Golf balls comprising highly-neutralized acid polymers

• US 6,939,907 B2
• Filed: 02/06/2003
• Issued: 09/06/2005
• Est. Priority Date: 06/26/2001
• Status: Expired due to Term

• Current Assignee: Acushnet Company (FILA Holdings Corp.)
• Original Assignee: Acushnet Company (FILA Holdings Corp.)
• Inventors: Sullivan, Michael J., Rajagopalan, Murali
• Primary Examiner(s): Buttner, David J.
• Application Number:
  US10/360,233
• Publication Number:
  US 20030144087A1
• Time in Patent Office: 943 Days
• Field of Search: 524/322, 524/394, 524/399, 524/400, 473/372, 473/373, 473/377, 473/378
• US Class Current: 524/322
• CPC Class Codes: A63B 37/0004 Surface depressions or protrusions
• CPC Class Codes: A63B 37/0024 Materials other than ionomers or polyurethane
• CPC Class Codes: A63B 37/0026 Balata
• 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 37/0047 Density; Specific gravity
• CPC Class Codes: A63B 37/0051 Materials other than polybutadienes; Constructional details
• CPC Class Codes: A63B 37/0056 Hollow; Gas-filled
• CPC Class Codes: A63B 37/0061 Coefficient of restitution
• CPC Class Codes: A63B 37/0062 Hardness
• CPC Class Codes: A63B 37/0064 Diameter
• CPC Class Codes: A63B 37/0065 Deflection or compression
• CPC Class Codes: A63B 37/0075 Three piece balls, i.e. cover, intermediate layer and core
• CPC Class Codes: A63B 37/0076 Multi-piece balls, i.e. having two or more intermediate layers
• CPC Class Codes: A63B 37/0091 Density distribution amongst the different ball layers
• CPC Class Codes: A63B 37/00922 whereby hardness of the cover is lower than hardness of the intermediate layers
• CPC Class Codes: A63B 37/0097 Layers interlocking by means of protrusions or inserts, lattices or the like
• CPC Class Codes: A63B 37/02 Special cores balls with finger holes A63B37/0001, golf ball cores A63B37/005
• CPC Class Codes: C08L 2205/02 : containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 23/08 : Copolymers of ethene C08L23/16 takes precedence
• CPC Class Codes: C08L 23/0876 : Neutralised polymers, i.e. ionomers
• CPC Class Codes: C08L 2666/04 : Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Abstract

A golf ball comprising a core comprised of a polymer containing an acid group fully-neutralized by an organic acid or a salt, a cation source, or a suitable base thereof, the core having a first Shore D hardness, a compression of no greater than about 80, and a diameter of no less than about 1.53 inches; and a cover formed of a blend comprising polyurethanes and polyureas or a copolymer comprising urethane and urea segments.

Claims

1. A golf ball comprising:

a single layer core comprised of a polymer containing an acid group, an organic acid or salt, and sufficient a cation source, or a suitable base thereof to fully neutralize the acid groups of the polymer, the core having a first Shore D hardness, a compression of no greater than about 80, and a diameter of no less than about 1.53 inches; and

a cover formed of a blend comprising polyurethanes and polyureas or a copolymer comprising urethane and urea segments.

2. The golf ball of claim 1, wherein the polyurethane comprises a polyisocyanate, a polyol, and at least one curing agent.

3. The golf ball of claim 2, wherein the polyisocyanate comprises 4,4′

-diphenylmethane diisocyanate;

polymeric 4,4′

-diphenylmethane diisocyanate;

carbodiimide-modified liquid 4,4′

-diphenylmethane diisocyanate;

4,4′

-dicyclohexylmethane diisocyanate;

p-phenylene diisocyanate;

m-phenylene diisocyanate;

toluene diisocyanate;

3,3′

-dimethyl-4,4′

-biphenylene diisocyanate;

isophoronediisocyanate;

hexamethylene diisocyanate;

naphthalene diisocyanate;

xylene diisocyanate;

p-tetramethylxylene diisocyanate;

m-tetramethylxylene diisocyanate;

ethylene diisocyanate;

propylene-1,2-diisocyanate;

tetramethylene-1,4-diisocyanate;

cyclohexyl diisocyanate;

1,6-hexamethylene-diisocyanate;

dodecane-1,12-diisocyanate;

cyclobutane-1,3-diisocyanate;

cyclohexane-1,3-diisocyanate;

cyclohexane-1,4-diisocyanate;

1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;

methyl cyclohexylene diisocyanate;

triisocyanate of HDI;

triisocyanate of 2,4,4-trimethyl-1,6-hexane diisocyanate;

tetracene diisocyanate;

napthalene diisocyanate;

anthracene diisocyanate;

isocyanurate of toluene diisocyanate;

uretdione of hexamethylene diisocyanate;

di-isocyanates, tri-isocyanates, or tetra-isocyanates.

4. The golf ball of claim 2, wherein the polyisocyanate comprises less than about 0.1% free monomer groups or the polyisocyanate comprises less than about 7.5% unreacted NCO groups.

5. The golf ball of claim 2, wherein the polyol comprises polyether polyols, fully-hydrogenated hydroxy-terminated polybutadiene;

partially-hydrogenated hydroxy-terminated polybutadiene;

polyester polyols;

polycaprolactone polyols;

or polycarbonate polyols.

6. The golf ball of claim 2, wherein the curing agent comprises diols, triols, tetraols, hydroxy-terminated curatives, or polyamines.

7. The golf ball of claim 6, wherein the polyamine comprises 3,5-dimethylthio-2,4-toluenediamine and isomers thereof;

3,5-diethyltoluene-2,4-diamine and isomers thereof;

3,5-diethyltoluene-2,6-diamine;

4,4′

-bis-(sec-butylamino)-diphenylmethane;

1,4-bis-(sec-butylamino)-benzene, 4,4′

-methylene-bis-(2-chloroaniline);

4,4′

-methylene-bis-(3-chloro-2,6-diethylaniline);

polytetramethyleneoxide-di-p-aminobenzoate;

N,N′

-dialkyldiamino diphenyl methane;

p,p′

-methylene dianiline;

m-phenylenediamine;

4,4′

-methylene-bis-(2-chloroaniline);

4,4′

-methylene-bis-(2,6-diethylaniline);

4,4′

-methylene-bis-(2,3-dichloroaniline);

4,4′

-diamino-3,3′

-diethyl-5,5′

-dimethyl diphenylmethane;

2,2′

,3,3′

-tetrachloro diamino diphenylmethane;

or trimethylene glycol di-p-aminobenzoate.

8. The golf ball of claim 1, wherein the polyurea is formed from a prepolymer comprising a polyisocyanate and a polyamine, and at least one polyamine curing agent.

9. The golf ball of claim 8, wherein at least one of the polyamine in the prepolymer or the polyamine curing agent comprises polyether amines;

methyldiethanolamine;

polyoxyalkylenediamines;

polytetramethylene ether diamines;

polyoxypropylenetriamine;

polyoxypropylene diamines;

poly(ethylene oxide capped oxypropylene) ether diamines;

propylene oxide-based triamines;

triethyleneglycoldiamines;

trimethylolpropane-based triamines;

glycerin-based triamines;

ethylene diamine;

hexamethylene diamine;

1-methyl-2,6-cyclohexyl diamine;

tetrahydroxypropylene ethylene diamine;

2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine;

4,4′

-bis-(sec-butylamino)-dicyclohexylmethane;

1,4-bis-(sec-butylamino)-cyclohexane;

1,2-bis-(sec-butylamino)-cyclohexane;

derivatives of 4,4′

-bis-(sec-butylamino)-dicyclohexylmethane;

4,4′

-dicyclohexylmethane diamine;

1,4-cyclohexane-bis-(methylamine);

1,3-cyclohexane-bis-(methylamine);

diethylene glycol di-(aminopropyl) ether;

2-methylpentamethylene-diamine;

diaminocyclohexane;

diethylene triamine;

triethylene tetramine;

tetraethylene pentamine;

propylene diamine;

1,3-diaminopropane;

dimethylamino propylamine;

diethylamino propylamine;

dipropylene triamine;

imido-bis-propylamine;

monoethanolamine, diethanolamine;

triethanolamine;

monoisopropanolamine, diisopropanolamine;

isophoronediamine;

4,4′

-methylenebis-(2-chloroaniline);

3,5;

dimethylthio-2,4-toluenediamine;

3,5-dimethylthio-2,6-toluenediamine;

3,5-diethylthio-2,4-toluenediamine;

3,5;

diethylthio-2,6-toluenediamine;

4,4′

-bis-(sec-butylamino)-diphenylmethane and derivatives thereof;

1,4-bis-(sec-butylamino)-benzene;

1,2-bis-(sec-butylamino)-benzene;

N,N′

-dialkylamino-diphenylmethane;

N,N,N′

,N′

-tetrakis (2-hydroxypropyl) ethylene diamine;

trimethyleneglycol-di-p-aminobenzoate;

polytetramethyleneoxide-di-p-aminobenzoate;

4,4′

-methylenebis-(3-chloro-2,6-diethyleneaniline);

4,4′

-methylenebis-(2,6-diethylaniline);

m-phenylenediamine;

or p-phenylenediamine.

10. The golf ball of claim 8, wherein the polyamine curing agent comprises a hindered secondary diamine.

11. The golf ball of claim 8, wherein at least one of the polyamine in the prepolymer or the polyamine curing agent has a molecular weight of between about 100 and about 5000.

12. The golf ball of claim 1, wherein the blend comprises one or more saturated, unsaturated, aromatic, or cyclic groups.

13. The golf ball of claim 1, wherein the blend is substantially free of aromatic groups or moieties.

14. The golf ball of claim 1, wherein the blend further comprises polyurethane-ureas;

polyurea-urethanes;

epoxy resins;

polyethylenes;

polyamides;

polyesters;

polycarbonates;

or polyacrylins.

15. The golf ball of claim 1, wherein the cation source is selected from a group consisting of metal cations of lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, or aluminum.

16. The golf ball of claim 1, wherein the cover has a second Shore D hardness at least 10 points less than the first hardness.

17. The golf ball of claim 1, wherein the polymer comprises ionomeric copolymers and terpolymers, ionomer precursors, thermoplastics, thermoplastic elastomers, grafted metallocene-catalyzed polymers, non-grafted metallocene-catalyzed polymers, single-site polymers, high-crystalline acid polymers and their ionomers, or cationic ionomers.

18. The golf ball of claim 1, wherein the organic acid is selected from the group consisting of aliphatic organic acids, aromatic organic acids, saturated mono-functional organic acids, unsaturated mono-functional organic acids, and multi-unsaturated mono-functional organic acids.

19. The golf ball of claim 1, wherein the salt of an organic acid comprises the salts of barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin, calcium, stearic, bebenic, erucic, oleic, linoelic, dimerized derivatives, and mixtures thereof.

20. The golf ball of claim 1, wherein the core further comprises a second polymer component comprising ionomeric copolymers and terpolymers, ionomer precursors, thermoplastics, thermoplastic elastomers, polybutadiene rubber, balata, grafted metallocene-catalyzed polymers, non-grafted metallocene-catalyzed polymers, single-site polymers, high-crystalline acid polymers, or cationic ionomers, and wherein the second polymer component has a Shore D hardness less than the first hardness and is present in an amount sufficient to reduce the core compression to less than or equal to about 70.

21. The golf ball of claim 1, wherein the core has a diameter of about 1.58 inches or greater.

22. The golf ball of claim 21, wherein the core comprises two or more layers.

23. The golf ball of claim 1, wherein the cover is cast or reaction injection molded, injection molded, or compression molded over the core.

24. The golf ball of claim 1, wherein the cover comprises an inner cover layer and an outer cover layer.

25. The golf ball of claim 24, wherein the inner cover layer has material hardness of at least about 60 Shore D and the outer cover layer has a material hardness of no greater than about 60 Shore D.

26. The golf ball of claim 24, wherein the outer cover layer has material hardness of at least about 60 Shore D and the inner cover layer has a material hardness of no greater than about 60 Shore D.

27. A golf ball comprising:

a single layer core comprised of a polymer containing an acid group, an organic acid or salt, and sufficient, cation source, or a suitable base present in an amount to neutralize the polymer by at least about 80%, wherein the core has a first Shore D hardness, a compression of no greater than about 80, and a diameter of about 0.5 to 1.55 inches; and

at least one cover layer disposed over the core having a material hardness of about 70 Shore D or less and formed of a blend comprising polyurethanes and polyureas, the blend having a second Shore D hardness being at least 10 points less than the first hardness and comprising at least one of pigments;

TiO₂;

ZnO;

optical brighteners;

surfactants;

processing aids;

foaming agents;

density-controlling fillers;

UV stabilizers;

or light stabilizers.

28. The golf ball of claim 27, wherein the salt of an organic acid is present in an amount sufficient to neutralize the polymer by at least about 90%.

29. The golf ball of claim 28, wherein the salt of an organic acid is present in an amount sufficient to neutralize the polymer by at least about 100%.

30. The golf ball of claim 27, wherein the cation source is selected from a group consisting of metal cations of lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, or aluminum.

31. The golf ball of claim 27, further comprising an intermediate layer being comprised of a polymer, an organic acid or a salt, cation source, or a suitable base, the cation source, or a suitable base thereof being present in an amount sufficient to neutralize the polymer by at least about 100%.

32. The golf ball of claim 27, wherein the cover comprises an inner cover layer and an outer cover layer.

33. The golf ball of claim 32, wherein the inner cover layer has material hardness of at least about 60 Shore D and the outer cover layer has a material hardness of no greater than about 60 Shore D.

34. The golf ball of claim 32, wherein the outer cover layer has material hardness of at least about 60 Shore D and the inner cover layer has a material hardness of no greater than about 60 Shore D.

35. The golf ball of claim 27, wherein the core comprises a solid center and an outer core layer, the solid center comprising the polymer.

36. The golf ball of claim 27, wherein the core comprises a solid center and an outer core layer, the outer core layer comprising the polymer.