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  Rubber compositions comprising high levels of oily substance and the use thereof in golf ballsUSPTO Application #: 20070270239Title: Rubber compositions comprising high levels of oily substance and the use thereof in golf balls Abstract: The present invention is directed to golf balls having at least one layer formed from a rubber composition comprising a base rubber and from 5 to 100 parts of an oily substance, by weight per 100 parts of the base rubber. The rubber composition may be present in any one or more of a core layer, a cover layer, or an intermediate layer. (end of abstract)
Agent: Acushnet Company - Fairhaven, MA, US Inventors: Michael J. Sullivan, Derek A. Ladd, Peter R. Voorheis USPTO Applicaton #: 20070270239 - Class: 473354000 (USPTO) Related Patent Categories: Games Using Tangible Projectile, Golf, Ball, Liquid Interior The Patent Description & Claims data below is from USPTO Patent Application 20070270239. Brief Patent Description - Full Patent Description - Patent Application Claims
CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation of U.S. patent application Ser. No. 11/383,838, filed May 17, 2006, the entire disclosure of which is hereby incorporated herein by reference. FIELD OF THE INVENTION [0002] The present invention is directed to rubber compositions comprising high levels of an oily substance, such as plasticizer and/or process oil, and to the use of such compositions in golf balls. BACKGROUND OF THE INVENTION [0003] Rubber compositions containing high levels of plasticizer are known. For example, U.S. Pat. No. 4,429,068 to Nakahira discloses a cured rubber having specific physical properties obtained by curing a rubber composition comprising 100 parts by weight of a rubber component, 5 to 2,000 parts of a factice, and 20 to 2,000 parts of a softening agent. The reference states that the rubber composition can be used in golf ball cores. [0004] U.S. Pat. No. 5,776,294 to Nagel discloses a method of providing curable elastomers crosslinked with the aid of metal salts of .alpha.,.beta.-ethylenically unsaturated carboxylic acids and, optionally an alkyl aminoalkyl phenol vulcanization inhibitor. Examples are given of metal salts of acrylic and methacrylic acids mixed with ethylene propylene diene rubber and high levels of Sunpar 2280, a proprietary plasticizer available from Sun Refining and Marketing Company, Philadelphia, Pa. [0005] U.S. Pat. No. 6,380,291 to von Hellens discloses rubber compositions comprising an acrylate or methacrylate salt, an elastomer curable with a peroxide initiator, and a plasticizer having one or more epoxide groups per molecule. The reference states that the plasticizer should be present in the rubber composition in an amount of from about 2 to about 20 phr. The reference also states that golf balls are a typical end use. [0006] In the golf ball industry, rubber compositions containing high levels of plasticizer are known to be useful as the inner core layer material in thread wound golf balls. For example, U.S. Pat. Nos. 6,593,443 and 6,669,581 to Iwami and U.S. Pat. No. 6,846,247 to Kato disclose a wound golf ball, wherein the inner core layer is preferably obtained by vulcanizing and molding a rubber composition containing an oily substance, such as a petroleum compounding oil, a plasticizer, a rubber substitute (factice), alkylbenzene, and liquid rubber. The references state that the oily substance is preferably contained in the base rubber in an amount of about 30 to 500 parts, based on 100 parts of the base rubber. [0007] A desire remains for novel rubber compositions containing high levels of an oily substance, which are useful in solid golf ball applications. Such compositions may provide one or more of the following properties relative to previously known golf ball materials: low cost, ease of processing, reduced compression, and reduced velocity. The present invention describes such compositions and their use in a variety of golf ball core, cover, and intermediate layers. SUMMARY OF THE INVENTION [0008] In one embodiment, the present invention provides a solid golf ball comprising a core and a cover. The core has a diameter of 1.4 inches or less and is formed from a rubber composition comprising a base rubber and from 5 to 100 parts of an oily substance, by weight per 100 parts of the base rubber. The cover has an overall thickness of 0.1 inches or greater. [0009] In another embodiment, the present invention provides a solid golf ball comprising a rubber core, a polyurethane or polyurea outer cover layer, and an intermediate layer disposed between the core and the outer cover layer. The core has a diameter of 1.4 inches or less and is formed from a rubber composition comprising a base rubber and from 5 to 100 parts of an oily substance, by weight per 100 parts of the base rubber. The intermediate layer has a thickness of 0.1 inches or greater and is formed from a highly resilient material selected from partially- and fully-neutralized acid copolymers and blends thereof. DETAILED DESCRIPTION OF THE INVENTION [0010] Conventional golf balls can be divided into two general classes: solid and wound. Solid golf balls include one-piece, two-piece (i.e., solid core and a cover), and multi-layer (i.e., solid core of one or more layers and/or a cover of one or more layers) golf balls. Wound golf balls typically include a solid, hollow, or fluid-filled center, surrounded by a tensioned elastomeric material, and a cover. [0011] Golf balls of the present invention are solid golf balls having a variety of core structures, intermediate layers, covers, and coatings. Golf ball cores of the present invention may consist of a single, unitary layer, comprising the entire core from the center of the core to its outer periphery, or they may consist of a center surrounded by at least one outer core layer. Golf ball covers of the present invention may also contain one or more layers, such as a double cover having an inner and outer cover layer. Optionally, additional layers may be disposed between the core and the cover. [0012] Golf balls of the present invention have at least one layer which is formed from a rubber composition of the present invention. The layer comprising the rubber composition may be any one or more layers selected from an inner core layer, an intermediate core layer, an outer core layer, an inner cover layer, an intermediate cover layer, an outer cover layer, or an intermediate layer disposed between a core and a cover. In a particular embodiment, the rubber composition comprises all or part of the core layer of a two-piece golf ball. In another particular embodiment, the rubber composition comprises all or part of the inner core layer and/or outer core layer of a multi-layer golf ball. In yet another embodiment, the rubber composition comprises all or part of the inner cover layer of a multi-layer ball. Rubber Composition [0013] Rubber compositions of the present invention include a base rubber and a high level of an oily substance. For purposes of the present invention, a composition contains "a high level of an oily substance" if the oily substance is present in the composition in an amount of 2 parts or greater by weight per 100 parts of base rubber. In a particular embodiment, the oily substance is present in the composition in an amount of 2.5 parts or greater, or 5 parts or greater, by weight per 100 parts of base rubber. In another particular embodiment, the oily substance is present in the composition in an amount within the range having a lower limit of 2 parts, or 2.5 parts, or 3 parts, or 5 parts, or 10 parts, by weight per 100 parts of rubber, and an upper limit of 20 parts, or 25 parts, or 30 parts, or 50 parts, or 100 parts, or 200 parts, by weight per 100 parts of rubber. In another particular embodiment, the oily substance is present in the composition in an amount within the range having a lower limit of 10 parts, or 15 parts, or 20 parts, or 25 parts, by weight per 100 parts of rubber, and an upper limit of 100 parts, or 200 parts, by weight per 100 parts or rubber. [0014] The oily substance is generally selected from rubber processing oils, vegetable oils, vulcanized vegetable oils, animal oils, liquid rubbers, plasticizers, and combinations thereof. Suitable rubber processing oils include, for example, aromatic oils, naphthenic oils, and paraffinic oils, as classified by ASTM D2226. In a particular embodiment, the oily substance is selected from paraffinic oil, naphthenic oil, and combinations thereof Particularly suitable paraffinic and naphthenic oils include, for example, Sunpar.RTM. paraffinic oil, commercially available from Sunoco, Inc. of Philadelphia, Pa.; Paralux.RTM. paraffinic oil, commercially available from Chevron Corporation of San Ramon, Calif.; and Unithene naphthenic oil, commercially available from Ergon, Inc. of Jackson, Miss. Suitable vegetable oils include, for example, rapeseed, castor, linseed, soybean, and tung oil. Suitable vulcanized vegetable oils include, for example, semi-translucent factice, black factice, and brown factice; in particular, "F14" and "F17" sulfur vulcanized rapeseed oils, "K14D" sulfur vulcanized modified fatty acids, "Gloria 17" sulfur vulcanized rapeseed oil, "Hamburg 4" partially hydrogenated rapeseed oil, and "WP" peroxide crosslinked modified castor oil free of sulfur and chlorine, all of which are commercially available from RT Vanderbilt Company, Inc. of Norwalk, Conn. Suitable animal oils include, for example, whale oil and fish oil. Suitable liquid rubbers include, for example, liquid polybutadiene and liquid polyisoprene. Suitable plasticizers include, for example, adipates, e.g., dioctyl adipate, diisopropyl adipate, dibutyl adipate, bis(2-ethylhexyl)adipate, polypropylene adipate, diisodecyl adipate, bis(2-methylhexyl)adipate, dicapryl adipate, and octyldecyl adipate; phthalates, e.g., dioctyl phthalate, dibutyl phthalate, nonyl phthalate, butylbenzyl phthalate, diheptyl phthalate, dihexyl phthalate, dinonyl phthalate, ditridecyl phthalate, dicapryl phthalate, dilauryl phthalate, diisodecyl phthalate, dimethylglycol phthalate, butyl octyl phthalate, dicyclohexyl phthalate, butyl cyclohexyl phthalate, butyl lauryl phthalate, butylcoconutalkyl phthalate, octyldecanoyl phthalate, octyldecyl phthalate, bis(2-ethylhexyl)phthalate, bis(3,5,5-trimethylhexyl) phthalate, bis(diethyleneglycolmonomethylether) phthalate, butyl benzyl phthalate, and texanol benyl phthalate; phosphates, e.g., tricresyl phosphate, trimethyl phosphate, triethyl phosphate, isopropylated triphenyl phosphate, tributyl phosphate, trio ctyl phosphate, tri-2-ethyl hexyl phosphate, tributoxy phosphate, triphenyl phosphate, trixylenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris(2,6-dimethyl phenyl)phosphate, isodecyl diphenyl phosphate, mixed dodecyl and tetradecyl diphenyl phosphate, butylphenyl diphenyl phosphate, xylenyl diphenyl phosphate, phenyl dicresyl phosphate, xylenyl dicresyl phosphate, cresyl diphenyl phosphate, cresyl dixylenyl phosphate, diphenyl phosphate hydroquinone condensate, trichloroethyl phosphate, tri(.beta.-chloropropyl)phosphate, tri(dichloropropyl)phosphate, and tri(tribromoneopentyl)phosphate; sebacates, e.g., dioctyl sebacate and 2-ethyl hexyl sebacate; alkyl benzenes, e.g., 1-dodecyl-4-hexylbenzene, 1-dodecyl-3-hexylbenzene, and 1,2,3-hemimellitene; citrates, e.g., acetyl tributyl citrate, triethyl citrate, acetyl triethyl citrate, and tributyl citrate; glycolic acid esters, e.g., ethylphthalyl ethylene glycolate, methylphthalyl ethylene glycolate, and butylphthalyl ethylene glycolate; epoxy compounds, e.g., butylepoxy stearate, octylepoxy stearate, epoxybutyl oleate, epoxidized butyl oleate, epoxidized soybean oil, epoxidized linseed oil, epoxidized alkyl oil, and epoxidized alkyl oil alcohol esters; trimellitates, e.g., tri-2-ethyl hexyl trimellitate and tri-octyl trimellitate; fatty acid esters, e.g., butyl oleate; benzoates, e.g., diethylene glycol dibenzoate and dipropylene glycol dibenzoate; azelates; glutarates; alkyl alcohols; and combinations thereof. Suitable plasticizers also include those disclosed in U.S. Patent Application Publication No. 2005/0137030, the entire disclosure of which is hereby incorporated herein by reference. [0015] The base rubber is generally selected from polybutadiene rubber, polyisoprene rubber, natural rubber, ethylene propylene rubber, ethylene propylene diene rubber, styrene-butadiene rubber, and combinations of two or more thereof. A preferred base rubber is one or more polybutadiene(s). Particularly suitable polybutadiene blends are disclosed, for example, in U.S. Pat. No. 6,774,187, the entire disclosure of which is hereby incorporated herein by reference. Another preferred base rubber is one or more polybutadiene(s) optionally mixed with one or more elastomer(s) selected from polyisoprene rubber, natural rubber, ethylene propylene rubber, ethylene propylene diene rubber, styrene-butadiene rubber, polystyrene elastomers, polyethylene elastomers, polyurethane elastomers, polyurea elastomers, metallocene-catalyzed elastomers, and plastomers. When the rubber composition contains an additional elastomer (i.e., in addition to the base rubber), the additional elastomer is present in the rubber composition in an amount of less than 100 parts by weight per 100 parts of the base rubber. In a particular embodiment, the additional elastomer is present in an amount of 50 parts or less, or 45 parts or less, or 20 parts or less, or 5 parts or less, by weight per 100 parts of the base rubber. [0016] The base rubber is typically cured using a conventional curing process. Suitable curing processes include, for example, peroxide curing, sulfur curing, radiation, and combinations thereof. In one embodiment, the base rubber is peroxide cured. Organic peroxides suitable as free radical initiators include, for example, dicumyl peroxide; n-butyl-4,4-di(t-butylperoxy) valerate; 1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(t-butylperoxy) hexane; di-t-butyl peroxide; di-t-amyl peroxide; t-butyl peroxide; t-butyl cumyl peroxide; 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; di(2-t-butyl-peroxyisopropyl)benzene; dilauroyl peroxide; dibenzoyl peroxide; t-butyl hydroperoxide; and combinations thereof. Peroxide free radical initiators are generally present in the rubber compositions in an amount within the range having a lower limit of 0.05 parts, or 0.1 parts, or 0.25 parts, or 1 part, or 1.5 parts, by weight per 100 parts of the base rubber, and an upper limit of 2.5 parts, or 3 parts, or 5 parts, or 6 parts, or 10 parts, or 15 parts, by weight per 100 parts of the base rubber. Coagents can be used with peroxides to increase the state of cure. Suitable coagents include, for example, metal salts of unsaturated carboxylic acids having from 3 to 8 carbon atoms; unsaturated vinyl compounds and polyfunctional monomers (e.g., trimethylolpropane trimethacrylate); phenylene bismaleimide; and combinations thereof. Particularly suitable metal salts include, for example, one or more metal salts of acrylates, diacrylates, methacrylates, and dimethacrylates, wherein the metal is selected from magnesium, calcium, zinc, aluminum, lithium, and nickel. In a particular embodiment, the coagent is selected from zinc salts of acrylates, diacrylates, methacrylates, and dimethacrylates. In another particular embodiment, the coagent is zinc diacrylate. When the agent is zinc diacrylate and/or zinc dimethacrylate, the coagent is typically included in the rubber composition in an amount within the range having a lower limit of 1 part, or 5 parts, or 10 parts, or 20 parts, by weight per 100 parts of the base rubber, and an upper limit of 25 parts, or 30 parts, or 3 5 parts, or 40 parts, or 50 parts, or 60 parts, by weight per 100 parts of the base rubber. When one or more less active coagents are used, such as zinc monomethacrylate and various liquid acrylates and methacrylates, the amount of less active coagent used may be the same as or higher than for zinc diacrylate and zinc dimethacrylate coagents. [0017] Sulfur and sulfur-based curing agents with optional accelerators may be used in combination with or in replacement of the peroxide initiators to crosslink the base rubber. Suitable curing agents and accelerators include, for example, sulfur; N-oxydiethylene 2-benzothiazole sulfenamide; N,N-diorthotolylguanidine; bismuth dimethyldithiocarbamate; N-cyclohexyl 2-benzothiazole sulfenamide; N,N-diphenylguanidine; 4-morpholinyl-2-benzothiazole disulfide; dipentamethylenethiuram hexasulfide; thiuram disulfides; mercaptobenzothiazoles; sulfenamides; dithiocarbamates; thiuram sulfides; guanidines; thioureas; xanthates; dithiophosphates; aldehyde-amines; dibenzothiazyl disulfide; tetraethylthiuram disulfide; tetrabutylthiuram disulfide; and combinations thereof. [0018] High energy radiation sources capable of generating free radicals may also be used to crosslink the base rubber. Suitable examples of such radiation sources include, for example, electron beams, ultra-violet radiation, gamma radiation, X-ray radiation, infrared radiation, heat, and combinations thereof. Continue reading... Full patent description for Rubber compositions comprising high levels of oily substance and the use thereof in golf balls Brief Patent Description - Full Patent Description - Patent Application Claims Click on the above for other options relating to this Rubber compositions comprising high levels of oily substance and the use thereof in golf balls patent application. ###  How KEYWORD MONITOR works... a FREE service from FreshPatents1. Sign up (takes 30 seconds). 2. Fill in the keywords to be monitored. 3. Each week you receive an email with patent applications related to your keywords. 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