CASTABLE POLYURETHANE COVERS BASED ON ISOCYANATE BLENDS FOR GOLF BALLS
A method for making a golf ball having a cover material comprising a polyurethane or polyurea composition is provided. The composition is prepared from a reactive mixture of a polyurethane or polyurea prepolymer and curative blend, wherein the blend comprises: i) a curing agent, ii) a freezing point depressing agent; and iii) pigment. The composition is cast over a ball subassembly to form the cover. The resulting cover material has many advantages including improved thermal-stability, light-stability, durability, toughness, and cut/tear-resistance. The preferred isocyanates in the blend include isophorone diisocyanate (“IPDI”); 1,6-hexamethylene diisocyanate (“HDI”); 4,4′-dicyclohexylmethane diisocyanate (“H 12 MDI”); 4,4′-diphenylmethane diisocyanate (4,4′-MDI); toluene diisocyanate (“TDI”); and homopolymers and copolymers thereof.
1 . A method of manufacturing a multi-piece golf ball, comprising the steps of:
providing a golf ball subassembly;
providing a castable composition, the composition comprising a reactive mixture of a polyurethane or polyurea prepolymer and curative blend, the curative blend comprising: i) a curing agent, ii) a freezing point depressing agent, and iii) pigment;
forming a cover layer over the golf ball subassembly by providing first and second mold cavities; dispensing the castable composition into at least one mold cavity, positioning the core in one mold cavity; and mating the mold cavities together.
2 . The method of claim 1 , wherein the prepolymer is a polyurethane prepolymer formed by reacting: i) a blend of two or more of: isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-dicyclohexylmethane diisocyanate (H 12 MDI), 4,4′-dicyclohexylmethane diisocyanate (4,4′-MDI), and toluene diisocyanate (TDI), and homopolymers and copolymers thereof, wherein the blend has an average NCO functionality in the range of 2.05 to 2.35; and ii) a polyol compound.
3 . The method of claim 2 , wherein the blend comprises isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI) homopolymer.
4 . The method of claim 2 , wherein the blend comprises 4,4′-dicyclohexylmethane diisocyanate (H 12 MDI) and hexamethylene diisocyanate (HDI) homopolymer.
5 . The method of claim 2 , wherein the blend comprises 4,4′-dicyclohexylmethane diisocyanate (4,4′-MDI) and toluene diisocyanate (TDI) homopolymer.
6 . The method of claim 1 , wherein the blend comprises 4,4′-dicyclohexylmethane diisocyanate (4,4′-MDI) and hexamethylene diisocyanate (HDI) homopolymer.
7 . The method of claim 1 , wherein the prepolymer is a polyurea prepolymer formed by reacting: i) a blend of two or more of: isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-dicyclohexylmethane diisocyanate (H 12 MDI), 4,4′-dicyclohexylmethane diisocyanate ( 4 , 4 ′-MDI), and toluene diisocyanate (TDI), and homopolymers and copolymers thereof, wherein the blend has an average NCO functionality in the range of 2.05 to 2.35; and ii) a polyamine compound.
8 . The method of claim 1 , wherein the cover layer comprises polyurethane, polyurea, or hybrid of polyurethane and polyurea.
9 . The method of claim 1 , wherein the curing agent in the curative blend is a hydroxyl-terminated compound selected from the group consisting of ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polytetramethylene ether glycol, polyethylene propylene glycol, polyoxypropylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, and mixtures thereof.
10 . The method of claim 1 , wherein the curing agent in the curative blend is an amine-terminated compound selected from the group consisting of 4,4′-diamino-diphenylmethane; 3,5-diethyl-(2,4- or 2,6-) toluenediamine; 3,5-dimethylthio-(2,4- or 2,6-)toluenediamine; 3,5-diethylthio-(2,4- or 2,6-) toluenediamine: 2,2′-dichloro-3,3′,5,5′-tetraethyl-4,4′-diamino-diphenylmethane; polytetramethyleneglycol-di(p-aminobenzoate); 4,4′-bis(sec-butylamino)-dicyclohexylmethane; and mixtures thereof.
11 . The method of claim 1 , wherein the pigment in the curative blend is selected from the group consisting of titanium dioxide; red or yellow iron oxides; carbon black; ultramarine blue; phthalocyanine blue; phthalocyanine green; carbazole violets; and naphthol reds; and mixtures thereof.
12 . The method of claim 1 , wherein the freezing point depressing agent in the curative blend is a hydroxyl-terminated compound selected from the group consisting of 1,3-propanediol; 2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol; 1,2-butanediol; 1,3-butanediol; ethylene glycol; diethylene glycol; 1,5-pentanediol; polytetramethylene glycol; propylene glycol; dipropylene glycol; and mixtures thereof.
13 . The method of claim 1 , wherein the freezing point depressing agent in the curative blend is an amine-terminated compound selected from the group consisting of hexamethylene diamine; diethanolamine; triethanol amine; diisopropanolamine; and triisopropanolamine.
14 . The method 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.
15 . The method of claim 1 , wherein the golf ball subassembly is a single piece core, the core comprising a polybutadiene rubber composition.
16 . The method of claim 15 , 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 method of claim 1 , wherein the golf ball subassembly is dual-core having an inner core and outer core layer, and wherein at least one of the core layers comprises a polybutadiene rubber composition.
18 . The method of claim 1 , wherein the golf ball subassembly comprises a core and intermediate layer disposed about the core.
19 . The method of claim 18 , wherein the intermediate layer comprises ethylene acid copolymer ionomer.
20 . The method of claim 16 , 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.