Golf ball cover compositions and method of making same

• US 6,121,384 A
• Filed: 12/18/1998
• Issued: 09/19/2000
• Est. Priority Date: 11/21/1995
• Status: Expired due to Term

• 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:
  US09/215,370
• Time in Patent Office: 641 Days
• Field of Search: 525/221, 525/330.6, 525/539, 473/371, 473/372, 473/378, 473/385
• US Class Current: 525/221
• CPC Class Codes: C08F 210/00 Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 210/02 Ethene
• CPC Class Codes: C08F 8/44 Preparation of metal salts or ammonium salts

Abstract

A process for forming a golf ball cover composition, which process comprises: a) forming a polymer comprising (1) a first monomeric component comprising an olefinic monomer having from 2 to 8 carbon atoms; (2) a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms; and (3) an optional third monomeric component comprising at least one monomer 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 vinyl ether of an alkyl acid having from 4 to 21 carbon atoms; b) applying a sufficient amount of heat to the polymer to convert it to a substantially molten state; c) adding an inorganic metal base to the molten polymer to form a mixture; and d) saponifying the mixture to form a polymer salt particularly adapted for forming improved golf ball covers.

Claims

1. A golf ball comprising a cover and a core, said cover optionally comprising more than one layer and said core optionally comprising more than one layer, wherein at least one of said cover layers comprises a saponified polymer prepared by a process which comprises:

a) forming a polymer comprising (1) a first monomeric component comprising a first olefinic monomer having from 2 to 8 carbon atoms;

(2) a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms; and

(3) an optional third monomeric component comprising at least one monomer selected from the group consisting of carbon monoxide, sulfur dioxide, an anhydride monomer, an unsaturated monocarboxylic acid, a second 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;

b) applying a sufficient amount of heat to said polymer to convert said polymer to a substantially molten state;

c) forming a mixture by adding an inorganic metal base to said molten polymer such that the viscosity of the mixture remains substantially unchanged from the viscosity of the molten polymer;

followed by

d) saponifying said mixture to produce a polymer salt adapted for forming improved golf ball cover layers, wherein a sufficient amount of the inorganic metal base is added to said molten polymer in forming said mixture to obtain a degree of saponification of said polymer ranging between about 1 and 50 percent.

2. The golf ball of claim 1, wherein the metal base is comprised of at least one metallic cation selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, Cd, Hg, La, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ni, Pd, Pt, Cu, Ag, B, Al, Sn, and Pb.

3. The golf ball of claim 1, wherein the first monomeric component has the general formula:

##STR7## wherein;

R₁ is hydrogen or an alkyl group; and

R₂ is hydrogen, lower alkyl including C₁ -C₅ ;

carbocyclic, aromatic or heterocyclic.

4. The golf ball of claim 1, wherein the second monomeric component is an unsaturated acrylate class ester having the general formula:

##STR8## wherein;

R₃ is hydrogen or an alkyl group;

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

R₅ is selected from the group consisting of C_n H_2n+1, for n=1 to 18 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, NH₃, succinic anhydride and their salts, F, Cl, Br, I, OH, SH, epoxy, silicone, lower alkyl esters, lower alkyl ethers, and aromatic or heterocyclic rings with the proviso that R₄ and R₅ can be combined to form a bicyclic ring.

5. The golf ball of claim 1, wherein the third monomeric component is at least one of the monomers selected from the group consisting of:

##STR9## wherein;

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

R₇ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic;

R₈ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic;

R₉ is hydrogen, lower alkyl including C₁ -C₅ ;

R₁₀ is hydrogen, or is selected from the group consisting of C_R H_2n+1, for n=1 to 18 and phenyl, in which from 0 to 5 H within R₁₀ can be replaced by substituents selected from the group consisting of COOH, SO₃ H, NH₃ and their salts, F, Cl, Br, I, OH, SH, silicon, lower alkyl esters, lower alkyl ethers and aromatic or heterocyclic rings with the proviso that R₉ and R₁₀ can be combined to form a bicyclic ring;

R₁₁ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic;

R₁₂ is hydrogen or lower alkyl including C₁ -C₅ ;

R₁₃ is hydrogen, or is selected from the group consisting of C_R H_2n+1, for n=1 to 18 and phenyl, in which from 0 to 5 H within R₁₃ can be replaced by substituents selected from the group consisting of COOH, SO₃ H, NH₃ and their salts, F, Cl, Br, I, OH, SH, silicon, lower alkyl esters, lower alkyl ethers and aromatic or heterocyclic rings with the proviso that R₁₂ and R₁₃ can be combined to form a bicyclic ring.

6. The golf ball of claim 1, wherein said polymer is grafted by addition of a grafting agent.

7. The golf ball of claim 1, wherein said saponified polymer is blended with at least one additional thermoplastic ionomer.

8. The golf ball of claim 7, wherein said thermoplastic ionomer is at least one ionomer selected from the group consisting of ethylene methacrylic acid ionomers, ethylene acrylic acid ionomers, terpolymer ionomers comprising ethylene and methacrylic acid monomeric units, and terpolymer ionomers comprising ethylene and acrylic acid monomeric units.

9. The golf ball of claim 1, wherein said saponified polymer is blended with at least one non-ionic thermoplastic.

10. The golf ball of claim 9, wherein said non-ionic thermoplastic is at least one polymer selected from the group consisting of poly(butyl acrylate), poly(2-ethylbutyl acrylate), poly(heptyl acrylate), poly(silanes), block poly(ether-ester) copolymers, styrene-butadiene-styrene block copolymers, styrene-(ethylene-propylene)-styrene block copolymers, styrene-(ethylene-butylene)-styrene block copolymers, styrene-butadiene-styrene block copolymers comprising maleic anhydride functionality, styrene-(ethylene-propylene)-styrene block copolymers comprising maleic anhydride functionality, styrene-(ethylene-butylene)-styrene block copolymers comprising maleic anhydride functionality, styrene-butadiene-styrene block copolymers comprising sulfonic functionality, styrene-(ethylene-propylene)-styrene block copolymers comprising sulfonic functionality, styrene-(ethylene-butylene)-styrene block copolymers comprising sulfonic functionality, ethylene-acrylate copolymers, ethylene methacrylate copolymers, ethylene-octene copolymers made from metallocene catalysts, ethylene-alpha olefin copolymers and terpolymers made from metallocene catalysts, block poly(urethane-ester) copolymers, block poly(urethane-ether) copolymers, block poly(urethane-caprolactone) copolymers, polycaprolactone, polyesters, polyamides, ethylene-propylene-(diene monomer) terpolymers, sulfonated derivatives of ethylene-propylene-(diene monomer) terpolymers, and carboxylated derivatives of ethylene-propylene-(diene monomer) terpolymers.

11. A golf ball comprising a cover and a core, said cover optionally comprising more than one layer and said core optionally comprising more than one layer, wherein at least one of said cover layers comprises a saponified polymer prepared by a process which comprises:

(a) forming a polymer comprising;

(1) a first monomeric component comprising a first olefinic monomer having from 2 to 8 carbon atoms;

(2) a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms; and

(3) an optional third monomeric component comprising at least one monomer selected from the group consisting of carbon monoxide, sulfur dioxide, an anhydride monomer, an unsaturated monocarboxylic acid, a second 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;

(b) introducing the polymer into an inlet zone of an extruder comprising an inlet and at least one addition zone;

(c) melting and mixing the polymer in the inlet zone;

(d) passing the molten polymer through an addition zone within said extruder;

(e) forming a mixture at a first temperature above the melting temperature of the polymer and below a second temperature at which saponification takes place by adding a solution consisting essentially of at least one metal base and at least one nonaqueous solvent into the molten polymer as it passes through the addition zone such that the viscosity of the mixture remains substantially unchanged from the viscosity of the molten polymer;

followed by

(f) saponifying said mixture at the second temperature to produce a polymer salt adapted for use in forming a golf ball cover layer, wherein a sufficient amount of the inorganic metal base is added to said molten polymer in forming said mixture to obtain a degree of saponification of said polymer ranging between about 1 and 50 percent.

12. The golf ball of claim 11, wherein the extruder has at least two addition zones connected in series and wherein a portion of said metal base solution is added in each said addition zone.

13. The golf ball of claim 11, wherein said saponified polymer is blended with at least one additional thermoplastic ionomer.

14. The golf ball of claim 13, wherein said thermoplastic ionomer is at least one ionomer selected from the group consisting of ethylene methacrylic acid ionomers, ethylene acrylic acid ionomers, terpolymer ionomers comprising ethylene and methacrylic acid monomeric units, and terpolymer ionomers comprising ethylene and acrylic acid monomeric units.

15. The golf ball of claim 11, wherein said saponified polymer is blended with at least one non-ionic thermoplastic.

16. The golf ball of claim 15, wherein said non-ionic thermoplastic is at least one polymer selected from the group consisting of poly(butyl acrylate), poly(2-ethylbutyl acrylate), poly(heptyl acrylate), poly(silanes), block poly(ether-ester) copolymers, styrene-butadiene-styrene block copolymers, styrene-(ethylene-propylene)-styrene block copolymers, styrene-(ethylene-butylene)-styrene block copolymers, styrene-butadiene-styrene block copolymers comprising maleic anhydride functionality, styrene-(ethylene-propylene)-styrene block copolymers comprising maleic anhydride functionality, styrene-(ethylene-butylene)-styrene block copolymers comprising maleic anhydride functionality, styrene-butadiene-styrene block copolymers comprising sulfonic functionality, styrene-(ethylene-propylene)-styrene block copolymers comprising sulfonic functionality, styrene-(ethylene-butylene)-styrene block copolymers comprising sulfonic functionality, ethylene-acrylate copolymers, ethylene methacrylate copolymers, ethylene-octene copolymers made from metallocene catalysts, ethylene-alpha olefin copolymers and terpolymers made from metallocene catalysts, block poly(urethane-ester) copolymers, block poly(urethane-ether) copolymers, block poly(urethane-caprolactone) copolymers, polycaprolactone, polyesters, polyamides, ethylene-propylene-(diene monomer) terpolymers, sulfonated derivatives of ethylene-propylene-(diene monomer) terpolymers, and carboxylated derivatives of ethylene-propylene-(diene monomer) terpolymers.

17. A one-piece golf ball comprising a saponified polymer prepared by a process which comprises:

a) forming a polymer comprising (1) a first monomeric component comprising a first olefinic monomer having from 2 to 8 carbon atoms;

(2) a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms; and

(3) an optional third monomeric component comprising at least one monomer selected from the group consisting of carbon monoxide, sulfur dioxide, an anhydride monomer, an unsaturated monocarboxylic acid, a second 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;

b) applying a sufficient amount of heat to said polymer to convert said polymer to a substantially molten state;

c) forming a mixture by adding an inorganic metal base to said molten polymer such that the viscosity of the mixture remains substantially unchanged from the viscosity of the molten polymer;

followed by

d) saponifying said mixture to produce a polymer salt adapted for forming improved golf balls, wherein a sufficient amount of the inorganic metal base is added to said molten polymer in forming said mixture to obtain a degree of saponification of said polymer ranging between about 1 and 50 percent.

18. The golf ball of claim 17, wherein the metal base is comprised of at least one metallic cation selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, Cd, Hg, La, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ni, Pd, Pt, Cu, Ag, B, Al, Sn, and Pb.

19. The golf ball of claim 17, wherein the first monomeric component has the general formula:

##STR10## wherein;

R₁ is hydrogen or an alkyl group; and

R₂ is hydrogen, lower alkyl including C₁ -C₅ ;

carbocyclic, aromatic or heterocyclic.

20. The golf ball of claim 17, wherein the second monomeric component is an unsaturated acrylate class ester having the general formula:

##STR11## wherein;

R₃ is hydrogen or an alkyl group;

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

R₅ is selected from the group consisting of C_n H_2n+1, for n=1 to 18 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, NH₃, succinic anhydride and their salts, F, Cl, Br, I, OH, SH, epoxy, silicone, lower alkyl esters, lower alkyl ethers, and aromatic or heterocyclic rings with the proviso that R₄ and R₅ can be combined to form a bicyclic ring.

21. The golf ball of claim 17, wherein the third monomeric component is at least one of the monomers selected from the group consisting of:

##STR12## wherein;

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

R₇ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic;

R₈ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic;

R₉ is hydrogen, lower alkyl including C₁ -C₅ ;

R₁₀ is hydrogen, or is selected from the group consisting of C_R H_2n+1, for n=1 to 18 and phenyl, in which from 0 to 5 H within R₁₀ can be replaced by substituents selected from the group consisting of COOH, SO₃ H, NH₃ and their salts, F, Cl, Br, I, OH, SH, silicon, lower alkyl esters, lower alkyl ethers and aromatic or heterocyclic rings with the proviso that R₉ and R₁₀ can be combined to form a bicyclic ring;

R₁₁ is hydrogen, lower alkyl including C₁ -C₅, carbocyclic, aromatic or heterocyclic;

R₁₂ is hydrogen or lower alkyl including C₁ -C₅ ;

R₁₃ is hydrogen, or is selected from the group consisting of C_R H_2n+1, for n=1 to 18 and phenyl, in which from 0 to 5 H within R₁₃ can be replaced by substituents selected from the group consisting of COOH, SO₃ H, NH₃ and their salts, F, Cl, Br, I, OH, SH, silicon, lower alkyl esters, lower alkyl ethers and aromatic or heterocyclic rings with the proviso that R₁₂ and R₁₃ can be combined to form a bicyclic ring.

22. The golf ball of claim 17, wherein said polymer is grafted by addition of a grafting agent.

23. A one-piece golf ball comprising a saponified polymer prepared by a process which comprises:

(a) forming a polymer comprising;

(1) a first monomeric component comprising a first olefinic monomer having from 2 to 8 carbon atoms;

(2) a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms; and

(3) an optional third monomeric component comprising at least one monomer selected from the group consisting of carbon monoxide, sulfur dioxide, an anhydride monomer, an unsaturated monocarboxylic acid, a second 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;

(b) introducing the polymer into an inlet zone of an extruder comprising an inlet and at least one addition zone;

(c) melting and mixing the polymer in the inlet zone;

(d) passing the molten polymer through an addition zone within said extruder;

(e) forming a mixture at a first temperature above the melting temperature of the polymer and below a second temperature at which saponification takes place by adding a solution consisting essentially of at least one metal base and at least one nonaqueous solvent into the molten polymer as it passes through the addition zone such that the viscosity of the mixture remains substantially unchanged from the viscosity of the molten polymer;

followed by

(f) saponifying said mixture at the second temperature to produce a polymer salt adapted for use in forming a golf ball, wherein a sufficient amount of the inorganic metal base is added to said molten polymer in forming said mixture to obtain a degree of saponification of said polymer ranging between about 1 and 50 percent.

24. The one-piece golf ball of claim 23, wherein the extruder has at least two addition zones connected in series and wherein a portion of said metal base solution is added in each said addition zone.