Methods and compositions for cross-linking thermoplastic polyurethane covers for golf balls
Golf balls having covers made of thermoplastic polyurethane compositions are provided. Multi-piece golf balls can be made. In one embodiment, the outer cover layer is formed from a composition comprising a thermoplastic polyurethane and acid copolymer ionomer. The cover composition also can contain hydroxyl-containing compounds. The golf ball having the thermoplastic polyurethane cover can be treated with an isocyanate compound. The golf ball also can be treated with a hydroxyl and/or silane-containing compound. The cover composition and surface coatings can further include catalysts, ultraviolet (UV)-light stabilizers, and other additives. The coating methods have many benefits and the finished balls have good physical properties.
1. A method for treating a cover for a golf ball, comprising the steps of:
providing a golf ball sub-assembly comprising at least one core layer;
forming an outer cover layer over the sub-assembly, wherein the outer cover layer is formed from a composition comprising:
a) a thermoplastic polyurethane,
b) an acid copolymer of ethylene and an α,β-unsaturated carboxylic acid, optionally including a softening monomer selected from the group consisting of alkyl acrylates and methacrylates; and
c) a multi-functional hydroxyl-containing compound; and
d) a cation source present in an amount sufficient to neutralize from about 0 to about 100% of all acid groups present in the composition;
applying a composition comprising: i) at least one compound selected from the group consisting of multi-functional isocyanates; multi-functional hydroxyl-containing compound; and
a silane-containing compound to the outer cover to form at least a partially cross-linked cover for the golf ball.
2. The method of claim 1 , wherein the multi-functional hydroxyl compound is selected from the group consisting of polyether polyols, hydroxy-terminated polybutadiene, polyester polyols, polycaprolactone polyols, polycarbonate polyols, polyvinyl alcohol, hydroxyl-functional acrylics, polyethylene glycol, polypropylene glycol, starch-based polymers, cellulosic polymers, polylactic acid, and mixtures thereof.
3. The method of claim 1 , wherein the multi-functional isocyanate is selected from the group consisting of 4,4′-methylene diphenyl diisocyanate; 2,4′-methylene diphenyl diisocyanate; toluene 2,4-diisocyanate; toluene 2,6-diisocyanate; 4,4′-dicyclohexylmethane diisocyanate; p-phenylene diisocyanate; and isophorone diisocyanate; and homopolymers and copolymers and blends thereof.
4. The method of claim 1 , wherein the silane is selected from the group consisting of N-(2-aminoethyl-3-aminopropyl) trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, and mixtures thereof.
5. The method of claim 1 , wherein the polyurethane composition further comprises an ultraviolet (UV) light stabilizer.
6. The method of claim 1 , wherein the polyurethane composition further comprises a catalyst.
7. The method of claim 6 , wherein the catalyst is selected from the group consisting of dibutyl tin dilaurate, dibutyl tin acetylacetonate, dibutyl tin dibutoxide, dibutyl tin sulphide, dibutyl tin di-2- ethylhexanoate, dibutyl tin (IV) diacetate, dialkyltin (IV) oxide, tributyl tin laurylmercaptate, dibutyl tin dichloride, organo lead, tetrabutyl titanate, tertiary amines, mercaptides, stannous octoate, potassium octoate, zinc octoate, diazo compounds, and potassium acetate, and mixtures thereof.
8. The method of claim 1 , wherein the polyurethane is the reaction product of multi-functional polyisocyanate and polyol compounds and hydroxyl-terminated chain extender.
9. The method of claim 8 , wherein the hydroxyl-terminated chain extender is selected from the group consisting of 1,4-butylene glycol, ethylene glycol, diethylene glycol, butanediol, hexanediol, trimethylolpropane, and poly(tetramethylene ether) glycol; and mixtures thereof.
10. The method of claim 1 , wherein the sub-assembly comprises an inner core and surrounding outer core layer.
11. The method of claim 1 , wherein the inner core comprises at least one thermoset rubber material selected from the group consisting of polybutadiene, ethylene-propylene rubber, ethylene-propylene-diene rubber, polyisoprene, styrene-butadiene rubber, polyalkenamer rubber, and mixtures thereof.
12. A golf ball having an outer cover produced by the method of claim 1 .
13. A method for treating a cover for a golf ball, comprising the steps of:
providing a golf ball sub-assembly comprising at least one core layer;
forming an outer cover layer over the sub-assembly, wherein the outer cover layer is formed from a composition comprising:
a) a thermoplastic polyurethane,
b) an acid copolymer of ethylene and an α,β-unsaturated carboxylic acid, optionally including a softening monomer selected from the group consisting of alkyl acrylates and methacrylates; and
c) a cation source present in an amount sufficient to neutralize from about 0 to about 100% of all acid groups present in the composition;
applying a composition comprising: i) at least one compound selected from the group consisting of multi-functional isocyanates; multi-functional hydroxyl-containing compound; and
a silane-containing compound to the outer cover to form at least a partially cross-linked cover for the golf ball.
14. The method of claim 13 , wherein the multi-functional hydroxyl compound is selected from the group consisting of polyether polyols, hydroxy-terminated polybutadiene, polyester polyols, polycaprolactone polyols, polycarbonate polyols, polyvinyl alcohol, hydroxyl-functional acrylics, polyethylene glycol, polypropylene glycol, starch-based polymers, cellulosic polymers, polylactic acid, and mixtures thereof.
15. The method of claim 13 , wherein the multi-functional isocyanate is selected from the group consisting of 4,4′-methylene diphenyl diisocyanate; 2,4′-methylene diphenyl diisocyanate; toluene 2,4-diisocyanate; toluene 2,6-diisocyanate; 4,4′-dicyclohexylmethane diisocyanate; p-phenylene diisocyanate; and isophorone diisocyanate; and homopolymers and copolymers and blends thereof.
16. The method of claim 13 , wherein the silane is selected from the group consisting of N-(2-aminoethyl-3-aminopropyl) trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, and mixtures thereof.
17. A golf ball having an outer cover formed by the method of claim 13 .