Golf balls incorporating foamed metallocene catalyzed polymer

• US 5,824,746 A
• Filed: 06/05/1996
• Issued: 10/20/1998
• Est. Priority Date: 01/24/1995
• Status: Expired due to Term

• Current Assignee: Acushnet Company (FILA Holdings Corp.)
• Original Assignee: Acushnet Company (FILA Holdings Corp.)
• Inventors: Rajagopalan, Murali, Harris, Kevin M.
• Primary Examiner(s): WEBER, THOMAS
• Application Number:
  US08/658,338
• Time in Patent Office: 867 Days
• Field of Search: 525/196, 525/221, 473/351, 473/373, 473/378, 473/385
• US Class Current: 525/196
• CPC Class Codes: A63B 37/0003 Golf balls
• CPC Class Codes: A63B 37/0043 Hardness
• CPC Class Codes: A63B 37/0045 Thickness
• CPC Class Codes: A63B 37/0052 Liquid cores
• CPC Class Codes: A63B 37/0064 Diameter
• 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 37/0086 Flexural modulus; Bending stiffness
• CPC Class Codes: A63B 37/04 Rigid cores
• 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: C08F 222/06 Maleic anhydride
• CPC Class Codes: C08F 255/00 Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: C08L 23/04 Homopolymers or copolymers of ethene
• CPC Class Codes: C08L 23/08 Copolymers of ethene C08L23/16 takes precedence
• CPC Class Codes: C08L 23/0815 Copolymers of ethene with aliphatic 1-olefins
• CPC Class Codes: C08L 23/0876 Neutralised polymers, i.e. ionomers
• CPC Class Codes: C08L 23/10 Homopolymers or copolymers of propene
• CPC Class Codes: C08L 2314/06 Metallocene or single site catalysts
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 : Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 51/06 : grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• CPC Class Codes: H04B 1/005 : adapting radio receivers, transmitters andtransceivers for operation on two or more bands, i.e. frequency ranges
• CPC Class Codes: H04B 1/006 : using switches for selecting the desired band H04B1/0057 takes precedence

Abstract

The disclosed invention provides novel golf ball compositions which contain olefinic based ionomers and non-ionic olefinic copolymers produced by use of metallocene catalysts. These compositions exhibit improved mechanical properties such as tensile and flexural properties, and can be foamed or unfoamed. Golf balls that employ at least one layer of these blends in any of the golf ball cover, core, or a mantle situated between the cover and the core provide ball properties and performance similar to and in some cases better than the state of the art ionomer based golf balls.

Claims

1. A golf ball comprising a cover and a core, the cover having at least one foamed layer, the foamed layer formed of a metallocene catalyzed polymer blend, comprising at least one metallocene catalyzed polymer and at least one ionomer, wherein the metallocene catalyzed polymer is of the formula:

##STR3## wherein R₁ is hydrogen, aromatic, heterocyclic, or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, and C₄ H₉ ;

R₂ is hydrogen, aromatic, heterocyclic, or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, C₄ H₉, and C₅ H₁₁ ;

R₃ is hydrogen or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, C₄ H₉, and C₅ H₁₁ ;

R₄ is selected from the group consisting of H, CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₇ H₁₅, C₈ H₁₇, C₉ H₁₉, C₁₀ H₂₁, and phenyl, in which from 0 to 5 H within R₄ can be replaced by substituents selected from the group consisting of COOH, SO₃ H, NH₂, F, Cl, Br, I, OH, SH, silicone, lower alkyl esters and lower alkyl ethers, with the proviso that R₃ and R₄ can be combined to form a bicyclic ring;

R₅ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic;

R₆ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic; and

wherein x ranges from 99 to 50 weight per cent of the polymer, y ranges from 1 to 50 weight per cent of the polymer and z ranges from 0 to 49 weight per cent of the polymer.

2. The golf ball according to claim 1, wherein the layer has a Shore D hardness of from about 15 to about 80.

3. The golf ball according to claim 1, wherein the layer has a thickness of from about 0.005 to about 0.125 inch.

4. The golf ball according to claim 1, wherein the core comprises at least one core layer, the core layer comprising a blend of from about 1 to about 100 phr of at least one metallocene catalyzed polymer and from about 99 to 0 phr of at least one ionomer, wherein the metallocene catalyzed polymer is of the formula:

##STR4## wherein R₁ is hydrogen, aromatic, heterocyclic, or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, and C₄ H₉ ;

R₂ is hydrogen, aromatic, heterocyclic, or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, and C₄ H₉ or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, C₄ H₉, and C₅ H₁₁ ;

R₃ is hydrogen or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, C₄ H₉, and C₅ H₁₁ ;

R₄ is selected from the group consisting of H, CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₇ H₁₅, C₈ H₁₇, C₉ H₁₉, C₁₀ H₂₁, and phenyl, in which from 0 to 5 H within R₄ can be replaced by substituents selected from the group consisting of COOH, SO₃ H, NH₂, F, Cl, Br, I, OH, SH, silicone, lower alkyl esters and lower alkyl ethers, with the proviso that R₃ and R₄ can be combined to form a bicyclic ring;

R₅ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic;

R₆ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic; and

wherein x ranges from 99 to 50 weight per cent of the polymer, y ranges from 1 to 50 weight per cent of the polymer and z ranges from 0 to 49 weight per cent of the polymer.

5. The golf ball according to claim 4, wherein the core comprises a liquid center.

6. The golf ball according to claim 4, wherein the core layer has a foamed structure.

7. The golf ball according to claim 4, wherein the core layer has a Shore D hardness of from about 15 to about 80.

8. The golf ball according to claim 4, wherein the core has a diameter of from about 1.0 to about 1.63 inch, and the core layer has a thickness of from about 0.005 to about 0.125 inch.

9. The golf ball according to claim 1, further comprising a mantle situated between the cover and the core.

10. The golf ball according to claim 9, wherein the core comprises a liquid or solid center wrapped in elastomeric windings.

11. The golf ball according to claim 1, wherein the metallocene catalyzed polymer is chosen from the group consisting of polyethylene and copolymers of ethylene with butene, hexene, and octene.

12. The golf ball according to claim 1, wherein the metallocene catalyzed polymer has a flexural modulus of from about 500 psi to 200,000 psi, and the ionomer has a flexural modulus of from about 50 psi to about 150,000 psi.

13. The golf ball according to claim 1, wherein the metallocene catalyzed polymer blend has a foamed structure, and, further wherein the metallocene polymer blend has a flexural modulus of from about 1000 to about 150,000 psi.

17. The golf ball according to claim 11, wherein the metallocene catalyzed polymer is a copolymer of ethylene with 1-butene.

14. A golf ball comprising a cover and a core and a mantle situated between the cover and the core, wherein at least one of the cover, the core, and the mantle comprises at least one layer, the layer formed of a metallocene catalyzed polymer blend, comprising from about 1 to about 100 phr of at least one metallocene catalyzed polymer and from about 99 to 0 phr of at least one ionomer, wherein the metallocene catalyzed polymer is of the formula:

##STR5## wherein R₁ is hydrogen, aromatic, heterocyclic, or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, and C₄ H₉ ;

R₂ is hydrogen, aromatic, heterocyclic, or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, and C₄ H₉ or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, C₄ H₉, and C₅ H₁₁ ;

R₃ is hydrogen or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, C₄ H₉, and C₅ H₁₁ ;

R₄ is selected from the group consisting of H, CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₇ H₁₅, C₈ H₁₇, C₉ H₁₉, C₁₀ H₂₁, and phenyl, in which from 0 to 5 H within R₄ can be replaced by substituents selected from the group consisting of COOH, SO₃ H NH₂, F, Cl, Br, I, OH, SH, silicone, lower alkyl esters and lower alkyl ethers, with the proviso that R₃ and R₄ can be combined to form a bicyclic ring;

R₅ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic;

R₆ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic; and

wherein x ranges from 99 to 50 weight per cent of the polymer, y ranges from 1 to 50 weight per cent of the polymer and z ranges from 0 to 49 weight per cent of the polymer.

15. The golf ball according to claim 14, wherein the layer has a foamed structure.

16. The golf ball according to claim 14, wherein the metallocene catalyzed polymer is chosen from the group consisting of copolymers of ethylene with butene, hexene, and octene.

18. The golf ball according to claim 14, wherein the layer forms at least a portion of the mantle.

19. The golf ball according to claim 18, wherein the core has a diameter of from about 1 to about 1.63 inch, the cover has a thickness of from about 0.005 to about 0.125 inch, and the mantle has a thickness of from about 0.005 to about 0.125 inch.

28. The golf ball according to claim 16, wherein the metallocene catalyzed polymer is a copolymer of ethylene with 1-butene.

20. A golf ball comprising a cover and a core, the core having at least one layer, the layer formed of a metallocene catalyzed polymer blend, comprising from about 1 to about 100 phr of at least one metallocene catalyzed polymer and from about 99 to 0 phr of at least one ionomer, wherein the metallocene catalyzed polymer is of the formula:

##STR6## wherein R₁ is hydrogen, aromatic, heterocyclic, or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, and C₄ H₉ ;

R₂ is hydrogen, aromatic, heterocyclic, or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, and C₄ H₉ or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, C₄ H₉, and C₅ H₁₁ ;

R₃ is hydrogen or lower alkyl selected from the group consisting of CH₃, C₂ H₅, C₃ H₇, C₄ H₉, and C₅ H₁₁ ;

R₄ is selected from the group consisting of H, CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₇ H₁₅, C₈ H₁₇, C₉ H₁₉, C₁₀ H₂₁, and phenyl, in which from 0 to 5 H within R₄ can be replaced by substituents selected from the group consisting of COOH, SO₃ H, NH₂, F, Cl, Br, I, OH, SH, silicone, lower alkyl esters and lower alkyl ethers, with the proviso that R₃ and R₄ can be combined to form a bicyclic ring;

R₅ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic;

R₆ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic; and

wherein x ranges from 99 to 50 weight per cent of the polymer, y ranges from 1 to 50 weight per cent of the polymer and z ranges from 0 to 49 weight per cent of the polymer.

21. The golf ball according to claim 20, wherein the layer has a foamed structure.

22. The golf ball according to claim 20, wherein the cover comprises a density increasing filler material.

23. The golf ball according to claim 20, wherein the core comprises a liquid center.

24. The golf ball according to claim 20, wherein the layer has a Shore D hardness of from about 15 to about 80.

25. The golf ball according to claim 20, wherein the core has a diameter of from about 1.0 to about 1.63 inch, and the layer has a thickness of from about 0.005 to about 0.125 inch.

26. The golf ball according to claim 20, wherein the metallocene catalyzed polymer is chosen from the group consisting of copolymers of ethylene with butene, hexene, and octene.

27. The golf ball according to claim 26, wherein the metallocene catalyzed polymer is a copolymer of ethylene with 1-butene.

29. A golf ball comprising at least one layer, the layer formed of a metallocene catalyzed polymer blend, comprising from about 1 to about 100 phr of at least one metallocene catalyzed polymer and from about 99 to 0 phr of at least one ionomer, wherein the metallocene catalyzed polymer comprises a copolymer of ethylene or propylene with butene, hexene, or octene.

30. The golf ball according to claim 29, wherein the metallocene catalyzed polymer further comprises functional groups introduced by a post-polymerization reaction.

31. The golf ball according to claim 30, wherein the functional groups introduced by a post-polymerization reaction include COOH, SO₃ H, NH₂, anhydrides, and salts thereof, OH, SH, siloxane, and silicone functional groups.