JP5491986B2 - Multi-layer golf ball - Google Patents

Description

  The present invention relates generally to golf balls, and more specifically to a hard, highly compressed center, a rigid outer cover layer, and a relatively soft intermediate layer disposed between the center and outer cover layer. The present invention relates to a golf ball.

  U.S. Pat. No. 4,863,167 (Matsuki et al., US Pat. No. 5,697,097) discloses a three-piece golf ball having improved rebound characteristics and a high initial speed, which is located above the center portion and the center portion. And an outer layer disposed on the outer layer and a cover disposed on the outer layer. The golf ball preferably has a higher hardness on the outer layer than on the inner layer.

  U.S. Pat. No. 5,048,838 (Chikaraishi et al., U.S. Pat. No. 6,057,077) discloses a three-piece golf ball having a two-piece solid core consisting of an inner layer and an outer layer and a cover surrounding the core. The case describes a golf ball in which the inner core layer is the same hardness or soft as the outer core layer and the cover composition is softer than both the inner and outer core layers.

  U.S. Pat. No. 5,184,828 (Kim et al., US Pat. No. 5,697,897) discloses a solid three-piece golf ball having a core assembly and a cover realized by an inner core and an outer layer and having the following characteristics. doing. That is, this feature is that a) the inner core diameter is in the range of 23-35 mm, its hardness (Shore D) is in the range of 30-62, and b) the outer layer diameter is in the range of 31-41 mm, The hardness (Shore D) is in the range of 30-56, and c) the golf ball has a maximum in the range of 46-62 at the outer site of the inner core disposed at the interface between the inner core and the outer layer of the golf ball. It has a hardness (Shore D), the hardness of which decreases towards both the inside and the outside. The inner and outer core layers are formed from rubber compositions having 35-50 parts by weight and 25-40 parts by weight, respectively, of co-crosslinking agents such as zinc diacrylate and zinc dimethacrylate, respectively.

  U.S. Pat. No. 7,015,300 (Rajagopalan et al., US Pat. No. 5,057,049) is arranged around a core, with a hardness of about 30 Shore D or greater, and a flexural modulus of about 1000 psi to about 80000 psi. A layer made from a thermoplastic composition having a thickness of about 0.01 inches to about 0.100 inches and comprising p-phenylene diisocyanate, a hardness of about 20 Shore D or greater, and a flexural modulus of about 1000 psi. And about 30,000 psi and a thickness of about 0.01 inches to about 0.05 inches and a cover made from a thermoset material.

  U.S. Pat. No. 6,926,620 (Dalton et al., US Pat. No. 5,637,097) describes a core comprising one or more layers, a cover comprising one or more layers, and a mantle layer disposed between the core and the cover. A golf ball is disclosed. The mantle layer has a thermoplastic material, preferably a hardness greater than 60 Shore D, and a Bashore resilience greater than 34, and a Vicat point (vicat) greater than 350 ° F. (176.7 ° C.). Has thermoplastic material.

  Background reference techniques are also described, for example, in U.S. Pat. Nos. 4,714,253 and 5,002,281 (Nakahara et al.), And U.S. Pat. No. 5,935,022 (Sugimoto). No. 4,781,383 (Kamada et al.), No. 4,625,964 (Yamada), No. 6,838,519 (Rajagopalan et al.), No. 7, etc. , 005,479 (Morgan et al.), And 6,905,648 (Sullivan et al.).

US Pat. No. 4,863,167 US Pat. No. 5,048,838 US Pat. No. 5,184,828 US Pat. No. 7,015,300 US Pat. No. 6,926,620

  In one embodiment, the present invention includes a center, an outer cover layer, and an intermediate layer disposed between the center and the outer cover layer, and the hardness of the outer surface of the intermediate layer is that of the center and the outer cover layer. A golf ball with a hardness lower than both is realized. The center is manufactured from a polybutadiene composition, its diameter is less than 1.500 inches and its compression is greater than 60. The intermediate layer is made from a polyurea composition and has an outer surface hardness of less than 50 Shore D. The cover layer is made from an ionomer composition having a flexural modulus greater than 40,000 psi.

  In another embodiment, the invention consists essentially of a center, an outer cover layer, and an intermediate layer disposed between the center and outer cover layer, wherein the hardness of the outer surface of the intermediate layer is center and A golf ball smaller than the hardness of both outer cover layers is realized. The center is manufactured from a polybutadiene composition, its diameter is less than 1.500 inches and its compression is greater than 60. The intermediate layer is made from a polyurea composition and has an outer surface hardness of less than 50 Shore D. The cover layer is made from an ionomer composition having a flexural modulus greater than 40,000 psi.

  In another embodiment, the present invention includes a center, an outer cover layer, and an intermediate layer disposed between the center and the outer cover layer, and the hardness of the outer surface of the intermediate layer is the center and the outer cover layer. A golf ball smaller than both hardness is realized. The center diameter is less than 1.500 inches, the overall compression is greater than 60, and the center has two layers made from the same or different highly neutralized polymer compositions. The hardness of the outer surface of the intermediate layer is less than 50 Shore D, and the intermediate layer is made from a polyurea composition. The cover layer is made from an ionomer composition having a flexural modulus greater than 40,000 psi.

  In another embodiment, the invention consists essentially of a center, an outer cover layer, and an intermediate layer disposed between the center and outer cover layer, wherein the hardness of the outer surface of the intermediate layer is center and A golf ball smaller than the hardness of both outer cover layers is realized. The center diameter is less than 1.500 inches, the overall compression is greater than 60, and the center consists of two layers made from the same or different highly neutralized polymer compositions. The hardness of the outer surface of the intermediate layer is less than 50 Shore D, and the intermediate layer is made from a polyurea composition. The cover layer is made from an ionomer composition having a flexural modulus greater than 40,000 psi.

  The present invention is directed to a golf ball having a hard, highly compressed center, a rigid outer cover layer, and a relatively soft intermediate layer disposed between the center and outer cover layer. The outer diameter of the hard, high compression center, or the entire core of the double core embodiment (ie, the golf ball subassembly to be surrounded by the intermediate layer) has a lower limit of 0.500 or 0.750 or 0.800. Or 1.000 or 1.200 or 1.300 inches with an upper limit of 1.350 or 1.400 or 1.450 or 1.500 or 1.530 or 1.550 or 1.580 or 1.600. Or in the range of 1.630 inches.

  The compression of the center, or the entire core of the dual core embodiment (ie, the golf ball subassembly to be surrounded by the intermediate layer) is preferably 40 or more, or more than 40, or 50 or more, or more than 50, or 60 or more, or more than 60, or more than 70, or more than 70, or more than 80, or more than 80, or more than 90, or more than 90, or more than 100, or more than 100, or more than 110, or 110 Or the compression has a lower limit of 40 or 50 or 60 or 70 or 80, an upper limit of 95 or 105 or 110 or 120, and a coefficient of restitution (“COR”) of 0.750 or more. , Or 0.790 or more, or 0.800 or more, or 0.810 or more, or 0.820 or more A.

  In one embodiment, compression of a golf ball subassembly having a center, an intermediate layer, and any optional layers disposed between the center and intermediate layer is disposed between the center and the center and intermediate layer. The golf ball subassembly compression is the same as or smaller than the optional optional layer, except the intermediate layer itself. In a specific aspect of this embodiment, the compression of the first golf ball subassembly having a center, an intermediate layer, and any optional layer disposed between the center and the intermediate layer comprises: The compression of the first golf ball subassembly and the second golf ball are smaller than the compression of the second golf ball subassembly, with any optional layer disposed between the center and the intermediate layer, but excluding the intermediate layer itself. The difference between the compression of the ball subassembly is 10 compression points or more, or more than 10 compression points, or 15 compression points or more, or more than 15 compression points, or more than 20 compression points, or more than 20 compression points. Or more than 25 compression points, or more than 25 compression points, or more than 30 compression points. More than 30 compression points.

  In one embodiment, a golf ball subassembly having a center, an intermediate layer, and any optional layers disposed between the center and intermediate layer has a COR of 0.740 or higher, or 0.760 or higher, Or it is 0.780 or more.

  The hardness of the outer surface of the center, or the entire core of the dual core embodiment (ie, the golf ball subassembly to be surrounded by the intermediate layer) is greater than the hardness of the intermediate layer. In one embodiment, the hardness of the outer surface of the entire core of the center or double core embodiment is 70 Shore C or higher, or 75 Shore C or higher, or 80 Shore C or higher, or 82 Shore C or higher, or , 85 Shore C or higher. In another embodiment, the hardness of the outer surface of the center, or the entire core of the dual core embodiment, has a lower limit of 70 or 75 or 80 or 82 or 85 Shore C and an upper limit of 90 or 92 or 93 or 95 Shore C. Range. In another embodiment, the hardness of the outer surface of the center or the entire core of the dual core embodiment has a lower limit of 50 or 53 or 55 or 58 Shore D and an upper limit of 60 or 62 or 64 or 70 Shore D. It is.

  The thickness of the relatively soft intermediate layer has a lower limit of 0.005 or 0.010 or 0.020 or 0.030 or 0.035 or 0.040 or 0.050 or 0.060 or 0.070 inches The upper limit is in the range of 0.100 or 0.110 or 0.125 or 0.150 or 0.200 or 0.225 inches. The hardness of the outer surface of the intermediate layer is less than the hardness of both the center (or the entire core of the dual core embodiment) and the outer cover layer. In one embodiment, the hardness of the outer surface of the intermediate layer is 70 Shore C or less, or less than 70 Shore C, or 65 Shore C or less, or 65 Shore C or less, or 60 Shore C or less, or less than 60 Shore C, or The lower limit is 25 or 30 or 35 or 40 or 45 or 50 or 55 Shore C, and the upper limit is 60 or 65 or 70 or 75 or 80 Shore C.

  The hardness of the outer surface of the golf ball is obtained from the average of a number of measurements taken from the opposing hemisphere, and care is taken not to make measurements on core separation lines or surface defects, such as holes or protrusions. The hardness is measured according to ASTM D-2240 “Durometer rubber and plastic dent hardness”. Because of the curved surface, it is necessary to handle the core so that the golf ball or golf ball subassembly is centered directly under the durometer indenter before the surface hardness is read. One calibrated digital durometer capable of reading up to 0.1 hardness units was used for all hardness measurements and was set to take a hardness reading 1 second after the maximum reading was obtained. The digital durometer must be mounted on the base of the auto stand with its legs parallel so that the weight and attack speed on the durometer conforms to ASTM D-2240.

  The hardness point should be measured only once at any geometric location.

  Each of the entire core, intermediate layer, and optional optional layers of the center and intermediate layers of the center or dual core embodiment is described in US Pat. Nos. 7,537,530 and 7,537,529. It may be accompanied by a zero or negative hardness gradient as disclosed in the specification and may be accompanied by a fairly steep gradient as disclosed in U.S. Patent Application Publication Nos. 2008/0161130 and 2008/0161132. Here, as disclosed in US Pat. No. 7,544,730, it may optionally be made using a resorcinol compound, and these layers are also described in US Pat. No. 7,429,221. And the same gradient as disclosed in US Pat. No. 7,410,429. The contents of these documents are incorporated herein by reference. In a specific embodiment, the entire core of the center or double core embodiment is accompanied by a negative hardness gradient, a zero hardness gradient, or a positive hardness gradient up to 45 Shore C. In other examples, the intermediate layer has a negative hardness gradient, a zero hardness gradient, or a positive hardness gradient up to 15 Shore C.

  For purposes of disclosing the invention, the hardness gradient of a golf ball is defined by the hardness specific values of the outer surface of the layer and the inner surface of the layer. The terms “negative” and “positive” refer to the result of subtracting the hardness value of the innermost portion of the golf ball part from the hardness value of the outer surface of the part. For example, if the hardness value of the outer surface of the solid core is less than the center (ie, the surface is softer than the center), the hardness gradient is considered a “negative” gradient.

  The hardness gradient is, for example, U.S. Patent Application No. 11 / 832,163 filed on Aug. 1, 2007, U.S. Patent Application No. 11 / 939,634 filed on Nov. 14, 2007, Nov. 14, 2007. U.S. Patent Application No. 11 / 939,63 of application and U.S. Patent Application No. 11 / 939,637 filed November 14, 2007, the contents of which are hereby incorporated by reference.

  In one embodiment, the center is produced from a rubber-based composition that includes a base rubber, an initiator, a coagent, and optional one or more zinc oxides, stearic acid or zinc stearate, an antioxidant, and Has a softening and speeding agent. Suitable base rubbers include natural rubber and synthetic rubber, which include, but are not limited to, polybutadiene, polyisoprene, ethylene propylene rubber (“EPR”), styrene-butadiene rubber, styrene block copolymer rubber (eg, SI, SIS, SB, SBS, SIBS, etc., where “S” is styrene, “I” is isobutylene, “B” is butadiene), butyl rubber, halobutyl rubber, polystyrene elastomer, polyethylene elastomer, polyurethane elastomer, polyurea Elastomers, metallocene catalyzed elastomers, and plastomers, copolymers of isobutylene and para-alkylstyrene, halogenated copolymers of isobutylene and para-alkylstyrene, copolymers of butadiene with acrylonitrile , Including polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber, and combinations of two or more thereof. Diene rubbers, particularly polybutadiene, styrene-butadiene, and mixtures of polybutadiene with other elastomers are preferred, wherein the amount of polybutadiene is present by at least 40 wt% based on the total polymer weight of the mixture. Particularly preferred polybutadienes include high cis neodymium catalyzed polybutadiene and cobalt-, neckel-, or lithium-catalyzed polybutadiene. Suitable examples of commercially available polybutadiene include, but are not limited to, Buna CB high cis neodymium catalyzed polybutadiene rubber, such as Buna 23, and Takten ™ high cis, commercially available from LANXESS. Cobalt-catalyzed polybutadiene rubbers such as Takten ™ 220 and 221; SE BR-1220 commercially available from Dow Chemical; Europrene ™ NEOCIS (commercially available from Polymeri Europa ™) Trademarks) BR40 and BR60; UBEPOL-BR ™ rubber commercially available from UBE Industry; and BR01 commercially available from Japan Synthetic Rubber. And Neodene high cis neodymium-catalyzed polybutadiene rubber, such as Neodene BR 40, commercially available from Karbochem.

  Suitable peroxide initiators include organic peroxides, high energy radiation sources capable of generating free radicals, and combinations thereof. High energy radiation sources capable of generating free radicals include, but are not limited to, electron beams, ultraviolet radiation, gamma radiation, X-ray radiation, infrared radiation, heat, and combinations thereof. Suitable organic peroxides include, but are not limited to, dicumyl peroxide; n-butyl-4,4-bis (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-butylcumyl peroxide; , 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; di (2-t-butyl-peroxyisopropyl) benzene; dilauroyl peroxide; dibenzoyl peroxide; t-butyl hydroperoxide; lauryl peroxide; Benzoyl peroxide; and mixtures thereof. Examples of suitable commercially available peroxides include, but are not limited to, Perkadox ™ BC dicumyl peroxide, commercially available from Akzo Nobel, Varox ™, commercially available from RT Vanderbilt. ) Peroxides such as Varox ™ ANS benzoyl peroxide and Varox ™ 231 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane. The peroxide initiator is generally present in the rubber composition in an amount of at least 0.05 parts by weight based on 100 parts base rubber, or 0.05 parts by weight or 0.1 parts by weight based on 100 parts base rubber. 2.5 parts or 3 parts or 3.5 parts or 5 parts or 6 parts per 100 parts base rubber on the basis of a lower limit of 1 part or 0.8 parts or 1 part or 1.25 parts or 1.5 parts and weight Present in an amount within the range having an upper limit of 10 parts or 15 parts.

  Coagents are commonly used with peroxides to increase the cure state. Suitable coagents include, but are not limited to, metal salts of unsaturated carboxylic acids; unsaturated vinyl compounds and polyvalent monomers (eg, trimethylolpropane trimethacrylate); phenylene bismaleimides; and mixtures thereof. Specific examples of suitable metal salts include, but are not limited to, one or more metal salts of acrylates, diacrylates, methacrylates, and dimethacrylates. However, the metal is selected from magnesium, calcium, zinc, aluminum, lithium, nickel, and sodium. In a specific embodiment, the coagent is selected from acrylate, diacrylate, methacrylate and zinc salts of dimethacrylate and combinations thereof. In another specific embodiment, the coagent is zinc diacrylate. The rubber composition for producing the center of the golf ball of the present invention is preferably 35 parts or more, or more than 35 parts, or more than 40 parts, or more than 40 parts based on 100 parts by weight. Or more than 45 parts, or more than 45 parts, more than 50 parts, or more than 50 parts, more than 55 parts, or more than 55 parts, or more than 60 parts, or more than 60 parts. When one or more non-active coagents are used, such as zinc monomethacrylate and various liquid acrylates and methacrylates, the amount of non-active coagent used is relative to the zinc diacrylate and zinc dimethacrylate coagents. It can be the same or more than the amount. The desired compression may be achieved by adjusting the amount of crosslinker, which can be achieved, for example, by changing the type and amount of coagent.

  An optional curing agent may be used in the composition of this invention. Suitable curing agents include, but are not limited to, sulfur; N-oxydiethylene 2-benzothiazole sulfenamide; N, N-di-ortho-tolylguanidine; bismuth dimethyldithiocarbamate; N-cyclohexyl 2-benzothiazole sulf N, N-diphenylguanidine; 4-morpholinyl-2-benzothiazole disulfide; dipentamethylene thiuram hexasulfide; thiuram disulfide; mercaptobenzothiazole; sulfenamide; dithiocarbamate; thiuram sulfide; guanidine; thiourea; Dithiophosphate; aldehyde-amine; dibenzothiazyl disulfide; tetraethyl thiuram disulfide; tetrabutyl thiuram disulfide; and combinations thereof No.

  The rubber composition of this invention optionally contains one or more antioxidants. Antioxidants are compounds that prevent or inhibit the oxidative breakdown of rubber. Some antioxidants also act as free radical scavengers. Therefore, when an antioxidant is included in the rubber composition, the amount of free radicals used is equal to or greater than the amount disclosed herein. Suitable antioxidants include, for example, dihydroquinoline antioxidants, amine-type antioxidants, and phenol-type antioxidants.

  The rubber composition may also include one or more fillers to adjust the density and / or specific gravity of the core or cover. Examples of fillers are precipitated hydrated silica, clay, talc, asbestos, glass fiber, aramid fiber, mica, calcium metasilicate, zinc sulfate, barium sulfate, zinc sulfide, lithopone, silicate, silicon carbide, diatomaceous earth, polychlorinated Vinyl, carbonate (eg, calcium carbonate, magnesium carbonate), metal (eg, titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, lead, copper, boron, cobalt, beryllium, zinc, tin), metal alloy (eg, Steel, brass, bronze, boron carbide whiskers, tungsten carbide whiskers), oxides (eg, zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide), particulate carbonaceous materials (eg, graphite, carbon) Black, cotton frock, natural bitumen Including Men, cellulose floc, leather fiber), metal stearates, microballoons (e.g., glass, ceramics), fly ash, regrind (i.e. core material to be recycled is pulverized), nanofillers, and combinations thereof. The amount of particulate material present in the rubber composition is typically a lower limit of 5 or 10 parts per 100 parts base rubber on a weight basis and 30 or 50 parts per 100 parts base rubber on a weight basis. Part or 100 parts. The filler material may be a dual function filler such as zinc oxide (which may be used as a filler / acid scavenger) and titanium dioxide (which may be used as a filler / brightener).

  Rubber compositions optionally include processing aids, processing oils, plasticizers, colorants, fragrances, chemical blowing or blowing agents, defoamers, stabilizers, softeners, impact modifiers, free radical scavengers, accelerators, scorches One or more additives selected from retarders and others may also be included. The amount of additive typically present in the rubber composition is typically a lower limit of 0 parts per 100 parts base rubber by weight and 20 parts or 50 parts per 100 parts base rubber by weight. Part or 100 parts or 150 parts.

  The rubber composition may contain an optional softening and speeding agent. As used herein, a “soft and fast agent” makes the core 1) softer under a certain COR than when prepared without a softening and speeding agent. (Small compression) or 2) Any compound or blend thereof, or any combination that causes a greater COR with equal compression. Preferably, the rubber composition contains from about 0.05 phr to about 10.0 phr of a softening and speeding agent. In one embodiment, the softening and speeding agent is 0.05 or 0.1 or 0.2 or 0.5 phr lower limit and 1.0 or 2.0 or 3.0 or 5.0 phr upper limit range. Exists in the amount. In other embodiments, the softening and speeding agent is present in the range of 2.0 phr to 5.0 pr, or 2.35 phr to 4.0 phr, or 2.35 phr to 3.0 phr. In an alternative high concentration embodiment, the softening and speeding agent is present in the range of 5.0 phr to 10.0 pr, or 6.0 phr to 9.0 phr, or 7.0 phr to 8.0 phr. In other embodiments, the softening and speeding agent is present in an amount of 2.6 phr.

  Suitable softening and speeding agents include, but are not limited to, organic sulfur or metal-containing organic sulfur compounds; mono-, di- and organic sulfur compounds including polysulfides, thiols and mercapto compounds; inorganic sulfur compounds; Blends with inorganic sulfur compounds; Group VIA compounds; substituted or unsubstituted aromatic organic compounds that do not contain sulfur or metals; aromatic organometallic compounds; hydroquinones; benzoquinones; quinhydrones; catechols; resorcinols; Including.

As used herein, the term “organosulfur compound” refers to any compound containing carbon, hydrogen and sulfur, where the sulfur is bonded directly to at least one carbon. As used herein, the term “sulfur compound” means a compound that is elemental sulfur, polymeric sulfur, or a combination thereof. Further, it should be understood that “elemental sulfur” refers to a ring structure of S ₈ and “polymeric sulfur” is a structure that includes at least one additional sulfur relative to elemental sulfur.

式中、Ｒ_１〜Ｒ_５はいずれの順番であってもよく、Ｃ_１〜Ｃ_８アルキル基；ハロゲン基；チオール基（−ＳＨ）、カルボキシレート基；スルホネート基；、及び水素であってよく、また、ペンタフルオロチオフェノール；２−フルオロチオフェノール；３−フルオロチオフェノール；４−フルオロチオフェノール；２，３−フルオロチオフェノール；２，４−フルオロチオフェノール；３，４−フルオロチオフェノール；３，５−フルオロチオフェノール；２，３，４−フルオロチオフェノール；３，４，５−フルオロチオフェノール；２，３，４，５−テトラフルオロチオフェノール；２，３，５，６−テトラフルオロチオフェノール；４−クロロテトラフルオロチオフェノール；ペンタクロロチオフェノール；２−クロロチオフェノール；３−クロロチオフェノール；４−クロロチオフェノール；２，３−クロロチオフェノール；２，４−クロロチオフェノール；３，４−クロロチオフェノール；３，５−クロロチオフェノール；２，３，４−クロロチオフェノール；３，４，５−クロロチオフェノール；２，３，４，５−テトラクロロチオフェノール；２，３，５，６−テトラクロロチオフェノール；ペンタブロモチオフェノール；２−ブロモチオフェノール；３−ブロモチオフェノール；４−ブロモチオフェノール；２，３−ブロモチオフェノール；２，４−ブロモチオフェノール；３，４−ブロモチオフェノール；３，５−ブロモチオフェノール；２，３，４−ブロモチオフェノール；３，４，５−ブロモチオフェノール；２，３，４，５−テトラブロモチオフェノール；２，３，５，６−テトラブロモチオフェノール；ペンタヨードチオフェノール；２−ヨードチオフェノール；３−ヨードチオフェノール；４−ヨードチオフェノール；２，３−ヨードチオフェノール；２，４−ヨードチオフェノール；３，４−ヨードチオフェノール；３，５−ヨードチオフェノール；２，３，４−ヨードチオフェノール；３，４，５−ヨードチオフェノール；２，３，４，５−テトラヨードチオフェノール；２，３，５，６−テトラヨードチオフェノール；及びこれらの亜鉛塩であってよい。好ましくはハロゲン化した有機硫黄化合物はペンタクロロチオフェノールであり、これは純粋な形態で市場から入手可能であり、又はペンタクロロチオフェノールを４５パーセント（２．４部のＰＣＴＰに相当する）付加した硫黄化合物を含むクレイをベースとするキャリヤであるＳＴＲＵＫＴＯＬ（登録商標）の商標名で入手可能である。ＳＴＲＵＫＴＯＬ（商標）はオハイオ州ストウのＳｔｒｕｋｔｏｌＣｏｍｐａｎｙｏｆＡｍｅｒｉｃａから商業的に入手可能である。ＰＣＴＰは商業的にカリフォルニア州サンフランシスコのｅＣｈｉｎａｃｈｅｍから純粋な形態で入手可能であり、サンフランシスコのｅＣｈｉｎａｃｈｅｍから塩の形態で入手可能である。最も好ましくは、ハロゲン化した有機硫黄化合物はペンタクロロチオフェノールの亜鉛塩であり、これはサンフランシスコのｅＣｈｉｎａｃｈｅｍから商業的に入手可能である。最も好ましくは、ハロゲン化した有機硫黄化合物はペンタクロロチオフェノールの亜鉛塩であり、これはサンフランシスコのｅＣｈｉｎａｃｈｅｍから商業的に入手可能である。適切な有機硫黄化合物は、さらに、例えば、米国特許第６，６３５，７１６号、同第６，９１９，３９３号、同第７，００５，４７９号、および同第７，１４８，２７９号に開示されており、その内容は参照してここに組み入れる。 Particularly suitable softening / acceleration agents are organic sulfur compounds having the general formula:

In the formula, R _{1 to} R ₅ may be in any order, and may be a C _{1 to} C ₈ alkyl group; a halogen group; a thiol group (—SH), a carboxylate group; a sulfonate group; and hydrogen. 2-fluorothiophenol; 3-fluorothiophenol; 4-fluorothiophenol; 2,3-fluorothiophenol; 2,4-fluorothiophenol; 3,4-fluorothiophenol; 3,3,4-fluorothiophenol; 3,3,4-fluorothiophenol; 2,3,4,5-tetrafluorothiophenol; 2,3,5,6-tetra 4-chlorotetrafluorothiophenol; pentachlorothiophenol; 2-chlorothiopheno 3-chlorothiophenol; 4-chlorothiophenol; 2,3-chlorothiophenol; 2,4-chlorothiophenol; 3,4-chlorothiophenol; 3,5-chlorothiophenol; 4-chlorothiophenol; 3,4,5-chlorothiophenol; 2,3,4,5-tetrachlorothiophenol; 2,3,5,6-tetrachlorothiophenol; pentabromothiophenol; 2-bromo 3-bromothiophenol; 4-bromothiophenol; 2,3-bromothiophenol; 2,4-bromothiophenol; 3,4-bromothiophenol; 3,5-bromothiophenol; , 4-bromothiophenol; 3,4,5-bromothiophenol; 2,3,4,5-tetrabromothiopheno 2,3,5,6-tetrabromothiophenol; pentaiodothiophenol; 2-iodothiophenol; 3-iodothiophenol; 4-iodothiophenol; 2,3-iodothiophenol; 3,4-iodothiophenol; 3,5-iodothiophenol; 2,3,4-iodothiophenol; 3,4,5-iodothiophenol; 2,3,4,5-tetraiodo It may be thiophenol; 2,3,5,6-tetraiodothiophenol; and zinc salts thereof. Preferably the halogenated organic sulfur compound is pentachlorothiophenol, which is commercially available in pure form, or added 45 percent of pentachlorothiophenol (equivalent to 2.4 parts of PCTP). It is available under the trade name STRUKTOL®, a clay-based carrier containing sulfur compounds. STRUKTOL ™ is commercially available from StruktolCompanyof America, Stow, Ohio. PCTP is commercially available in pure form from eChinachem, San Francisco, California, and is available in salt form from eChinachem, San Francisco. Most preferably, the halogenated organic sulfur compound is a zinc salt of pentachlorothiophenol, which is commercially available from eChinachem, San Francisco. Most preferably, the halogenated organic sulfur compound is a zinc salt of pentachlorothiophenol, which is commercially available from eChinachem, San Francisco. Suitable organic sulfur compounds are further disclosed, for example, in US Pat. Nos. 6,635,716, 6,919,393, 7,005,479, and 7,148,279. The contents of which are incorporated herein by reference.

  Suitable metal-containing organosulfur compounds are, but are not limited to, cadmium, copper, lead, and tellurium analogs of diethyldithiocarbamate, diamyldithiocarbamate, and dimethyldithiocarbamate, or mixtures thereof. Additional examples are disclosed in US Pat. No. 7,005,479, the contents of which are incorporated herein by reference.

  Suitable disulfides include, but are not limited to, 4,4′-diphenyl disulfide; 4,4′-ditolyl disulfide; 2,2′-benzamide diphenyl disulfide; bis (2-aminophenyl) disulfide; Aminophenyl) disulfide; bis (3-aminophenyl) disulfide; 2,2′-bis (4-aminonaphthyl) disulfide; 2,2′-bis (3-aminonaphthyl) disulfide; 2,2′-bis (4 -Aminonaphthyl) disulfide; 2,2'-bis (5-aminonaphthyl) disulfide; 2,2'-bis (6-aminonaphthyl) disulfide; 2,2'-bis (7-aminonaphthyl) disulfide; 2′-bis (8-aminonaphthyl) disulfide; 1,1′-bis (2-aminonaphthyl) dis 1,1'-bis (3-aminonaphthyl) disulfide; 1,1'-bis (3-aminonaphthyl) disulfide; 1,1'-bis (4-aminonaphthyl) disulfide; 1,1'-bis (5-aminonaphthyl) disulfide; 1,1′-bis (6-aminonaphthyl) disulfide; 1,1′-bis (7-aminonaphthyl) disulfide; 1,1′-bis (8-aminonaphthyl) disulfide; 1,2′-diamino-1,2′-dithiodinaphthalene; 2,3′-diamino-1,2′-dithiodinaphthalene; bis (4-chlorophenyl) disulfide; bis (2-chlorophenyl) disulfide; 3-chlorophenyl) disulfide; bis (4-bromophenyl) disulfide; bis (2-bromophenyl) disulfide; bis ( Bis (4-fluorophenyl) disulfide; bis (4-iodophenyl) disulfide; bis (2,5-dichlorophenyl) disulfide; bis (3,5-dichlorophenyl) disulfide; bis (2,4-dichlorophenyl) Bis (2,6-dichlorophenyl) disulfide; bis (2,5-dibromophenyl) disulfide; bis (3,5-dibromophenyl) disulfide; bis (2-chloro-5-bromophenyl) disulfide; 2,4,6-trichlorophenyl) disulfide; bis (2,3,4,5,6-pentachlorophenyl) disulfide; bis (4-cyanophenyl) disulfide; bis (2-cyanophenyl) disulfide; Nitrophenyl) dis Bis (2-nitrophenyl) disulfide; 2,2'-dithiobenzoic acid ethyl ester; 2,2'-dithiobenzoic acid methyl ester; 2,2'-dithiobenzoic acid; 4,4'-dithiobenzoic acid Bis (4-acetylphenyl) disulfide; bis (2-acetylphenyl) disulfide; bis (4-formylphenyl) disulfide; bis (4-carbamoylphenyl) disulfide; 1,1′-dinaphthyl disulfide; 1,2′-dinaphthyl disulfide; 1,2′-dinaphthyl disulfide; 2,2′-bis (1-chlorodinaphthyl) disulfide; 2,2′-bis (1-bromonaphthyl) disulfide; Bis (2-chloronaphthyl) disulfide; 2,2′-bis (1-cyanonaphthyl) disulfide De; 2,2'-bis (1-acetyl-naphthyl) disulfide and the like; is or mixtures thereof.

  Suitable inorganic sulfide components include, but are not limited to, titanium sulfide, manganese sulfide, and similar sulfides of iron, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, tin, and bismuth. To do.

  Suitable Group VIA compounds include, but are not limited to, elemental sulfur and polymeric sulfur, such as those available commercially from Elastochem, Chardon, Ohio; PB (RM-S), each available from Elastochem Sulfur catalyst compounds containing -80 elemental sulfur and PB (CRST) -65 polymer sulfur; tellurium catalysts such as TELLOY ™, and selenium catalysts such as VANDEX ™, each commercially available from RT Vanderbilt Including things.

Suitable substituted or unsubstituted aromatic organic compounds that do not contain sulfur or metals include, but are not limited to, 4,4′-diphenylacetylene, azobenzene, or mixtures thereof. The aromatic organic group is preferably in the range of C _{6 to} C ₂₀ and more preferably in the range of C _{6 to} C _{10 in} size.

Suitable substituted or unsubstituted aromatic organic compounds include, but are not limited to, compounds having the formula (R ₁ ) _x —R ₃ —M—R ₄ — (R ₂ ) _y , wherein R ₁ and R ₂ is hydrogen, or substituted or unsubstituted C ₁ -C ₂₀ linear, branched or cyclic alkyl, alkoxy or alkylthio groups, or monocyclic, polycyclic or condensed ring C ₆ -C _{24, respectively.} X and y are each an integer of 0 to 5; R ₃ and R ₄ are each selected from a monocyclic, polycyclic or condensed ring C _{6 to} C ₂₄ aromatic group; M is an azo group or a metal component. R ₃ and R ₄ are each preferably selected from C _{6 to} C ₁₀ aromatic groups, more preferably selected from phenyl, benzyl, naphthyl, benzamide and benzothiazyl. R ₁ and R ₂ are each preferably selected from substituted or unsubstituted C ₁ -C ₁₀ linear, branched or cyclic alkyl, alkoxy or alkylthio groups, or C ₆ -C ₁₀ aromatic groups . When R ₁ , R ₂ , R ₃ or R ₄ is substituted, the substituent may include one or more of the following substituents: hydroxy and its metal salt; mercapto and its metal salt; halogen; Amino, nitro, cyano and amide; carboxyls including esters, acids and metal salts thereof; silyl; acrylates and metal salts thereof; sulfonyl or sulfonamides; and phosphates and phosphites. When M is a metal component, M can be any suitable elemental metal available to those skilled in the art. Typically, the metal is a transition metal, but is preferably tellurium or selenium.

  Suitable hydroquinones are further disclosed, for example, in US Patent Application Publication No. 2007/0213440, the contents of which are hereby incorporated by reference. Suitable benzoquinones are further disclosed, for example, in US Patent Application Publication No. 2007/0213442, the contents of which are hereby incorporated by reference. Suitable quinhydrones are further disclosed, for example, in US Patent Application Publication No. 2007/0213441, the contents of which are hereby incorporated by reference. Suitable catechols are further disclosed, for example, in US Patent Application Publication No. 2007/0213144, the contents of which are hereby incorporated by reference.

  In a specific embodiment, the center composition is a softening selected from zinc pentachlorothiophenol, pentachlorothiophenol, ditolyl disulfide, diphenyl disulfide, dixylyl disulfide, 2-nitroresorcinol, and combinations thereof.・ Contains a speeding agent.

  Particularly suitable rubber compositions for producing centers are 40 to 55 phr zinc diacrylate, 5 to 50 phr zinc oxide, 0 to 20 phr zinc stearate, and 0.05 to 3.5 phr peroxide. Have

  The center rubber composition optionally includes 1 to 100 phr of stiffening agent. Suitable stiffening agents include, but are not limited to, ionomers, acid copolymers and terpolymers, polyamides, and polyesters. Stiffening agents are further disclosed, for example, in US Pat. Nos. 6,120,390 and 6,284,840, the contents of which are hereby incorporated by reference. Trans polyisoprene (for example, TP-301 trans polyisoprene commercially available from Kuraray) or transbutadiene rubber may also be added to impart rigidity to the core layer and / or to improve ambient temperature production characteristics. This may facilitate the molding of the outer shell half of the core layer in the golf ball manufacturing process to improve processability. When included in the core layer, the stiffening agent is preferably present in an amount of 5 to 10 pph.

  For types and amounts of base rubber initiators, coagents, curing agents, fillers, and additives, see, for example, US Pat. Nos. 6,566,483, 6,695,718, and 6,939. 907, No. 7,041,721, and No. 7,138,460, the contents of which are incorporated herein by reference.

  In other embodiments, the center is made from a highly neutralized polymer composition. Suitable highly neutralized polymeric core compositions are further disclosed, for example, in US Pat. No. 7,230,045, the contents of which are hereby incorporated by reference.

  In another embodiment, the center is manufactured from a first highly neutralized polymer composition, and the golf ball additionally has a core layer disposed between the center and the intermediate layer, the center and intermediate layer The core layer disposed between is made from a second highly neutralized polymer composition. Cores comprising two layers made from highly neutralized polymer composition (s) are further disclosed, for example, in US Pat. Nos. 7,211,008 and 7,207,903, the contents of which are Are incorporated herein by reference.

  The intermediate layer is manufactured from a rubber composition or a thermoplastic composition disclosed below. The interlayer composition preferably involves a solid single core compression of 40 or less, or less than 40, or 30 or less, or less than 30, or 20 or less, or less than 20. For the purposes of this disclosure, “solid single core compression” refers to the compression of 1.550 inch solid spheres made from the composition. In one embodiment, the single layer core compression of the middle layer is less than the center compression, and in a specific aspect of the embodiment, at least 10 compression points, or more than 10 compression points, or at least 20 compression. Less than center compression by only points, or more than 20 compression points, at least 25 compression points, or more than 25 compression points, or at least 30 compression points, or more than 30 compression points.

  In examples where the interlayer is made from a rubber composition, the interlayer composition comprises: With a solid single core COR of less than 0770, or 0.750. For purposes of this disclosure, “solid single core COR” refers to the COR of a 1.550 inch solid sphere made from the composition.

  Suitable rubber compositions for producing the intermediate layer include those previously disclosed as suitable for producing the center, but the rubber composition for producing the intermediate layer is preferably 100 parts of base rubber. The difference is that it has less than 40 parts by weight of agent. In a specific embodiment, the rubber composition of the intermediate layer is present in an amount of 35 parts or less, or less than 30 parts, or 25 parts or less, or 20 parts or less by weight with respect to 100 parts of the base rubber, or , By weight with respect to 100 parts of base rubber, with a lower limit of 0, 1 or 5 or 10 parts and in an upper limit of 15 or 20 or 25 or 30 or 35 parts.

Suitable thermoplastic compositions for producing the intermediate layer include grafted copolymers of partially or highly neutralized ionomers, ionomers and polyamides, optionally blended with maleic anhydride grafted non-ionomer polymers, and the following: Non-ionomeric polymers of these, including homopolymers and copolymers thereof, and at least one grafted or copolymerized functional group such as maleic anhydride, amine, epoxy, isocyanate, hydroxyl, sulfonate, Including their derivatives, which are compatible with phosphates and others.
(A) Polyesters, particularly polyesters modified with compatible groups such as sulfonates or phosphates. This includes modified poly (ethylene terephthalate), modified poly (butylene terephthalate), modified poly (propylene terephthalate), modified poly (trimethylene terephthalate), modified poly (ethylene naphthaleate), and US Pat. , 353,050 and 6,001,930, and blends of two or more thereof. The contents of these documents are incorporated herein by reference.
(B) polyamides, polyamide-ethers, and polyamide-esters, and those disclosed in US Pat. Nos. 6,187,864, 6,001,930, and 5,981,654, and A blend of two or more of these. The contents of these documents are incorporated herein by reference.
(C) Polyurethanes, polyureas, polyurethane-polyurea hybrids, and blends of two or more thereof.
(D) Fluoropolymers such as those disclosed in US Pat. Nos. 5,691,066, 6,747,110, and 7,009,002, and blends of two or more thereof. The contents of these documents are incorporated herein by reference.
(E) non-ionomeric acid polymers such as E / Y- and E / X / Y-type copolymers, where E is an olefin (eg ethylene) and Y is a carboxylic acid such as acrylic acid, methacrylic acid, croton An acid, maleic acid, fumaric acid or itaconic acid, and X is a softening comonomer, for example a vinyl estate of an aliphatic carboxylic acid wherein the acid has 2 to 10 carbons, 1 to 10 alkyl groups Alkyl ethers comprising carbon, and alkyl acrylates wherein the alkyl group comprises 1 to 10 carbons; and blends of two or more thereof.
(F) Metallocene-catalyzed polymers, such as disclosed in US Pat. Nos. 6,274,669, 5,919,862, 5,981,654, and 5,703,166 And blends of two or more of these. The contents of these documents are incorporated herein by reference.
(G) Polystyrene, such as poly (styrene-co-maleic anhydride), acrylonitrile-butadiene-styrene, poly (styrene sulfonate), polyethylene styrene, and blends thereof.
(H) Polypropylene and polyethylene, especially grafted polypropylene and grafted polyethylene modified with functional groups such as maleic anhydride, and blends of two or more thereof.
(I) Polyvinyl chloride and grafted polyvinyl chloride, and blends of two or more thereof.
(J) Polyvinyl acetate, preferably comprising less than about 9% by weight vinyl acetate, and blends of two or more thereof.
(K) Polycarbonate, polycarbonate / acrylonitrile-butadiene styrene blend, polycarbonate / polyurethane blend, and polycarbonate / polyester blend, and blends of two or more thereof.
(L) Polyvinyl alcohol and blends of two or more thereof.
(M) Polyethers, such as polyarylene ethers, polyphenylene oxides, block copolymers of alkene aromatic hydrocarbons with vinyl aromatic hydrocarbons and poly (amidate esters), and blends of two or more thereof.
(N) Polyimide, polyetherketone, polyamideimide, and blends of two or more thereof.
(O) Polycarbonate / polyester copolymers and blends.
(P) A combination of two or more of the aforementioned thermoplastic polymers.

  An ionomer composition suitable for producing the intermediate layer has one or more acid polymers, optional additives, fillers, and / or melt flow modifiers, each partially or highly neutralized. Suitable acid polymers are salts of homopolymers or copolymers of α, β-ethylenically unsaturated mono- or dicarboxylic acids, and combinations thereof, which optionally include a softening monomer, preferably from 1 wt% It has an acid content (before neutralization) of 30 wt%, more preferably 5 wt% to 20 wt%. The acid polymer is neutralized by a suitable cation source, such as a metal cation or salt thereof, an organic amine compound, ammonia, and combinations thereof, to 70% or more and to 100%. The preferred cation source is a metal cation and its cation when the metal is preferably lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum, manganese, nickel, chromium, copper, or combinations thereof. Salt. Suitable additives and fillers include, for example, chemical expansion and foaming agents, optical brighteners, colorants, fluorescent agents, whitening agents, UV absorbers, light stabilizers, antifoaming agents, processing aids, mica, Talc, nanofillers, antioxidants, stabilizers, softeners, perfume ingredients, plasticizers, impact modifiers, acid copolymer waxes, surfactants; inorganic fillers such as zinc oxide, titanium dioxide, tin oxide, calcium oxide , Magnesium oxide, Barium sulfate, Zinc sulfate, Calcium carbonate, Zinc carbonate, Barium carbonate, Mica, Talc, Clay, Silica, Lead silicate, etc .; High specific metal powder filler, eg, tungsten powder, molybdenum powder, etc .; A core material recycled by grinding; and a nanofiller. Suitable melt flow modifiers include, for example, fatty acids and salts thereof, polyamides, polyesters, polyacrylates, polyurethanes, polyethers, polyureas, polyhydric alcohols, and combinations thereof. Suitable ionomer compositions are highly neutralized, for example, partially neutralized ionomers as disclosed in US Patent Application Publication No. 2006/0128904, incorporated herein by reference. And blends with other polymers (ie, those that are neutralized at least 70%). Suitable ionomer compositions also include blends of one or more partially or highly neutralized polymers with additional thermoplastic and thermoset materials, including but not limited to non-ionomeric acid copolymers. Engineering thermoplastics, fatty acid / salt based highly neutralized polymers, polybutadiene, polyurethane, polyurea, polyester, polycarbonate / polyester blends, thermoplastic elastomers, maleic anhydride grafted metallocene catalyst polymers and other conventional Containing polymeric materials. Suitable ionomer compositions are further described in U.S. Patent Nos. 6,653,382, 6,756,436, 6,777,472, 6,894,098, 919,393, and 6,953,820 and US Patent Application Publication No. 2006/0106175, the contents of which are incorporated herein by reference.

  Examples of commercially available thermoplastic materials suitable for forming the intermediate core layer include, but are not limited to, Pebax ™ thermoplastic polyether block amide, commercially available from Arkema Inc; (Trademark) ionomer resin, Hytrel (TM) thermoplastic polyester elastomer, ionomer materials sold under the trademark DuPont (TM) HPF1000 and HPF2000, all I. Commercially available from DuPont; Iotek ™ ionomer available commercially from ExxonMobil Chemical; ionomer of Amplify ™ IO ethylene acrylic acid copolymer commercially available from The Dow Chemical Company; A. Clarix ionomer resin commercially available from Schulman Inc; Elastollan ™ polyurethane blend-based thermoplastic elastomer commercially available from BASF; and Xylex ™ commercially available from SABIC Innovative Plastics Contains a polycarbonate / polyester blend.

  In a specific embodiment, the intermediate layer is made from a polyurea composition. In a specific aspect of this example, the flexural modulus of the interlayer composition is less than the outer cover layer, preferably 100,000 psi or less, or less than 100,000, or 50,000 psi or less, or 50,000. Less than 000, or less than 30,000 psi, or less than 30,000, or a lower limit of 500 psi and an upper limit of 25,000 psi, or 30,000 psi, or 50,000 psi, or 100,000 psi. In other specific aspects of this embodiment, the intermediate layer has a material hardness of 60 Shore D or less, or less than 60 Shore D, or 50 Shore D or less, or less than 50 Shore D, or 45 Shore D or less, or 45 Less than Shore D, or 40 Shore D or less, or less than 40 Shore D, or a lower limit of 15 or 35 Shore D and an upper limit of 35 or 40 or 50 or 60 Shore D. In yet another specific aspect of this example, the polyurea composition of the intermediate layer is, for example, US patent application Ser. No. 12 / 122,406 filed May 16, 2008; filed May 16, 2008. No. 12 / 122,333; filed May 16, 2008 No. 12 / 122,370; filed May 16, 2008 No. 12 / 122,384; filed May 16, 2008; and May 2008 No. 12 / 122,3960, filed 16 days ago, is a dual cured polyurea, the contents of which are incorporated herein by reference.

  In other specific embodiments, the intermediate layer comprises polybutadiene, ionomer, metallocene catalyzed polyolefin, polyether ester, polyether amide, maleic anhydride grafted non-ionomeric polymer, polyurethane, polyurea, polyurethane and polyurea copolymer. And a blend, and a composition selected from ethylene propylene diene rubber. In a specific aspect of this example, the intermediate layer has a polybutadiene composition, preferably 0 to 20 phr of a coagent selected from the group consisting of diacrylate, dimethacrylate, and monomethacrylate metal salts. Manufactured from. In another specific aspect of this example, the intermediate layer is made from a polyetherester composition. In other specific aspects of this example, the flexural modulus of the intermediate layer composition is less than that of the outer cover layer, preferably 100,000 psi or less, or less than 100,000, or 50,000 psi or less, or Less than 50,000, or less than 30,000 psi, or less than 30,000, or a lower limit of 500 psi and an upper limit of 25,000 psi, or 30,000 psi, or 50,000 psi, or 100,000 psi. In other specific aspects of this embodiment, the intermediate layer has a material hardness of 60 Shore D or less, or less than 60 Shore D, or 50 Shore D or less, or less than 50 Shore D, or 40 Shore D or less, or 40 Less than Shore D, or a lower limit of 15 or 35 Shore D and an upper limit of 35 or 40 or 50 or 60 Shore D.

  The intermediate layer composition may include a stiffening agent. Suitable stiffening agents include those previously disclosed for use in center compositions. Preferably, if a stiffening agent is included, the stiffening agent is included in the center and not in the intermediate layer.

  The golf ball of the present invention includes a cover having one or more layers. Suitable cover materials include, but are not limited to, ionomer resins and blends thereof (Surlyn ™ ionomer resins commercially available from EI DuPont, DuPont HPF 1000 and HPF 2000, commercially available from ExxonMobil Chemical). Iotek ™ ionomer available; Amplify ™ IO ethylene acrylic acid copolymer ionomer commercially available from The Dow Chemical Company; A. Schulman Inc. commercially available Clarkix ionomer resin); polyurethane Polyurea; copolymers and blends of polyurethane and polyurea; for example, low density polyethylene, linear low density polyethylene, and high density Polyethylene containing reethylene; polypropylene; rubber reinforced olefin polymer; acid copolymer that does not form part of ionomer copolymer; plastomer; flexomer; styrene / butadiene / styrene block copolymer; styrene / ethylene-butylene / styrene block copolymer; dynamically vulcanized Elastomers; ethylene vinyl acetate; ethylene methyl acrylate; polyvinyl chloride resins; polyamides, amide-ester elastomers, and ionomers and polyamides, including, for example, Pebax ™ thermoplastic polyether block amide commercially available from Arkema A graft copolymer of: cross-linked trans-polyisoprene and blends thereof; polyester-based thermoplastic elastomers such as , E.C. I. Hytel ™ commercially available from DuPont de Nemours and Company; polyurethane-based thermoplastic elastomers such as Elastollan ™ commercially available from BASF; synthetic or natural vulcanizates; and these Including a combination of

An ionomer or a composition having two or more ionomers is particularly suitable for the cover material. Preferred ionomer compositions include, but are not limited to:
(A) A composition comprising a “high acid ionomer” (ie an acid content greater than 16 wt%), such as Surlyn 8150 ™.
(B) a composition comprising a high acid ionomer and a maleic anhydride grafted non-ionomeric polymer (eg, Fusbond ™ functionalized polymer. A particularly preferred blend of high acid ionomer and maleic anhydride grafted polymer is Surlyn 8150 ™ and A blend of 84% by weight / 16% by weight of Fusabond ™, blends of high acid ionomers with maleic anhydride grafted polymers are further described, for example, in US Patent Nos. 6,992,135 and 6,677,401. The contents of which are incorporated herein by reference.
(C) A composition having a 50/45/5 blend of Surlyn ™ 8940 / Surlyn ™ 9650 / Nucrel ™ 960, preferably with a material hardness of 80 to 85 Shore C.
(D) A composition having a 50/25/25 blend of Surlyn ™ 8940 / Surlyn ™ 9650 / Surlyn ™ 9910, preferably with a material hardness of about 90 Shore C.
(E) A composition having a 50/50 blend of Surlyn ™ 8940 / Surlyn ™ 9650, preferably with a material hardness of about 86 Shore C.
(F) A composition having a blend of Surlyn ™ 7940 / Surlyn ™ 8940 and optionally including a melt flow modifier.
(G) having a blend of a first high acid ionomer and a second high acid ionomer, wherein the first high acid ionomer is neutralized with a different cation than the second high acid ionomer (eg, Surlyn ™ 8150); / Surlyn ™ 9150 is also a 50/50 blend), optionally comprising one or more melt flow modifiers, such as ionomers, ethylene acid copolymers or ester terpolymers.
(H) a first high acid ionomer and a second high acid ionomer and a blend of 0 to 10 wt% ethylene / acid / ester ionomer, wherein the first high acid ionomer is a different cation than the second high acid ionomer. The ethylene / acid / ester ionomer is the same cation as the first high acid ionomer or the second high acid ionomer, or a cation different from either the first high acid ionomer or the second high acid ionomer. Composition to be neutralized (eg, a blend of 40-50 wt% Surlyn ™ 8140, 40-50 wt% Surlyn ™ 9120, and 0-10 wt% Surlyn ™ 6320).

  Surlyn 8150 ™, Surlyn ™ 8940, and Surlyn ™ 8140 are different grades of E / MAA copolymers with acid groups partially neutralized by sodium ions. Surlyn (TM) 9650, Surlyn (TM) 9910, Surlyn (TM) 9150, and Surlyn (TM) 9120 are different grades of E / MAA copolymers with acid groups partially neutralized by zinc ions. Surlyn ™ 7940 is an E / MAA copolymer in which the acid groups are partially neutralized with lithium ions. Surlyn ™ 6320 is a very low elasticity magnesium ionomer with an intermediate acid content. Nucrel ™ 960 is an E / MAA copolymer resin made with nominally 15 wt% methacrylic acid. Surlyn ™ ionomer, Fusbond ™ polymer, and Nuclel copolymer are available from E.I. I. Commercially available from DuPont de Nemours and Company.

  The ionomer cover composition may be blended with a nonionic thermoplastic resin. Suitable nonionic thermoplastic resins include, but are not limited to, polyurethanes, poly-ether-esters, poly-amide-ethers, poly-ether-ureas, thermoplastic polyether block amides (eg, commercially available from Arkema Inc. Pebax ™ block copolymer), styrene-butadiene-styrene block copolymer, styrene (ethylene-butylene) -styrene block copolymer, polyamide, polyester, polyolefin (eg, polyethylene, polypropylene, ethylene-propylene copolymer, polyethylene) -(Methacrylate) acrylate, polyethylene- (methacrylic acid) acrylic acid, polymer functionalized by maleic anhydride grafting, commercially available from EI DuPont Possible Fusabond (R) functionalized polymer, the functionalized polymer by epoxidation, elastomers (e.g., ethylene propylene diene monomer rubber, metallocene-catalyzed polyolefins), and a ground powder of the thermoplastic elastomer.

  Suitable ionomer cover materials further include, for example, U.S. Patent Nos. 6,653,382, 6,756,436, 6,894,098, 6,919,393, and No. 6,953,820, the contents of which are incorporated herein by reference.

  Polyurethanes, polyureas, and polyurethane / polyurea blends and hybrids are also particularly suitable for forming the cover layer. When employed as a cover layer material, polyurethane and polyurea may be thermoset or thermoplastic. The thermosetting material can be formed into the golf ball layer by conventional casting or reactive injection molding techniques. The thermoplastic material can be formed into the golf ball layer by conventional compression or injection molding techniques.

  The polyurethane cover compositions of this invention include those made from the reaction product of at least one polyisocyanate and at least one curing agent. The curing agent may include, for example, one or more diamines, one or more polyols, or combinations thereof. The at least one polyisocyanate may be combined with one or more polyols to form a prepolymer, which is then combined with the at least one curing agent. Where polyols are described herein, they are suitable for use in one or both of the components of the polyurethane material, ie as part of the prepolymer, or as in the curing agent. The curing agent includes a polyol curing agent, preferably ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; polypropylene glycol; low molecular weight polytetramethylene ether glycol; 1,3-bis (2-hydroxyethoxy) benzene; 3-bis [2- (2-hydroxyethoxy) ethoxy] benzene; 1,3-bis {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} benzene; 1,4-butanediol; 1,6-hexanediol; resorcinol-di- (β-hydroxyethyl) ether; hydroquinone-di- (β-hydroxyethyl) ether; trimethylolpropane; and a polyol selected from the group consisting of these Cure It is an agent.

  Suitable polyurethane cover compositions of the present invention comprise a reaction product of at least one isocyanate and at least one curing agent, or a reaction product of at least one isocyanate, at least one polyol, and at least one curing agent. Includes manufactured products. Preferred isocyanates are 4,4′-diphenylmethane diisocyanate, polymeric 4,4′-diphenylmethane diisocyanate, carbodiimide-modified liquid 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, toluene diisocyanate. A selected from the group consisting of isophorone diisocyanate, p-methylxylene diisocyanate, m-methylxylene diisocyanate, o-methylxylene diisocyanate, and combinations thereof. Preferred polyols include those selected from the group consisting of polyether polyols, hydroxy-terminated polybutadienes, polyester polyols, polycaprolactone polyols, polycarbonate polyols, and combinations thereof. Preferred curing agents include polyamine curing agents, polyol curing agents, and combinations thereof. Polyamine curing agents are particularly preferred. The polyamine curing agent is, for example, 3,5-dimethylthio-2,4-toluenediamine or its isomer; 3,5-diethyltoluene-2,4-diamine or its isomer; 4,4′-bis- (sec-butyl) Amino) -diphenylmethane; 1,4-bis- (sec-butylamino) -benzene, 4,4′-methylene-bis- (2-chloroaniline); 4,4′-methylene-bis- (3-chloro-) 2,6-diethylaniline); trimethylene glycol-di-p-aminobenzoate; polytetramethylene oxide-di-p-aminobenzoate; N, N′-dialkyldiaminodiphenylmethane; p, p′-methylenedianiline; Diamine; 4,4'-methylene-bis- (2-chloroaniline); 4,4'-methylene-bis (2,6-diethylaniline); 4,4′-diamino-3,3′-diethyl-5,5′-dimethyldiphenylmethane; 2,2′-3,3′-tetrachlorodiaminodiphenylmethane; -Methylene-bis- (3-chloro-2,6-diethylaniline); and combinations thereof.

This invention is not limited by the use of specific polyisocyanates in the cover composition. Suitable polyisocyanates include, but are not limited to, 4,4′-diphenylmethane diisocyanate (“MDI”), polymeric MDI, carbodiimide-modified liquid MDI, 4,4′-dicyclohexylmethane diisocyanate (“H ₁₂ MDI”), p-phenylene diisocyanate ("PPDI"), toluene diisocyanate ("TDI"), 3,3'-dimethyl-4,4'-biphenylene diisocyanate ("TODI"), isophorone diisocyanate ("IPDI"), hexamethylene diisocyanate ( "HDI"), naphthalene diisocyanate ("NDI"), xylene diisocyanate ("XDI"), para-tetramethylxylene diisocyanate ("p-TMXDI"), meta-tetramethylxylene diisocyanate "M-TMXDI"), ethylene diisocyanate, propylene-1,2-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexyl diisocyanate, 1,6-hexamethylene-diisocyanate ("HDI"); dodecane-1,12- Cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane; methylcyclohexylene diisocyanate; HDI Triisocyanate; 2,4,4-trimethyl-1,6-hexane diisocyanate triisocyanate ("TMDI"); tetracene diisocyanate; Isocyanate; anthracene diisocyanate; and combinations thereof. Polyisocyanates are known to those skilled in the art as having one or more isocyanate groups, such as di-, tri- and tetraisocyanates. Preferably, the polyisocyanate comprises MDI, PPDI, TDI, and mixtures thereof. More preferably the polyisocyanate comprises MDI. As used herein, the term “MDI” refers to 4,4′-diphenylmethane diisocyanate, polymeric MDI, carbodiimide modified liquid MDI, and combinations thereof, and further the diisocyanate used is a “low free monomer”. It should be understood by those skilled in the art that the amount of “free” monomer is a low isocyanate group, typically that the amount of free monomer group is less than about 0.1%. is there. Examples of “low free monomer” diisocyanates include, but are not limited to, low free monomer MDI, low free monomer TDI, and low free monomer PPDI.

  The at least one polyisocyanate described above should have less than 14% unreacted NCO groups. Preferably the at least one polyisocyanate is no more than 8.5% NCO, more preferably 2.5% to 8.0%, even more preferably 4.0% to 7.2%, most preferably 5.0%. % To 6.5%.

  This invention is not limited by the use of a specific polyol in the cover composition. In one example, the molecular weight of the polyol is from about 200 to about 6000. Examples of polyols include, but are not limited to, polyether polyols, hydroxy-terminated polybutadienes (including partially / fully hydrogenated derivatives), polyester polyols, polycaprolactone polyols, and polycarbonate polyols. Particularly preferred are polytetramethylene ether glycol (“PTMEG”), polyethylene propylene glycol, polyoxypropylene glycol, and combinations thereof. The hydrocarbon chain can have saturated or unsaturated bonds and substituted or unsubstituted aromatic and cyclic groups. Preferably, the polyol of this invention comprises PTMEG. Suitable polyester polyols include, but are not limited to, polyethylene adipate glycol, polybutylene adipate glycol, polyethylene propylene adipate glycol, ortho-phthalate-1,6-hexanediol; and combinations thereof. The hydrocarbon chain can have saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups. Suitable polycaprolactone polyols include, but are not limited to, 1,6-hexanediol-initiated polycaprolactone, diethylene glycol initiated polycaprolactone, trimethylolpropane initiated polycaprolactone, neopentyl glycol initiated polycaprolactone, 1,4-butanediol initiated Polycaprolactone, PTMEG initiated polycaprolactone, and combinations thereof. The hydrocarbon chain can have saturated or unsaturated, or substituted or unsubstituted aromatic and cyclic groups. Suitable polycarbonates include, but are not limited to, polyphthalate carbonate. The hydrocarbon chain can have saturated or unsaturated, or substituted or unsubstituted aromatic and cyclic groups.

  Polyamine hardeners are also suitable for use in the hardeners of the polyurethane compositions of this invention and have been found to improve the cut resistance, shear resistance, and impact resistance of product balls. Preferred polyamine curing agents include, but are not limited to, 3,5-dimethylthio-2,4-toluenediamine and its isomer; 3,5-diethyltoluene-2,4-diamine and its isomer, such as 3,5-diethyl Toluene-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); polytetramethylene oxide-di-p-aminobenzoate; N, N'-dialkyldiaminodiphenylmethane; p, p'-methylenedianiline ("MDA"); m-phenylenediamine ("MPDA"); 4,4'-methylene-bis (2-chloroaniline) ("MOCA"); 4,4'-methylene-bis- (2,6-diethylaniline); 4,4'-diamino-3,3'-diethyl-5,5'-dimethyl 2,2′-3,3′-tetrachlorodiaminodiphenylmethane; 4,4′-methylene-bis- (3-chloro-2,6-diethylaniline); trimethylene glycol di-p-aminobenzoate; These combinations are included. Preferably, the curing agent of this invention comprises 3,5-dimethylthio-2,4-toluenediamine and its isomers, such as ETHACURE 300. Suitable polyamine curing agents include both primary and secondary amines, and preferably have a molecular weight in the range of about 64 to about 2000.

  At least one diol, triol, tetraol, or hydroxy-terminated curing agent can be added to the polyurethane composition described above. Suitable diol, triol, and tetraol groups include: ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; polypropylene glycol; low molecular weight polytetramethylene ether glycol; 1,3-bis (2-hydroxyethoxy) benzene; 1,3-bis- [2- (2-hydroxyethoxy) ethoxy] benzene; 1,3-bis- {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} benzene; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; resorcinol-di- (β-hydroxyethyl) ether; hydroquinone-di- (β-hydroxyethyl) ether; and combinations thereof. Preferred hydroxy-terminated curing agents include ethylene glycol; diethylene glycol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol, trimethylolpropane, and combinations thereof. Preferably, the molecular weight of the hydroxy-terminated curing agent ranges from about 48 to about 2000. Here, the molecular weight is an absolute weight average molecular weight, as understood by those skilled in the art.

  Both the hydroxy terminus and the amine curing agent can contain one or more saturated, unsaturated, aromatic, and cyclic groups. In addition, the hydroxy terminus and the amine curing agent can include one or more halogen groups. Polyurethane compositions can be made by blends or mixtures of curing agents. However, if desired, the polyurethane composition can be made with a single curing agent.

  Any known technique can be used to combine the polyisocyanates, polyols, and curing agents of the present invention. One suitable technique is known in the art as a one-shot process, where the polyisocyanate, polyol, and curing agent are mixed simultaneously. This method results in a heterogeneous (more random) mixture and the manufacturer is more difficult to control the molecular structure of the manufactured composition. This neat technique of mixing is known as the prepolymer process. In this method, the polyisocyanate and polyol are mixed separately prior to addition of the curing agent. This method achieves a more uniform mixing, resulting in a more uniform polymer composition.

  Suitable polyurethanes further include, for example, U.S. Pat. Nos. 5,334,673, 6,506,851, 6,756,436, 6,867,279, 960,630, and 7,105,623, the contents of which are incorporated herein by reference. Suitable polyureas are further disclosed, for example, in US Pat. Nos. 5,484,870 and 6,835,794, and US patent application 60 / 401,047, the contents of which are referred to And are also disclosed in US Patent Application Publication Nos. 2009/0286624, 2009/0286625, 2009/0286626, 2009/0286627, and 2009/0283932. Double cured polyureas are also included, the contents of which are incorporated herein by reference.

  The golf ball cover layer may include a flow modifier, including but not limited to, for example, Nucrel ™ acid copolymer resin, and specifically, Nucrel ™ 960. Nucrel ™ acid copolymer resin is available from E.I. I. Commercially available from DuPont de Nemours and Company.

  The cover composition may comprise one or more fillers, for example fillers provided for the gol composition of the invention (for example titanium dioxide, barium sulphate etc.) and / or additives, for example colorants, fluorescent agents , Whitening agents, antioxidants, dispersants, UV absorbers, light stabilizers, plasticizers, surfactants, compatibilizers, foaming agents, reinforcing agents, release agents, and the like.

  Suitable cover materials and structures include, but are not limited to, US Patent Application Publication No. 2005/0164810, US Pat. Nos. 5,919,100, 6,117,025, 6,767,940. No. 6,960,630 and those disclosed in PCT Publications WO 00/23519 and WO 00/29129, the contents of which are hereby incorporated by reference.

  In a specific embodiment, the cover comprises an ionomer, a metallocene-catalyzed polyolefin, a maleic anhydride grafted non-ionomeric polymer (eg, Fusbond functionalized polymer), polyurethane, polyurea, polyurethane and polyurea copolymers and blends, polyether amide And an outer cover layer made from a composition selected from polyester, polybutadiene rubber, ethylene propylene diene rubber, and combinations thereof. In a specific aspect of this example, the outer cover layer is made from a composition selected from a Li / Na ionomer blend, a Li / Mg ionomer end, and a Li / Na / Mg ionomer blend. In other specific aspects of this example, the flexural modulus of the outer cover layer composition is greater than or equal to 40000 psi, or greater than 40000 psi, or greater than 50000 psi, or greater than 50000 psi, or greater than 60000 psi, or greater than 60000 psi, or The lower limit is in the range of 40000 or 50000 or 60000 psi and the upper limit is 120,000 psi. In another specific aspect of this example, the material hardness of the outer cover layer composition is greater than 60 Shore D, or a lower limit of 60 Shore D and an upper limit of 66, 70, or 80 Shore D.

  For the purposes of the disclosure herein, material hardness is measured according to ASTM D2240 and is generally associated with measuring the hardness of a flat “slab” or “button” made from the material. It should be understood that “material hardness” and “hardness measured directly on the surface of a golf ball” are fundamentally different. Hardness as measured directly at the surface of a golf ball (or other spherical surface) typically results in a hardness value that is different from the material hardness. This difference in hardness values includes, but is not limited to, ball structure (ie, core type, number of cores and / or cover layers, etc.), ball (or sphere) diameter, and material composition of each adjacent layer. It comes from several factors. It should also be understood that the two measurement methods do not correlate linearly and therefore one hardness value cannot be easily correlated with the other hardness value. Unless otherwise stated, the hardness values given here for cover materials are those according to ASTM D2340, all values reported according to the conditions of 50% relative humidity and 10 days at 23 ° C. Has been.

  A water vapor barrier layer is optionally adopted between the core and the cover. The water vapor barrier layer may further include, for example, US Pat. Nos. 6,632,147, 6,838,028, 6,932,720, 7,004,854, and 7, , 182,702, and US Patent Application Publication Nos. 2003/0069082, 2003/0069085, 2003/0130062, 2004/0147344, 2004/0185963, 2006 / Nos. 0068938, 2006/0128505, and 2007/0129172, the contents of which are incorporated herein by reference.

  In addition to the materials described above, either the core or the cover layer may include one or more of the following materials. Thermoplastic elastomers, thermosetting elastomers, synthetic rubbers, thermoplastic vulcanizates, copolymeric ionomers, terpolymeric ionomers, polycarbonates, polyolefins, polyamides, copolymeric polyamides, polyesters, polyester-amides, polyether-amides, Polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polyarylate, polyacrylate, polyphenylene ether, impact-modified polyphenylene ether, high-impact polystyrene, diallyl phthalate polymer, metallocene-catalyzed polymer styrene-acrylonitrile (SAN), olefin-modified SAN, Acrylonitrile-styrene-acrylonitrile, styrene-maleic anhydride (S / MA) polymer, styrene copolymer , Functional styrene copolymer, functional styrene terpolymer, styrene terpolymer, cellulose polymer, liquid crystal polymer (LCP), ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), ethylene propylene rubber (EPR) ), Ethylene vinyl acetate, polyurea, and polysiloxane. Polyamides suitable for use as additional materials in the compositions disclosed herein include resins obtained as follows. (1) As (a) dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, or 1,4-cyclohexanedicarboxylic acid, (b) diamine such as ethylenediamine, tetraethylenediamine, pentamethylenediamine, hexamethylene Polymerization is carried out with diamine, decamethylenediamine, 1,4-cyclohexylamine or m-xylylenediamine. As (2), ring-opening polymerization of a cyclic lactam such as epsilon caprolactam or omega laurolactam is performed. As (3), an aminocarboxylic acid such as 6-aminocaproic acid, 9-aminocaproic acid, 11-aminocaproic acid or 12-aminocaproic acid is polymerized. Alternatively, as (4), a cyclic lactam is copolymerized with a dicarboxylic acid and a diamine. Specific examples of suitable polyamides are nylon 6, nylon 66, nylon 11, nylon 12, copolymer nylon, nylon MXD6 and nylon 46.

  Other preferred materials suitable for use as additional materials in the golf ball compositions disclosed herein are Skypel polyester elastomers commercially available from SK Chemicals, Korea; trademark from Kuraray, Kurashiki, Japan Name commercially available Septon ™ diblock and triblock copolymers, and Kraton ™ diblock or triblock copolymers commercially available from Kraton Polymers LLC of Houston, Texas.

  The ionomer composition used to make the golf ball layer of this invention may be blended with a non-ionomer thermoplastic resin, particularly to manipulate product properties. Examples of suitable non-ionomeric thermoplastics include, but are not limited to, polyurethanes, poly-ether-esters, poly-amide-ethers, polyether-ureas, Pebax ™ commercially available from Arkema Inc. ) Thermoplastic polyether block amide, styrene-butadiene-styrene block copolymer, styrene (ethylene-butylene) -styrene block copolymer, polyamide, polyester, polyolefin (eg, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene- (meth) acrylate) , Polymers functionalized by ethylene- (meth) acrylic acid, maleic anhydride grafting, epoxidation, etc., elastomers (eg EPDM, metallocene-catalyzed polyethylene) and heat Including ground powder of resistance elastomer.

  The compositions disclosed herein may be foamed and filled with a density adjusting material to achieve the desired golf ball properties.

  The present invention is not limited by any specific process for producing a golf ball layer. Note that the layers can be manufactured by any suitable technique, including compression molding, injection molding, casting, and reactive injection molding.

  When employing injection molding, the composition is typically in the form of a pallet or granule that can be easily fed from the entrance of the injection molding machine, where it is 150 ° F. to 600 ° F., preferably within the heated barrel. Is transported after being melted by a screw at a temperature of 200 ° F. to 500 ° F. The melted composition is ultimately injected into a closed mold cavity, which may be cooled at ambient or elevated temperature, but typically at a temperature of 50 ° F. to 70 ° F. To be cooled. After placing in a closed mold for 1 to 300 seconds, preferably 20 to 120 seconds, the core and / or core plus one or more additional cores or cover layers are removed from the mold, It can be cooled at ambient or descending temperature, or placed in a cooling fluid such as water, ice water, dry ice in a solvent, etc.

  When employing compression molding to manufacture the core, the composition is first made into a preform or slag of material, typically a cylinder or approximately spherical shape, the weight of which is desired for the core being molded. Slightly heavier than weight. Prior to this step, the composition may be extruded through a mold or similarly melted and pressed and then cut into a cylindrical preform. The preform is placed in a compression mold cavity and compressed at a molding temperature of 150 ° F to 400 ° F, preferably 250 ° F to 350 ° F, more preferably 300 ° F to 400 ° F. When the cover layer is compression molded, the half shell of the cover layer is first formed by injection molding. The core is then enclosed in two half shells, and then placed in a compression mold cavity and compressed.

  The reactive injection molding process is further described, for example, in US Pat. Nos. 6,083,119, 7,208,562, 7,281,997, 7,282,169, 7,338,391 and U.S. Patent Application Publication No. 2006/0247073, the contents of which are incorporated herein by reference.

  Here, the thermoplastic layer may be treated in such a way as to form a positive or negative hardness gradient. If a thermoset rubber is used, the golf ball layer of the present invention can employ a gradient generation process and / or gradient generation rubber formulation. The gradient generation process and formulation is, for example, the United States application filed March 14, 2008. Patent Application No. 12 / 048,665; No. 11 / 829,461, filed July 27, 2007; No. 11 / 772,903, filed July 3, 2007; August 1, 2007 No. 11 / 832,163 of application; 11 / 832,197 filed Aug. 1, 2007, the contents of which are hereby incorporated by reference.

  The dimple coverage of the golf ball of the present invention is typically 60% or more, preferably 65% or more, more preferably 75% or more.

  The US Golf Association specification limits the minimum size of a competition golf ball to 1.680 inches. There is no specification regarding the maximum diameter, and golf balls of any size can be used for recreation play. The overall diameter of the golf ball of the present invention may be any size. The preferred diameter of the golf ball of the present invention is 1.68 inches to 1.800 inches. More preferably, the overall golf ball diameter of the present invention is from 1.680 inches to 1.760 inches, and more preferably from about 1.680 inches to 1.740 inches.

  Compression is an important factor in golf ball design. For example, core compression can affect the spin rate and feel of the ball as it leaves the driver. Compressed by Jeff Dalton, Compression by Any Other Name, Science and Golf IV, Proceedings of the World, Scientific Confidential of Golf (Eric Thaned, 200). Several different approaches can be used to do this, including Atti compression, Riehle compression, load / deflection measurements at various fixed loads and offsets, and effective modulus. For the purposes of this invention, “compression” refers to Atti compression and is measured using an Atti compression test apparatus according to known procedures. Here, the ball is pressed against the spring using a piston. The movement of the piston is fixed and the deflection of the spring is measured. Measurement of spring deflection is not initiated when the spring contacts the ball. Rather, there is an initial offset of about 1.25 mm (0.05 inch) of spring deflection. A very stiff core does not deflect the spring more than 1.25 mm and zero Atti compression is measured. Since the Atti compression tester is designed to measure objects with a diameter of 42.7 mm (1.68 inches), in order to measure the compression of the core with these testers, the core fills the gap and is 42.7 mm. Should be (1.68 inches) high. To convert Atti compression into Riehle (core), Riehle (ball), 100 kg deflection, 130-10 kg deflection or effective elastic modulus, it can be performed using the formula shown in “J. Dalton”.

As used herein, a COR launches a golf ball or golf ball subassembly (eg, a golf ball core) from an air cannon at two predetermined velocities at a speed of 38.1 m / s (125 ft / s). Is determined by calculating the COR. A plurality of ballistic light screens are placed between the air cannon and the steel plate at a fixed distance to measure ball speed. As the ball moves to the steel plate, each light screen is activated and measures the time on each light screen. This provides an incident transition time that is inversely proportional to the incident speed of the ball. The ball collides with the steel plate and rebounds through multiple light screens, measuring the time interval it takes to move between the light screens. As a result, a jumping transition time inversely proportional to the ball jumping speed is obtained. COR is the ratio of the incoming transit time interval of the transition time interval jumping out _is calculated as _{COR = V out / V in =} T in / T out.

  Flexural modulus is measured using a flex bar according to ASTM D790.

  Note that when a numerical upper limit and numerical lower limit are indicated, any combination of those values can be employed.

  Patent specifications, publications, test procedures, and other references cited herein, including priority documents, are to the extent that they do not conflict with the present invention, and such incorporation is permitted by law In scope, it is fully incorporated herein by reference.

  While embodiments of the present invention have been specifically described, various other modifications will be apparent to and readily made by those skilled in the art without departing from the spirit and scope of the invention. Please note that. Accordingly, the claims are not intended to be limited to the examples and description set forth herein, but are to be construed as including all of the novel patentable features inherent in this invention. And the features include all features that would be considered equivalent by those skilled in the art.

Claims (3)

Manufactured from a polybutadiene rubber composition having a zinc salt of acrylate, a zinc salt of diacrylate, a zinc salt of methacrylate, a zinc salt of dimethacrylate, and mixtures thereof in an amount of 35 parts or more per 100 parts of base rubber ; A center with an ATTI compression of greater than 90 and a diameter of 3.81 cm (1.500 inches) or less;
An outer cover layer made from an ionomer composition having a material hardness greater than 60 Shore D;
ATTI compression of a 3.94 cm (1.550 inch) solid sphere made from the composition , an intermediate layer disposed between the center and the outer cover layer and having an outer surface hardness of less than 70 Shore C Said intermediate layer made from a polyurea composition having a viscosity of 40 or less,
A golf ball characterized in that the outer surface hardness of the intermediate layer is smaller than that of both the center and the outer cover layer. The golf ball according to claim 1, wherein the center has a diameter of 2.54 cm (1.000 inches) to 3.43 cm (1.350 inches), and the center has an ATTI compression of 100 or more. The golf ball according to claim 1, wherein the center has a diameter of 2.54 cm (1.000 inches) to 3.43 cm (1.350 inches), and the center has an ATTI compression of 110 or more.