Golf balls based on thermoplastic polyurethanes comprising moisture-resistant polyols
View Patent ↗Golf balls containing at least one layer made from a thermoplastic polyurethane or polyurethane-urea that is the reaction product of a polyisocyanate with moisture-resistant polyol and a curing agent are provided. The moisture-resistant polyol may be prepared by dimerizing unsaturated aliphatic monocarboxylic acid or ester containing 10 to 60 carbon atoms followed by reacting it with a monomeric, oligomeric, or polymeric diol. In one preferred version, the moisture-resistant polyol is a branched polyester polyol containing 36 carbon atoms. The composition can be prepared using prepolymer or one-shot manufacturing techniques. The resulting golf ball has desirable playing performance properties including high resiliency, toughness, impact durability, moisture-resistance, and soft feel.
1. A golf ball, comprising:
a core having a first Shore C surface hardness of C 1 in the range of 50 to 90;
an intermediate layer surrounding the core; and
a cover layer surrounding the intermediate layer having a second Shore C surface hardness of C 2 in the range of 60 to 95, the cover layer being formed from a thermoplastic polyurethane or polyurethane-urea composition that is produced by a reaction of: i) an isocyanate compound, ii) a moisture-resistant polyol having a weight average molecular weight in the range of 500 to 10,000 grams per mole and a hydroxyl value in the range of 30 to 120, and iii) a curing agent selected from hydroxyl-terminated or amine-terminated curing agents, and mixtures thereof, and wherein the ratio of C 2 to C 1 is in the range of 0.6 to 1.4, wherein the cover layer has a moisture vapor transmission rate between 3 grams/m 2 ·day to 4 grams/m 2 ·day.
2. The golf ball of claim 1 , wherein the moisture-resistant polyol is the reaction product of dimer acid or dimer ester and polyolefin diol or polybutadiene polyol or polyisoprene diol.
3. The golf ball of claim 1 , wherein the moisture-resistant polyol is the reaction product of dimer acid or dimer ester and hydrogenated polybutadiene or polyisoprene diol.
4. The golf ball of claim 1 , wherein the moisture-resistant polyol is a polyether-ester diol is the reaction product of dimer acid or dimer ester and polyether diol.
5. The golf ball of claim 1 , wherein the moisture-resistant polyol is a polycaprolactone-ester diol is the reaction product of dimer acid and polycaprolactone diol.
6. The golf ball of claim 1 , wherein the isocyanate compound is selected from the group consisting of monomeric, oligomeric, or polymeric isophorone diisocyanate (IPDI);
hexamethylene diisocyanate (HDI); 1,4-cyclohexyl diisocyanate (CHDI); 4,4′-dicyclohexylmethane diisocyanate (H 12 MDI); 4,4′-dicyclohexylmethane diisocyanate (4,4′-MDI); 4,4′-diphenylmethane diisocyanate (“MDI”); toluene diisocyanate (TDI); p-phenylene diisocyanate (PPDI); 1,5-naphthalene diisocyanate (“NDI”); xylene diisocyanate (“XDI”); and tetramethylxylene diisocyanate (TMXDI”); and mixtures thereof.
7. The golf ball of claim 1 , wherein the moisture-resistant polyol is prepared by dimerizing unsaturated aliphatic monocarboxylic acid or ester containing 10 to 60 carbon atoms followed by reacting with a monomeric or polymeric diol.
8. The golf ball of claim 1 , wherein the moisture-resistant polyol is a branched polyester polyol containing 36 carbon atoms.
9. The golf ball of claim 1 , wherein the curing agent is an amine-terminated curing agent selected from the group consisting of 1,3-propane diamine, 1,4-butane diamine, 1,5-pentane diamine, 1,6-hexane diamine, 1,7-heptane diamine, 1,8-octane diamine, 1,9-nonane diamine, 1,10-decane diamine, 1,11-undecane diamine, and 1,12-dodecane diamine, polymethylene-di-p-aminobenzoates, polyethyleneglycol-bis(4-aminobenzoates), polytetramethylene etherglycol-di-p-aminobenzoate, polypropyleneglycol-di-p-aminobenzoate, and mixtures thereof.
10. The golf ball of claim 1 , wherein the curing agent is a hydroxyl-terminated curing agent selected from the group consisting of 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, 1,7-heptane diol, 1,8-octane diol, 1,9-nonane diol, 1,10-decane diol, 1,11-undecane diol, 1,12-dodecane diol, and alkyl or aryl substituted alkane diols, and mixtures thereof.
11. The golf ball of claim 1 , wherein the thermoplastic polyurethane or polyurethane-urea composition has a weight average molecular weight in the range of about 25,000 to about 750,000 grams per mole, a melting temperature of 80° to 200° C., and material Shore D hardness of about 30 to about 75.
12. The golf ball of claim 1 , wherein the thermoplastic polyurethane or polyurethane-urea composition is post cross-linked using a chemical or radiation cross-linking process.
13. The golf ball of claim 1 , wherein the reaction used to produce the thermoplastic polyurethane or polyurethane-urea composition is a one-step reaction.
14. The golf ball of claim 1 , wherein the reaction used to produce the thermoplastic polyurethane or polyurethane-urea composition is a two-step reaction, wherein the first step comprises reacting the isocyanate compound and moisture-resistant polyol to form a prepolymer and the second step comprises reacting the prepolymer with the curing agent.
15. The golf ball of claim 1 , wherein the intermediate layer is formed from a thermoset composition selected from the group consisting of polyurethanes, polyureas, and polyurethane-polyurea hybrids, epoxies, cross-linked thermoplastics, and mixtures thereof.
16. The golf ball of claim 1 , wherein the core has a diameter of about 1.26 to about 1.60 inches and surface hardness in the range of about 30 to about 65 Shore D.
17. The golf ball of claim 1 , wherein the intermediate layer has a thickness of about 0.015 to about 0.120 inches and surface hardness in the range of about 45 to about 75 Shore D.
18. The golf ball of claim 1 , wherein the cover layer has a thickness of about 0.015 to about 0.090 inches and material hardness in the range of about 40 to about 65 Shore D.
19. A golf ball having a multi-layered cover, comprising:
a core having a first Shore C surface hardness of C 1 in the range of 60 to 95;
an intermediate layer surrounding the core;
a cover surrounding the intermediate layer having a second Shore C surface hardness of C 2 in the range of 50 to 90; the cover comprising an inner cover layer and outer cover layer, at least one of the cover layers being formed from a thermoplastic polyurethane or polyurethane-urea composition that is produced by a reaction of: i) an isocyanate compound; ii) a moisture-resistant polyol having a weight average molecular weight in the range of 500 to 10,000 grams per mole and a hydroxyl value in the range of 30 to 120, and iii) a curing agent selected from hydroxyl-terminated or amine-terminated curing agents, and mixtures thereof, and wherein the ratio of C 2 to C 1 is in the range of 0.5 to 1.5, wherein the cover layer has a moisture vapor transmission rate between 3 grams/m 2 ·day to 4 grams/m 2 ·day.
20. A golf ball having a core and at least one surrounding layer formed from a composition comprising a thermoplastic polyurethane or polyurethane-urea composition that is produced by a reaction of: i) an isocyanate compound; ii) a moisture-resistant polyol having a weight average molecular weight in the range of 500 to 10,000 grams per mole and a hydroxyl value in the range of 30 to 120, and iii) a curing agent selected from hydroxyl-terminated or amine-terminated curing agents, and mixtures thereof, wherein the surrounding layer has a moisture vapor transmission rate between 3 grams/m 2 ·day to 4 grams/m 2 ·day.