consisting of linear and branch chained alkyl, substituted and unsubstituted carbocyclic, and heterocyclic groups;

polymers of formula

polymers of formula

and polymers of formula

where R₄ and R₅ are independently selected from the group consisting of hydrogen or an alkyl group containing from 1 to 8 carbon atoms;

a is an integer in the range of from 1 to about 2,000 and preferably from 1 to about 1000;

b, d and g are independently an integer in the range of from about 1 to about 10,000;

c is an integer in the range of from 1 to 2000;

e is an integer in the range of from 1 to about 6,000,

f is an integer from about 1 to about 200;

R₆ is an alkylene containing from 2 to 12 carbon atoms or is an oxyalkylene group of formula;

22. The golf ball according to claim 1, wherein the oxa ester is present in an amount of from about 1 to about 35 parts, based on 100 parts of the polymer blend.

23. The golf ball according to claim 22, wherein the oxa ester is present in an amount of from about 1 to about 25 parts, based on 100 parts of the polymer blend.

24. The golf ball according to claim 23, wherein the oxa ester is present in an amount of from about 1 to about 15 parts, based on 100 parts of the polymer blend.

25. The golf ball according to claim 1, wherein the polymer blend further comprises at least one saponified polymer.

26. The golf ball according to claim 25, wherein the polymer blend comprises from about 1 to about 35 parts of the oxa ester and from about 99 to about 65 parts of the saponified polymer, based on 100 parts of the polymer blend.

27. The golf ball according to claim 26, wherein the polymer blend comprises from about 1 to about 25 parts of the oxa ester and from about 99 to about 75 parts of the saponified polymer, based on 100 parts of the polymer blend.

28. The golf ball according to claim 27, wherein the polymer blend comprises from about 1 to about 15 parts of the oxa ester and from about 99 to about 85 parts of the saponified polymer, based on 100 parts of the polymer blend.

29. The golf ball of claim 25, wherein the saponified polymer 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.

30. The golf ball of claim 29, wherein the flexural modulus is about 1000 psi to about 100,000 psi.

31. The golf ball of claim 29, wherein the specific gravity is at least 0.75 to about 1.

32. The golf ball of claim 29, wherein the dynamic shear storage modulus is about 10⁶ to about 10¹⁰ dynes/cm².

33. The golf ball of claim 29, wherein the loss tangent is no more than 0.1 at 23°

C.

34. The golf ball according to claim 25, 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 the ester groups have been saponified with an inorganic metal base, and, optionally, 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.

35. The golf ball according to claim 34, 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, titanium, tungsten, zirconium, and aluminum, and at least one anion, selected from the group consisting of hydroxide, alkoxide, acetate, carbonate, bicarbonate, oxide, formate, and nitrate.

36. The golf ball according to claim 34, wherein the first monomeric component comprises an α

-olefin monomer having a terminal point of unsaturation.

37. The golf ball according to claim 36, wherein the first monomeric component has the formula

wherein:

R₁₂ is hydrogen or an alkyl group; and

R₁₃ is hydrogen, lower alkyl, carbocyclic, or aromatic.

38. The golf ball according to claim 36, wherein the first monomeric component is ethylene.

39. The golf ball according to claim 34, wherein the first monomeric component comprises from about 1 to about 99 percent by weight of the total polymer weight.

40. The golf ball according to claim 39, wherein the first monomeric component comprises from about 10 to about 95 percent by weight of the total polymer weight.

41. The golf ball according to claim 40, wherein the first monomeric component comprises from about 10 to about 70 percent by weight of the total polymer weight.

42. The golf ball according to claim 34, wherein the second monomeric component is an unsaturated acrylate class ester having the formula:

wherein;

R₁₄ is hydrogen or an alkyl group;

R₁₅ is hydrogen, lower alkyl, carbocyclic, or aromatic;

R₁₆ 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 R₁₆ can be replaced by substituents selected from the group consisting of COOH, SO₃H, NH₂, succinic anhydride and their salts, or R₁₆ 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 R₁₅ and R₁₆ can be combined to form a bicyclic ring.

43. The golf ball according to claim 42, wherein the second monomeric component comprises from about 99 to about 1 percent by weight of the total polymer weight.

44. The golf ball according to claim 43, wherein the second monomeric component comprises from about 90 to about 5 percent by weight of the total polymer weight.

45. The golf ball according to claim 44, wherein the second monomeric component comprises from about 90 to about 30 percent by weight of the total polymer weight.

46. The golf ball according to claim 34, wherein the optional third monomeric component is at least one of the monomers selected from the group consisting of:

wherein;

R₁₇, R₁₈, R₁₉ and R₂₂ are independently hydrogen, lower alkyl, carbocyclic, or aromatic;

R₂₀ and R₂₅ are independently hydrogen or lower alkyl;

R₂₁ is hydrogen, or 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 R₂₁ can be replaced by substituents selected from the group consisting of COOH, SO₃H, NH₂ and their salts, or R₂₁ can be replaced by substituents selected from the group consisting of F, Cl, Br, I, OH, SH, silicon, lower alkyl esters, lower alkyl ethers and aromatic rings, wherein optionally R₂₀ and R₂₁ can be combined to form a bicyclic ring;

R₂₄ is hydrogen, or 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 R₂₄ can be replaced by substituents selected from the group consisting of COOH, SO₃H, NH₂ and their salts, or R₂₄ can be replaced by substituents selected from the group consisting of F, Cl, Br, I, OH, SH, silicon, lower alkyl esters, lower alkyl ethers and aromatic rings, wherein optionally R₂₃ and R₂₄ can be combined to form a bicyclic ring.

47. The golf ball according to claim 34, wherein the optional third monomeric component comprises up to about 49 percent by weight of the total polymer weight.

48. The golf ball according to claim 34, wherein the saponified polymer is of a form selected from the group consisting of isotactic, syndiotactic, and atactic polymers and combinations thereof.

49. The golf ball according to claim 34, wherein the saponified polymer further comprises at least one functional pendant group added to the polymer by sulfonation, carboxylation, addition of an amine or hydroxy, or by grafting an ethylenically unsaturated monomer onto the saponified polymer using a post-polymerization reaction.

50. The golf ball according to claim 49, wherein the functional pendant group is an anhydride having the formula:

wherein;

R₂₅ and R₂₆ 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.

51. The golf ball according to claim 50, wherein the pendant group is present in an amount of between about 1 to about 50 percent by weight, based on the total weight of the polymer.

52. The golf ball according to claim 51, wherein the pendant group is present in an amount of between about 1 and about 25 percent by weight of the polymer.

53. The golf ball according to claim 1, wherein the polymer blend further comprises oxa acids, block copolymers of a poly(ether-ester), block copolymers of a poly(ether-amide), styrene-butadiene-styrene block copolymers, styrene-(ethylene-propylene)-styrene or styrene-(ethylene-butylene)-styrene block copolymers, styrene-butadiene-styrene block copolymers grafted with at least one of maleic anhydride or a sulfonic graft or functionality, olefinic copolymers, metallocene catalyzed polymers, block poly(urethane-ester), block poly(urethane-ether), block poly(urethane-caprolactone), polyethylene glycol, polycaprolactone, polycaprolactam, polyesters, polyamides, ethylene-propylene-(diene monomer) terpolymers and their sulfonated or carboxylated derivatives, and PP/EPDM and dynamically vulcanized rubbers.

54. The golf ball according to claim 1, wherein the polymer blend further comprises at least one ionomer, comprising an α

-olefin, an α

,β

-unsaturated carboxylic acid, and, optionally, an acrylate class ester as a softening monomer, wherein at least a portion the carboxylic acid groups on the polymer have been neutralized with at least one metal atom.

55. A method for forming a golf ball, the method comprising:

forming a polymer blend, which comprises at least one oxa ester; and

forming at least one layer of a golf ball from the polymer blend.

56. The method according to claim 55, further comprising:

forming a polymer comprising 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;

applying a sufficient amount of heat to the polymer to convert the polymer to a substantially molten state;

forming a mixture by adding an inorganic metal base to the molten polymer;

saponifying the mixture to form a saponified polymer,

wherein a sufficient amount of the inorganic metal base is added to the molten polymer in forming the mixture to obtain a degree of saponification of the polymer ranging between about 1 and 50 percent; and

blending the saponified polymer with the at least one oxa ester to form the polymer blend.

57. The method according to claim 56, further comprising forming the mixture of the inorganic metal base and the molten polymer at a temperature such that the mixture has a viscosity that remains substantially unchanged from that of the molten polymer.

58. The method according to claim 56, further comprising forming the polymer with 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.