Multi-layer golf ball

• US 8,177,665 B2
• Filed: 01/31/2006
• Issued: 05/15/2012
• Est. Priority Date: 02/01/2005
• Status: Active Grant

• Current Assignee: Taylor Made Golf Co., Inc.
• Original Assignee: Taylor Made Golf Co., Inc.
• Inventors: Loper, Eric, Snell, Dean, Kim, Hyun Jin
• Primary Examiner(s): Gorden, Raeann
• Application Number:
  US11/344,976
• Publication Number:
  US 20060172823A1
• Time in Patent Office: 2,296 Days
• Field of Search: 473/376, 473/368, 473/367
• US Class Current: 473/376
• 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 37/0043 Hardness
• CPC Class Codes: A63B 37/0045 Thickness
• CPC Class Codes: A63B 37/0049 Flexural modulus; Bending stiffness
• CPC Class Codes: A63B 37/0054 Substantially rigid, e.g. metal
• CPC Class Codes: A63B 37/0064 Diameter
• CPC Class Codes: A63B 37/0065 Deflection or compression
• CPC Class Codes: A63B 37/0069 Flexural modulus; Bending stiffness
• CPC Class Codes: A63B 37/0076 Multi-piece balls, i.e. having two or more intermediate layers
• CPC Class Codes: C08L 23/0869 Acids or derivatives thereof
• CPC Class Codes: C08L 23/0876 Neutralised polymers, i.e. ionomers
• CPC Class Codes: C08L 2666/06 Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof

Abstract

A four-piece solid golf ball construction is disclosed, including one or more core layers, an inner mantle layer, an outer mantle layer, and one or more cover layers. The inner mantle layer has a Shore D hardness in the range of 20 to 60, and the outer mantle layer has a Shore D hardness in the range of 40 to 80 and exceeding that of the inner mantle layer by at least 3. The solid golf ball provides a high spin rate when struck not only by a full 8-iron, but also by a soft pitching wedge, for short shots near a putting green.

Claims

1. A golf ball comprising:

(a) one or more core layers having a flexural modulus (F1) less than 30 kpsi;

(b) an inner mantle layer immediately adjacent to and surrounding the one or more core layers, wherein the inner mantle layer has a flexural modulus (F2) in the range of 15 to 60 kpsi and a thickness of less than 0.08 inches;

(c) an outer mantle layer immediately adjacent to and surrounding the inner mantle layer, wherein the outer mantle layer has a flexural modulus (F3) in the range of 30 to 120 kpsi; and

(d) one or more cover layers surrounding the outer mantle layer;

(e) wherein the flexural modulus (F2) of the inner mantle layer is greater than the flexural modulus (F1) of the one or more core layers by at least 3 kpsi;

(f) and wherein the flexural modulus (F3) of the outer mantle layer is greater than the flexural modulus (F2) of the inner mantle layer by at least 12 kpsi.

2. The golf ball of claim 1, wherein the inner mantle layer and/or the outer mantle layer comprises ionomeric polymer comprising:

(a) an ionomeric polymer comprising one or more E/X/Y copolymers, wherein E is ethylene, X is a C₃ to C₈ α

,β

ethylenically unsaturated carboxylic acid, and Y is a softening comonomer selected from the group consisting of alkyl acrylate and alkyl methacrylate, wherein the alkyl groups have from 1 to 8 carbon atoms, or ionomers of such E/X/Y copolymers, wherein X is in the range of about 5 to about 35 weight % of the E/X/Y copolymer and Y is in the range of 0 to about 50 weight % of the E/X/Y copolymer, and wherein the acid groups present in the ionomeric polymer are partially neutralized with a metal selected from the group consisting of zinc, sodium, lithium, calcium, magnesium, and combinations thereof;

or

(b) a bimodal ionomeric polymer comprising;

(i) a high molecular weight component having a molecular weight in the range of about 80,000 to about 500,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the high molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof, and

(ii) a low molecular weight component having a molecular weight in the range of about 2,000 to about 30,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the low molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof;

or

(c) a modified ionomeric polymer comprising;

(i) a blend composition comprising;

(1) ethylene,

(2) 5 to 25 weight percent (meth)acrylic acid (based on the total weight of the modified ionomeric polymer), and

(3) 0 to 40 weight percent of a C₁ to C₈-alkyl acrylate (based on the total weight of the modified ionomeric polymer), and

(4) about 5 to about 45 weight percent (based on the total weight of the modified ionomeric polymer) of a fatty acid or one or more metal salts of a fatty acid, or

(ii) a bimodal polymer blend composition comprising;

(1) a high molecular weight component having a molecular weight in the range of about 80,000 to about 500,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the high molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof,

(2) a low molecular weight component having a molecular weight in the range of about 2,000 to about 30,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the low molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof, and

(3) about 5 to about 45 weight percent (based on the total weight of the modified ionomeric polymer) of a fatty acid or one or more metal salts of a fatty acid;

or

(d) a blend composition comprising the reaction product of;

(i) one or more ionomers, and

(ii) a compound having a general formula (R₂N)_m—

R′

—

(X(O)_nOR_y)_m, wherein R is selected from the group consisting of

(1) hydrogen,

(2) one or more C₁-C₂₀ aliphatic systems,

(3) one or more cycloaliphatic systems,

(4) one or more aromatic systems, and

(5) combinations thereof,

wherein R′

is a bridging group comprising

(1) one or more unsubstituted C₁-C₂₀ straight chain or branched aliphatic or alicyclic groups, or

(2) one or more substituted straight chain or branched aliphatic or alicyclic groups, or

(3) one or more aromatic groups, or

(4) one or more oligomers each containing up to 12 repeating units,

wherein when X=C or S or P, m is 1-3,

wherein when X=C, n=1 and y=1,

wherein when X=S, n=2 and y=1, and

wherein when X=P, n=2 and y=2;

or

(e) combinations of (a), (b), (c), and (d).

3. The golf ball of claim 1, wherein the inner mantle layer and/or the outer mantle layer comprises:

(a) a matrix polymer selected from the group consisting of thermoplastics, thermosets, and combinations thereof; and

(b) one or more nanofillers substantially dispersed in the matrix polymer.

4. The golf ball of claim 3, wherein the nanofiller is intercalated within the matrix polymer.

5. The golf ball of claim 3, wherein the nanofiller is exfoliated within the matrix polymer.

6. The golf ball of claim 1, wherein the inner mantle layer and/or the outer mantle layer comprises a polymer selected from the group consisting of thermoplastic resins, thermoset resins, polyurethane resins, polyester resins, polyamide elastomer resins, polyamide-ionomer, polyurethane ionomer, thermoplastic copolyetherester block copolymer, thermoplastic copolyesterester block copolymer, thermoplastic elastomer, thermoset elastomer, synthetic rubber, thermoplastic vulcanizate, copolymeric ionomer, terpolymeric ionomer, polyurethane ionomer, polyamide ionomer, polycarbonate, polyolefin, polyamide, copolymeric polyamide, polyester, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polyarylate, polyacrylate, polyphenylene ether, impact-modified polyphenylene ether, high impact polystyrene, diallyl phthalate polymer, metallocene catalyzed polymer, styrene-acrylonitrile (SAN) (including olefin-modified SAN and acrylonitrile-styrene-acrylonitrile), styrene-maleic anhydride (S/MA) polymer, styrenic copolymer, functionalized styrenic copolymer, functionalized styrenic terpolymer, styrenic terpolymer, cellulose polymer, liquid crystal polymer (LCP), ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymers (EVA), ethylene-propylene copolymer, ethylene vinyl acetate, polyurea, polysiloxane, and combinations thereof.

7. The golf ball of claim 1, wherein at least one of the one or more cover layers comprises a material selected from the group consisting of thermoset polyurethane, thermoplastic polyurethane, ionomer, and combinations thereof.

8. The golf ball of claim 1, wherein at least one of the one or more cover layer comprises ionomeric polymer comprising:

(a) an ionomeric polymer comprising one or more E/X/Y copolymers, wherein E is ethylene, X is a C₃ to C₈ α

,β

ethylenically unsaturated carboxylic acid, and Y is a softening comonomer selected from the group consisting of alkyl acrylate and alkyl methacrylate, wherein the alkyl groups have from 1 to 8 carbon atoms, or ionomers of such E/X/Y copolymers, wherein X is in the range of about 5 to about 35 weight % of the E/X/Y copolymer and Y is in the range of 0 to about 50 weight % of the E/X/Y copolymer, and wherein the acid groups present in the ionomeric polymer are partially neutralized with a metal selected from the group consisting of zinc, sodium, lithium, calcium, magnesium, and combinations thereof;

or

(b) a bimodal ionomeric polymer comprising;

(i) a high molecular weight component having a molecular weight in the range of about 80,000 to about 500,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the high molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof, and

(ii) a low molecular weight component having a molecular weight in the range of about 2,000 to about 30,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the low molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof;

or

(c) a modified ionomeric polymer comprising;

(i) a blend composition comprising;

(1) ethylene,

(2) 5 to 25 weight percent (meth)acrylic acid (based on the total weight of the modified ionomeric polymer), and

(3) 0 to 40 weight percent of a C₁ to C₈-alkyl acrylate (based on the total weight of the modified ionomeric polymer), and

(4) about 5 to about 45 weight percent (based on the total weight of the modified ionomeric polymer) of a fatty acid or one or more metal salts of a fatty acid, or

(ii) a bimodal polymer blend composition comprising;

(1) a high molecular weight component having a molecular weight in the range of about 80,000 to about 500,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the high molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof,

(2) a low molecular weight component having a molecular weight in the range of about 2,000 to about 30,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the low molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof, and

(3) about 5 to about 45 weight percent (based on the total weight of the modified ionomeric polymer) of a fatty acid or one or more metal salts of a fatty acid;

or

(d) a blend composition comprising the reaction product of;

(i) one or more ionomers, and

(ii) a compound having a general formula (R₂N)_m—

R′

—

(X(O)_nOR_y)_m,

(iii) wherein R is selected from the group consisting of

(1) hydrogen,

(2) one or more C₁-C₂₀ aliphatic systems,

(3) one or more cycloaliphatic systems,

(4) one or more aromatic systems, and

(5) combinations thereof,

(iv) wherein R′

is a bridging group comprising

(1) one or more unsubstituted C₁-C₂₀ straight chain or branched aliphatic or alicyclic groups, or

(2) one or more substituted straight chain or branched aliphatic or alicyclic groups, or

(3) one or more aromatic groups, or

(4) one or more oligomers each containing up to 12 repeating units,

(v) wherein when X=C or S or P, m is 1-3,

(vi) wherein when X=C, n=1 and y=1,

(vii) wherein when X=S, n=2 and y=1, and

(viii) wherein when X=P, n=2 and y=2;

or

(e) combinations of (a), (b), (c), and (d).

9. The golf ball of claim 1, wherein at least one of the one or more cover layers comprises an ionomer and a block copolymer, the block copolymer comprising a first polymer block comprising an aromatic vinyl compound, a second polymer block comprising a conjugated diene compound, and a hydroxyl group located at a block copolymer, or its hydrogenation product, wherein the ratio of block copolymer to ionomer is in the range of about 51:

49 to about 95;

5 by weight.

10. The golf ball of claim 1, wherein at least one of the one or more cover layers comprises:

(a) a matrix polymer selected from the group consisting of thermoplastics, themosets and combinations thereof; and

(b) one or more nanofillers substantially dispersed in the matrix polymer.

11. The golf ball of claim 10, wherein the nanofiller is intercalated within the matrix polymer.

12. The golf ball of claim 10, wherein the nanofiller is exfoliated within the matrix polymer.

13. The golf ball of claim 1, wherein at least one of the one or more core layers comprises a modified ionomeric polymer comprising:

(a) an ionomeric polymer comprising one or more E/X/Y copolymers, wherein E is ethylene, X is a C₃ to C₈ α

,β

ethylenically unsaturated carboxylic acid, and Y is a softening comonomer selected from the group consisting of alkyl acrylate and alkyl methacrylate, wherein the alkyl groups have from 1 to 8 carbon atoms, or ionomers of such E/X/Y copolymers, wherein X is in the range of about 5 to about 35 weight % of the E/X/Y copolymer and Y is in the range of 0 to about 50 weight % of the E/X/Y copolymer, and wherein the acid groups present in the ionomeric polymer are partially neutralized with a metal selected from the group consisting of zinc, sodium, lithium, calcium, magnesium, and combinations thereof;

or

(b) a bimodal ionomeric polymer comprising;

a high molecular weight component having a molecular weight in the range of about 80,000 to about 500,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the high molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof, and

(ii) a low molecular weight component having a molecular weight in the range of about 2,000 to about 30,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the low molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof;

or

(c) a modified ionomeric polymer comprising;

(i) a blend composition comprising;

(1) ethylene,

(2) 5 to 25 weight percent (meth)acrylic acid (based on the total weight of the modified ionomeric polymer), and

(3) 0 to 40 weight percent of a C₁ to C₈-alkyl acrylate (based on the total weight of the modified ionomeric polymer), and

(4) about 5 to about 45 weight percent (based on the total weight of the modified ionomeric polymer) of a fatty acid or one or more metal salts of a fatty acid, or

(ii) a bimodal polymer blend composition comprising;

(1) a high molecular weight component having a molecular weight in the range of about 80,000 to about 500,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the high molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof,

(2) a low molecular weight component having a molecular weight in the range of about 2,000 to about 30,000 and comprising one or more ethylene/α

,β

-ethylenically unsaturated C_3-8 carboxylic acid copolymers and/or one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the low molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof, and

(3) about 5 to about 45 weight percent (based on the total weight of the modified ionomeric polymer) of a fatty acid or one or more metal salts of a fatty acid;

or

(d) a blend composition comprising the reaction product of;

(i) one or more ionomers, and

(ii) a compound having a general formula (R₂N)_m—

R′

—

(X(O)_nOR_y)_m,

(iii) wherein R is selected from the group consisting of

(1) hydrogen,

(2) one or more C₁-C₂₀ aliphatic systems,

(3) one or more cycloaliphatic systems,

(4) one or more aromatic systems, and

(5) combinations thereof,

(iv) wherein R′

is a bridging group comprising

(1) one or more unsubstituted C₁-C₂₀ straight chain or branched aliphatic or alicyclic groups, or

(2) one or more substituted straight chain or branched aliphatic or alicyclic groups, or

(3) one or more aromatic groups, or

(4) one or more oligomers each containing up to 12 repeating units,

(v) wherein when X=C or S or P, m is 1-3,

(vi) wherein when X=C, n=1 and y=1,

(vii) wherein when X=S, n=2 and y=1, and

(viii) wherein when X=P, n=2 and y=2;

or

(e) combinations of (a), (b), (c), and (d).

14. The golf ball of claim 1, wherein at least one of the one or more core layers comprises:

(a) at least one unsaturated polymer;

(b) at least one cross-linking agent;

(c) optionally, at least one co-cross-linking agent;

(d) optionally, at least one peptizer;

(e) optionally, at least one accelerator; and

(f) optionally, at least one filler.

15. The golf ball of claim 14, wherein:

(a) the unsaturated polymer has a Mooney viscosity (ML₁₊₄(100°

C.)) of from about 20 to about 80 and is selected from the group consisting of 1,2-polybutadiene, cis-1,4-polybutadiene, trans-1,4-polybutadiene, cis-polyisoprene, trans-polyisoprene, polychloroprene, polybutylene, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer and partially and fully hydrogenated equivalents, styrene-isoprene-styrene block copolymer and partially and fully hydrogenated equivalents, nitrile rubber, silicone rubber, and polyurethane, and combinations thereof;

(b) the cross-linking agent is present in an amount of from about 0.05 to about 5 parts by weight of the cross-linking agent per 100 parts by weight of the unsaturated polymer;

(c) the peptizer, if present, comprises

(i) an organic sulfur compound,

(ii) a metal salt of an organic sulfur compound,

(iii) a non-metal salt of an organic sulfur compound, or

(iv) combinations of (i), (ii), and/or (iii);

(d) the accelerator, if present, is present in an amount of from about 0.1 to about 10 parts by weight per 100 parts by weight of the unsaturated polymer; and

(e) the filler, if present, is selected from the group consisting of precipitated hydrated silica, limestone, clay, talc, asbestos, barytes, glass fibers, aramid fibers, mica, calcium metasilicate, barium sulfate, zinc sulfide, lithopone, silicates, silicon carbide, diatomaceous earth, carbonates such as calcium or magnesium or barium carbonate, sulfates such as calcium or magnesium or barium sulfate, metals, including tungsten steel copper, cobalt or iron, metal alloys, tungsten carbide, metal oxides, metal stearates, other particulate carbonaceous materials, and combinations thereof.

16. The golf ball of claim 14, wherein:

(a) the unsaturated polymer is cis-1,4-polybutadiene and has a Mooney viscosity (ML₁₊₄(100°

C.)) of from about 30 to about 60;

(b) the cross-linking agent is present in an amount of from about 0.2 to about 3 parts by weight per 100 parts by weight of the unsaturated polymer;

(c) the peptizer, if present, is

(i) present in an amount of from about 0.01 to about 10 parts by weight per 100 parts by weight of the unsaturated polymer, and

(ii) is selected from the group consisting of organic sulfur compounds, metal salts of an organic sulfur compound, non-metal salts of an organic sulfur compound, and combinations thereof; and

(d) the accelerator, if present, is present in an amount of from about 0.2 to about 5 parts by weight of the accelerator per 100 parts by weight of the unsaturated polymer.

17. The golf ball of claim 14, wherein:

(a) the unsaturated polymer is cis-1,4-polybutadiene and has a Mooney viscosity (ML₁₊₄(100°

C.)) of from about 35 to about 50;

(b) the cross-linking agent is present in an amount of from about 0.2 to about 2 parts by weight per 100 parts by weight of the unsaturated polymer;

(c) the peptizer, if present, is

(i) present in an amount of from about 0.1 to about 7 parts by weight per 100 parts by weight of the unsaturated polymer, and

(ii) selected from the group consisting of pentachlorothiophenol, dibenzamido diphenyldisulfide, a metal salt of pentachlorothiophenol, an ammonium salt of pentachlorothiophenol with the ammonium cation having the general formula [NR¹R²R³R⁴]⁺ where R¹, R², R³, and R⁴ is either hydrogen, or a C₁-C₂₀ aliphatic, cycloaliphatic or aromatic system, and combinations thereof; and

(d) the accelerator, if present, is present in an amount of from about 0.5 to about 1.5 parts by weight per 100 parts by weight of the unsaturated polymer and is selected from the group consisting of 2-mercaptobenzothiazole and a salt of 2-mercaptobenzothiazole.

18. The golf ball of claim 14, wherein the peptizer is present in an amount of from about 0.15 to about 5 parts by weight per 100 parts by weight of the unsaturated polymer, and is selected from the group consisting of pentachlorothiophenol, the zinc salt of pentachlorothiophenol, the NH₄⁺ salt of pentachlorothiophenol, and combinations thereof.

48. The golf ball of claim 15, wherein the peptizer is present.

49. The golf ball of claim 15, wherein the accelerator is present and is a salt of 2-mercaptobenzothiazole.

50. The golf ball of claim 16, wherein the peptizer is present.

51. The golf ball of claim 16, wherein the accelerator is present and is a salt of 2-mercaptobenzothiazole.

52. The golf ball of claim 17, wherein the accelerator is present and is a salt of 2-mercaptobenzothiazole.

19. A golf ball, comprising:

a molded core comprising a high cis-polybutadiene having a Mooney viscosity in the range of about 20 to about 70 and a PGA compression in the range of about 10 to about 100;

an inner mantle comprising an ionomer neutralized to 80% or more and having a Shore D hardness in the range of about 20to about 70;

an outer mantle comprising an ionomer having a Shore D hardness in the range of about 40 to about 90 and having a composition different from that of the inner mantle; and

a thermoset polyurethane/polyurea cover;

wherein the core has a flexural modulus less than 30 kpsi;

wherein the inner mantle is immediately adjacent to the core and has a flexural modulus in the range of 15 to 60 kpsi;

wherein the outer mantle is immediately adjacent to the inner mantle and has a flexural modulus in the range of 30 to 120 kpsi;

wherein the flexural modulus of the inner mantle is greater than the flexural modulus of the core by at least 3 kpsi; and

wherein the flexural modulus of the outer mantle is greater than the flexural modulus of the inner mantle by at least 12 kpsi.

20. The golf ball of claim 19, wherein the golf ball has a C.O.R. greater than about 0.790.

21. The golf ball of claim 20, wherein the core further comprises a peptizer.

22. The golf ball of claim 21, wherein the peptizer is pentachlorothiophenol or a metallic salt thereof.

23. The golf ball of claim 19, wherein the ionomer of the inner mantle is neutralized to about 90% or more.

24. The golf ball of claim 19, wherein the ionomer of the inner mantle is neutralized to about 100%.

25. The golf ball of claim 19, wherein the ionomer of the inner mantle is modified with a fatty acid or a salt thereof.

26. The golf ball of claim 25, wherein the fatty acid is stearic acid, oleic acid, a metal stearate, or a metal oleate.

27. The golf ball of claim 19, wherein the starting material of the inner mantle comprises an ethylene copolymer, an ethylene terpolymer or blends thereof.

28. The golf ball of claim 27, wherein the starting material of the inner mantle comprises a copolymer of ethylene and ethylene acrylate.

29. The golf ball of claim 19, wherein the polyurethane/polyurea cover is a cast or reaction-injection-molded cover.

53. The golf ball of claim 21, wherein the peptizer is an ammonium salt of pentachlorothiophenol with the ammonium cation having the general formula [NR¹R²R³R⁴]⁺ where R¹, R², R³, and R⁴ is either hydrogen, or a C₁-C₂₀ aliphatic, cycloaliphatic or aromatic system.

30. A golf ball, comprising:

a molded core comprising a high cis-polybutadiene having a Mooney viscosity in the range of about 20 to about 70 and a PGA compression in the range of about 10 to about 100;

an inner mantle comprising an ionomer having a Shore D hardness in the range of about 20 to about 70;

an outer mantle comprising an ionomer neutralized to 80% or more and having a Shore D hardness in the range of about 40 to about 90 and further having a composition different from that of the inner mantle; and

a thermoset polyurethane/polyurea cover;

wherein the core has a flexural modulus less than 30 kpsi;

wherein the inner mantle is immediately adjacent to the core and has a flexural modulus in the range of 15 to 60 kpsi;

wherein the outer mantle is immediately adjacent to the inner mantle and has a flexural modulus in the range of 30 to 120 kpsi;

wherein the flexural modulus of the inner mantle is greater than the flexural modulus of the core by at least 3 kpsi; and

wherein the flexural modulus of the outer mantle is greater than the flexural modulus of the inner mantle by at least 12 kpsi.

31. The golf ball of claim 30, wherein the core has a C.O.R. of greater than about 0.790.

32. The golf ball of claim 31, wherein the core further comprises a peptizer.

33. The golf ball of claim 30, wherein the ionomer of the outer mantle is neutralized to about 90% or more.

34. The golf ball of claim 30, wherein the ionomer of the outer mantle is neutralized to about 100%.

35. The golf ball of claim 30, wherein the ionomer of the outer mantle is modified with a fatty acid or a salt thereof.

36. The golf ball of claim 35, wherein the fatty acid is stearic acid, oleic acid, a metal stearate, or a metal oleate.

54. The golf ball of claim 32, wherein the peptizer is an ammonium salt of pentachlorothiophenol with the ammonium cation having the general formula [NR¹R²R³R⁴]⁺ where R¹, R², R³, and R⁴ is either hydrogen, or a C₁-C₂₀ aliphatic, cycloaliphatic or aromatic system.

37. A golf ball, comprising:

a molded core comprising a high cis-polybutadiene, pentachlorothiophenol or a metallic salt thereof;

an inner mantle having a flexural modulus and a thickness of less than 0.08 inches and including an ionomer resin comprising a copolymer of ethylene and ethylene acrylate neutralized to 80% or greater;

an ionomer skin having a composition different from that of the inner mantle; and

a thermoset polyurethane/polyurea cover produced by reaction-injection molding;

wherein the core has a flexural modulus less than 30 kpsi;

wherein the inner mantle is immediately adjacent to the core and has a flexural modulus in the range of 15 to 60 kpsi;

wherein the ionomer skin is immediately adjacent to the inner mantle and has a flexural modulus in the range of 30 to 120 kpsi;

wherein the flexural modulus of the inner mantle is greater than the flexural modulus of the core by at least 3 kpsi; and

wherein the flexural modulus of the ionomer skin is greater than the flexural modulus of the inner mantle by at least 12 kpsi.

38. A golf ball comprising:

one or more core layers having a flexural modulus (F1) less than 30 kpsi;

an inner mantle layer surrounding the one or more core layers, wherein the inner mantle layer has a flexural modulus (F2) in the range of 15 to 60 kpsi;

an outer mantle layer surrounding the inner mantle layer, wherein the outer mantle layer has a flexural modulus (F3) in the range of 30 to 120 kpsi; and

one or more cover layers surrounding the outer mantle layer;

wherein the flexural modulus (F2) of the inner mantle layer is greater than the flexural modulus (Fl) of the one or more core layers by at least 3 kpsi;

wherein the flexural modulus (F3) of the outer mantle layer is greater than the flexural modulus (F2) of the inner mantle layer by at least 3 kpsi; and

wherein the inner mantle layer and/or the outer mantle layer comprises a bimodal ionomeric polymer comprising;

(i) a high molecular weight component having a molecular weight in the range of about 80,000 to about 500,000and comprising one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the high molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof, and

(ii) a low molecular weight component having a molecular weight in the range of about 2,000 to about 30,000 and comprising one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the low molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof.

39. A golf ball comprising:

one or more core layers having a flexural modulus (F1) less than 30 kpsi;

an inner mantle layer immediately adjacent to and surrounding the one or more core layers, wherein the inner mantle layer has a flexural modulus (F2) in the range of 15 to 60 kpsi;

an outer mantle layer immediately adjacent to and surrounding the inner mantle layer, wherein the outer mantle layer has a flexural modulus (F3) in the range of 30 to 120 kpsi; and

one or more cover layers surrounding the outer mantle layer;

wherein the flexural modulus (F2) of the inner mantle layer is greater than the flexural modulus (F1) of the one or more core layers by at least 3 kpsi;

wherein the flexural modulus (F3) of the outer mantle layer is greater than the flexural modulus (F2) of the inner mantle layer by at least 3 kpsi; and

wherein at least one of the one or more core layers comprises;

(a) at least one unsaturated polymer;

(b) at least one cross-linking agent;

(c) at least one peptizer;

(e) optionally, at least one co-cross-linking agent;

(d) optionally, at least one accelerator; and

(f) optionally, at least one filler.

40. The golf ball of claim 39, wherein:

(a) the unsaturated polymer has a Mooney viscosity (ML₁₊₄(100°

C.)) of from about 20 to about 80 and is selected from the group consisting of 1,2-polybutadiene, cis-1,4-polybutadiene, trans-1,4-polybutadiene, cis-polyisoprene, trans-polyisoprene, polychloroprene, polybutylene, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer and partially and fully hydrogenated equivalents, styrene-isoprene-styrene block copolymer and partially and fully hydrogenated equivalents, nitrile rubber, silicone rubber, and polyurethane, and combinations thereof;

(b) the cross-linking agent is present in an amount of from about 0.05 to about 5 parts by weight of the cross-linking agent per 100 parts by weight of the unsaturated polymer;

(c) the peptizer comprises

(i) an organic sulfur compound,

(ii) a metal salt of an organic sulfur compound,

(iii) a non-metal salt of an organic sulfur compound, or

(iv) combinations of (i), (ii), and/or (iii);

(d) the accelerator, if present, is present in an amount of from about 0.1 to about 10 parts by weight per 100 parts by weight of the unsaturated polymer; and

(e) the filler, if present, is selected from the group consisting of precipitated hydrated silica, limestone, clay, talc, asbestos, barytes, glass fibers, aramid fibers, mica, calcium metasilicate, barium sulfate, zinc sulfide, lithopone, silicates, silicon carbide, diatomaceous earth, carbonates such as calcium or magnesium or barium carbonate, sulfates such as calcium or magnesium or barium sulfate, metals, including tungsten steel copper, cobalt or iron, metal alloys, tungsten carbide, metal oxides, metal stearates, other particulate carbonaceous materials, and combinations thereof.

41. The golf ball of claim 39, wherein:

(a) the unsaturated polymer is cis-1,4-polybutadiene and has a Mooney viscosity (ML₁₊₄(100°

C.)) of from about 30 to about 60;

(b) the cross-linking agent is present in an amount of from about 0.2 to about 3 parts by weight per 100 parts by weight of the unsaturated polymer;

(c) the peptizer is

(i) present in an amount of from about 0.01 to about 10 parts by weight per 100 parts by weight of the unsaturated polymer, and

(ii) is selected from the group consisting of organic sulfur compounds, metal salts of an organic sulfur compound, non-metal salt of an organic sulfur compound, and combinations thereof; and

(d) the accelerator, if present, is present in an amount of from about 0.2 to about 5 parts by weight of the accelerator per 100 parts by weight of the unsaturated polymer.

42. The golf ball of claim 39, wherein:

(a) the unsaturated polymer is cis-1,4-polybutadiene and has a Mooney viscosity (ML₁₊₄(100°

C.)) of from about 35 to about 50;

(b) the cross-linking agent is present in an amount of from about 0.2 to about 2 parts by weight per 100 parts by weight of the unsaturated polymer;

(c) the peptizer is

(i) present in an amount of from about 0.1 to about 7 parts by weight per 100 parts by weight of the unsaturated polymer, and

(ii) selected from the group consisting of pentachlorothiophenol, dibenzamido diphenyldisulfide, a metal salt of pentachlorothiophenol, an ammonium salt of pentachlorothiophenol with the ammonium cation having the general formula [NR¹R²R³R⁴]⁺ where R¹, R², R³, and R⁴ is either hydrogen, or a C₁-C₂₀ aliphatic, cycloaliphatic or aromatic system, and combinations thereof; and

(d) the accelerator, if present, is present in an amount of from about 0.5 to about 1.5 parts by weight per 100 parts by weight of the unsaturated polymer and is selected from the group consisting of 2-mercaptobenzothiazole and a salt of 2-mercaptobenzothiazole.

43. The golf ball of claim 39, wherein the peptizer is present in an amount of from about 0.15 to about 5 parts by weight per 100 parts by weight of the unsaturated polymer, and is selected from the group consisting of pentachlorothiophenol, the zinc salt of pentachlorothiophenol, the NH₄⁺ salt of pentachlorothiophenol, and combinations thereof.

55. The golf ball of claim 40, wherein the accelerator is present and is a salt of 2-mercaptobenzothiazole.

56. The golf ball of claim 41, wherein the accelerator is present and is a salt of 2-mercaptobenzothiazole.

57. The golf ball of claim 42, wherein the accelerator is present and is a salt of 2-mercaptobenzothiazole.

44. A golf ball, comprising:

a molded core comprising a high cis-polybutadiene having a Mooney viscosity in the range of about 20 to about 70 and a PGA compression in the range of about 10 to about 100;

an inner mantle comprising an ionomer neutralized to 80% or more and having a Shore D hardness in the range of about 20 to about 70 and a thickness of less than 0.08 inches;

an outer mantle comprising an ionomer having a Shore D hardness in the range of about 40 to about 90 and having a composition different from that of the inner mantle; and

a thermoset polyurethane/polyurea cover;

wherein the core has a flexural modulus less than 30 kpsi;

wherein the inner mantle is immediately adjacent to the core and has a flexural modulus in the range of 15 to 60 kpsi;

wherein the outer mantle is immediately adjacent to the inner mantle and has a flexural modulus in the range of 30 to 120 kpsi;

wherein the flexural modulus of the inner mantle is greater than the flexural modulus of the core by at least 3 kpsi; and

wherein the flexural modulus of the outer mantle is greater than the flexural modulus of the inner mantle by at least 12 kpsi.

58. The golf ball of claim 44, wherein:

the core further comprises a peptizer; and

the peptizer is an ammonium salt of pentachlorothiophenol with the ammonium cation having the general formula [NR¹R²R³R⁴]⁺ where R¹, R², R³, and R⁴ is either hydrogen, or a C₁-C₂₀ aliphatic, cycloaliphatic or aromatic system.

45. A golf ball, comprising:

a molded core comprising a high cis-polybutadiene having a Mooney viscosity in the range of about 20 to about 70 and a PGA compression in the range of about 10 to about 100;

an inner mantle comprising an ionomer having a Shore D hardness in the range of about 20 to about 70 and a thickness of less than 0.08 inches;

an outer mantle comprising an ionomer neutralized to 80% or more and having a Shore D hardness in the range of about 40 to about 90 and further having a composition different from that of the inner mantle; and

a thermoset polyurethane/polyurea cover;

wherein the core has a flexural modulus less than 30 kpsi;

wherein the inner mantle is immediately adjacent to the core and has a flexural modulus in the range of 15 to 60 kpsi;

wherein the outer mantle is immediately adjacent to the inner mantle and has a flexural modulus in the range of 30 to 120 kpsi;

wherein the flexural modulus of the inner mantle is greater than the flexural modulus of the core by at least 3 kpsi; and

wherein the flexural modulus of the outer mantle is greater than the flexural modulus of the inner mantle by at least 12 kpsi.

59. The golf ball of claim 45, wherein:

the core further comprises a peptizer; and

the peptizer is an ammonium salt of pentachlorothiophenol with the ammonium cation having the general formula [NR¹R²R³R⁴]⁺ where R¹, R², R³, and R⁴ is either hydrogen, or a C₁-C₂₀ aliphatic, cycloaliphatic or aromatic system.

46. A golf ball comprising:

one or more core layers having a flexural modulus (F1) less than 30 kpsi;

an inner mantle layer surrounding the one or more core layers, wherein the inner mantle layer has a flexural modulus (F2) in the range of 15 to 60 kpsi;

an outer mantle layer surrounding the inner mantle layer, wherein the outer mantle layer has a flexural modulus (F3) in the range of 30 to 120 kpsi; and

one or more cover layers surrounding the outer mantle layer;

wherein the flexural modulus (F2) of the inner mantle layer is greater than the flexural modulus (F1) of the one or more core layers by at least 3 kpsi;

wherein the flexural modulus (F3) of the outer mantle layer is greater than the flexural modulus (F2) of the inner mantle layer by at least 3 kpsi; and

wherein the inner mantle layer and/or the outer mantle layer comprises a modified ionomeric polymer comprising;

(i) a blend composition comprising;

(1) ethylene,

(2) 5 to 25 weight percent (meth)acrylic acid (based on the total weight of the modified ionomeric polymer), and

(3) 0 to 40 weight percent of a C₁ to C₈-alkyl acrylate (based on the total weight of the modified ionomeric polymer), and

(4) about 5 to about 45 weight percent (based on the total weight of the modified ionomeric polymer) of a fatty acid or one or more metal salts of a fatty acid, or

(ii) a bimodal polymer blend composition comprising;

(1) a high molecular weight component having a molecular weight in the range of about 80,000 to about 500,000 and comprising one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the high molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof,

(2) a low molecular weight component having a molecular weight in the range of about 2,000 to about 30,000 and comprising one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the low molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof, and

(3) about 5 to about 45 weight percent (based on the total weight of the modified ionomeric polymer) of a fatty acid or one or more metal salts of a fatty acid.

47. The golf ball of claim 46, wherein the modified ionomeric polymer comprises a bimodal polymer blend composition comprising:

(1) a high molecular weight component having a molecular weight in the range of about 80,000 to about 500,000 and comprising one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the high molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof;

(2) a low molecular weight component having a molecular weight in the range of about 2,000 to about 30,000 and comprising one or more ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, wherein the low molecular weight component is partially neutralized with metal ions selected from the group consisting of lithium, sodium, zinc, calcium, magnesium, and combinations thereof; and

(3) about 5 to about 45 weight percent (based on the total weight of the modified ionomeric polymer) of a fatty acid or one or more metal salts of a fatty acid.