CN102526994B - Comprise the multi-piece golf ball of soft gradient core - Google Patents

Abstract

A kind of golf ball, comprises by the single core that uniform rubber combination is formed substantially, covers in putting around described caryogamy, and outer covering. Described interior covering comprises ionomer material, and has the material hardness of about 60 Shore D or bigger. Described outer cover configures around described inner covering layer, is formed by casting type polyureas and urethane, and has the material hardness of about 60 Shore D or less. Described outside surface has the hardness of about 12% or less trans component content and about 71 to 88 Shore C, described geometric centre has the hardness of about 10% or less trans component content and about 70 to 80 Shore C, and core surface hardness is greater than geometric centre surface hardness about 1 to 10 Shore C to limit shallow positive hardness gradient.

Description

Comprise the multi-piece golf ball of soft gradient core

Cross reference

The application is the U. S. application No.12/647 submitted on December 28th, 2009, the co-pending part of 584 continues application, U. S. application No.12/647, 584 is the U. S. application No.12/558 submitted on September 14th, 2009, the part of 826 continues application, U. S. application No.12/558, 826 is the U. S. application No.7 submitted on August 6th, 2008, 803, the part of 069 continues application, U. S. application No.7, 803, 069 is the U. S. application No.7 submitted on August 1st, 2007, 410, the part of 429 continues application, U. S. application No.7, 410, 429 is the U. S. application No.7 submitted on July 27th, 2007, 537, the part of 530 continues application, U. S. application No.7, 537, 530 is the U. S. application No.7 submitted on July 3rd, 2007, 537, the part of 539 continues application, above-mentioned openly it is incorporated herein by reference at this.

Invention field

The present invention relates to the golf ball with the core containing one or more layers usually, and any layer all has ' bearing ' or the hardness gradient of ' just ', trans component gradient (transgradient), or both. It is believed that golf ball has one or more layers core, wherein (solid) core of at least one layer, preferably single entity has low ' just ' hardness gradient and comprises trans polybutadiene gradient simultaneously.

Background technology

Entity golf ball is made up of the coated entity core of coating cap rock (cover) usually, and tectum and core all can have multiple layer, and such as double-core has solid centre and outer kernel layer, or multilayer coverture has inside. In general, golf ball core and/or center are formed by thermoset rubber, normally based on the composition of polyhutadiene. Usually being heated by core and make it crosslinked to produce specific character, such as higher or lower compression, it can affect the speed of rotation of ball and/or provide better " sensation ". Such and other character can be adapted to have the needs of the golf player of different ability. From the angle of golf ball producer, the core of desired display wide region character, these character such as rebound resilience, weather resistance, rotation and " sensation " because manufacturers can be made like this to manufacture and sell the golf ball of the number of different types being suitable for different ability level.

Up to the present, most of single core golf ball core has traditional center from the surface of core to core by hard to soft hardness gradient, and this kind is also considered as " positive hardness gradient ". But, these gradients are usually relatively big, up to 15 Shore C hardness, 20 Shore C hardness, even up to 25 Shore C hardness or higher. Patent documentation comprises a large amount of reference, and in addition, it discusses the hardness gradient from hard-surface to soft-center across golf ball core.

The U.S. Patent No. 4 of the people such as Molitor, 650,193 disclose the hardness gradient in the upper layer of core in general manner, and it is formed as follows: utilize solidification to change agent (cure-alteringagent) and process the material block of curable elastomer and subsequently material block is shaped to core. As mentioned above, such process creates the core with different two regions of composition, first part be core hard, have elastic middle portion, this part is that residue is not processed, and second section is the skin of soft, mutability of core, this part changes agent process through solidification. Two " layers " of this core or region become overall each other, thus can obtain from pressure release surface to the such gradient in hard center.

The U.S. Patent No. 3,784,209 of the people such as Berman discloses soft to hard hardness gradient in general manner. Which disclose non-homogeneous, the shaping golf ball with " mixing " elastomer core. The center spheroid of the elastomer material not solidified is surrounded by the compatible but different elastomerics not solidified. When being exposed to solidifying agent for two layers of elastomerics simultaneously, they can form entirety each other, thus defines the core of mixing. The center of this core has the first elastomer material of higher concentration, and it is harder than skin. A shortcoming of this manufacture method is to manufacture the first elastomerics, and then manufacturing the 2nd elastomerics and then they being molded as one is a process consuming time.

Other patent discusses and core is carried out surface treatment thus makes it have soft " skin (skin) ". But, owing to the internal portion of these cores is unprocessed, therefore they have the gradient of similar crust to soft center, the same with traditional core. Such as, the U.S. Patent No. 6,113,831 of the people such as Nesbitt discloses traditional core in general manner and surrounds the independent moccasin skin of this core. This moccasin skin is prepared: in moulding process by following process, under the material block of preliminary shaping is exposed to steam (steam), so that maximum mold temperature exceedes steam cure point (steamsetpoint), and in moulding process, control the temperature of thermoforming. This skin comprises into 1/4 inch of radial outermost 1/32 inch��spherical nucleus. The U.S. Patent No. 5,976,443 of the people such as Nesbitt and No.5,733,206 all disclose and add water smoke to the outside surface of material block before shaping, and thus form moccasin skin. As mentioned above, it is necessary, crosslinked by what hinder on core surface, the water softening compression of core, thus manufactured the softer moccasin skin of the hard middle portion of encirclement.

In addition, multiple patent discloses multi-layer golf ball core, wherein each core layer has different hardness, thereby produces from core layer to the hardness gradient of core layer.

But, still there is following demand: with regard to the multi-layer golf ball (it has more shallow hard to soft (" just ") hardness gradient from surface to center) with individual layer core, obtain manufacturing the cheapness of such core and effective method.

Summary of the invention

The present invention relates to the golf ball comprising single core and two coverture. This single core has outside surface and geometric centre, and it is formed by uniform rubber combination substantially. This pair of coverture comprises inner covering layer and outer cover. Inner covering layer, it is put around described caryogamy, and it is formed by ionomer material. Inner covering layer has the material hardness of about 60 Shore D or bigger. Outer cover its configure around inner covering layer, it is formed by casting type (castable) polyureas or casting PU usually. This layer has the material hardness of about 60 Shore D or less. One preferred embodiment in, the outside surface of core has the hardness of about 12% or less trans component content (transcontent) and about 71 to 88 Shore C, geometric centre has the hardness of about 10% or less trans component content and about 70 to 80 Shore C, and core surface hardness 1 to 10 Shore C more about than geometric centre hardness is to limit shallow positive hardness gradient.

In one embodiment, described positive hardness gradient is about 2 to 8 Shore C, it is more preferable to be about 2.5 to 7 Shore C. Core preferably has the external diameter of about 1.45 to about 1.62 inches, it is more preferable to have the external diameter of about 1.50 to about 1.58 inches. The hardness at Nuclear goemetry center is generally about 72 to 78 Shore C, and the hardness on core surface is generally about 73 to 80 Shore C, it is more preferable to about 74 to 78 Shore C. Another preferred embodiment in, the outside surface of core has about 10% or less trans composition, and the geometric centre of core has about 8% or less trans composition.

The present invention also relates to golf ball, and it is formed by the single core of the external diameter with about 1.5 to 1.55 inches. This core is formed by uniform rubber combination substantially usually. Inner covering layer is put around caryogamy, and it is formed by the thermoplasticity ionomer material of the material hardness with about 66 to 80 Shore D usually. Outer cover configures around inner covering layer, and it has the thickness of about 0.04 inch. In this embodiment, outer cover is formed by the ionomer of the material hardness with about 64 to 68 Shore D, or is formed by the thermoset casting PU with about 51 to 55 Shore D hardness. Preferably, the outside surface of core has the hardness of about 12% or less trans component content and about 74 to 78 Shore C, geometric centre has the hardness of about 10% or less trans component content and about 72 to 78 Shore C, and core surface hardness 1 to 5 Shore C more about than geometric centre surface hardness is to limit shallow positive hardness gradient, core has Atti compression (Atticomprission) of about 50 to 70.

In one embodiment, golf ball also comprises the middle layer being configured between inner covering layer and core, and this middle layer has the thickness of about 0.06 inch and the hardness of about 43 to 47 Shore D. Usually covering hardness in is about 66 Shore D, and middle layer hardness is about 45 Shore D, and outer cover hardness is about 53 Shore D.

The present invention also relates to the golf ball comprising single core, and this single core has the external diameter of about 1.45 inches, outside surface, and geometric centre, and is formed by uniform rubber combination substantially. Inner covering layer is put around caryogamy. Interior covering has the external diameter of about 1.58 inches, and is formed by the thermoplasticity nonionic crosslinked polymeric materials of the material hardness with about 38 to 42 Shore D. Outer cover configures around described inner covering layer. Outer covering has the thickness of about 0.05 inch and is formed by the ionomer with about 66 to 70 Shore D material hardnesses.Preferably, the outside surface of core has the hardness of about 12% or less trans component content and about 74 to 78 Shore C, geometric centre has the hardness of about 10% or less trans component content and about 72 to 78 Shore C, and core surface hardness 1 to 5 Shore C more about than geometric centre hardness is to limit shallow positive hardness gradient.

Detailed Description Of The Invention

The golf ball of the present invention can comprise single layer (one piece) golf ball, and multi-layer golf ball, such as there is core and surround the golf ball of the coverture of core, but preferably by the core of solid centre (also referred to as kernel) and outer nuclear layer, inner covering layer and outer cover are formed. Certainly, any core and/or tectum can comprise more than one layer. In a preferred embodiment, core is formed by kernel and outer nuclear layer, wherein kernel and outer nuclear layer all have the outside surface from a composition and divide (namely to its penetralia, the center of kernel or the internal surface of outer nuclear layer) hardness gradient (" bearing " hardness gradient) of radial " soft to hard " inwardly, but also can expect other enforcement mode, wherein relate to the direction of the change of the hardness gradient between nuclear composition and combine (such as, " bearing " gradient at center and " just " the gradient coupling at outer nuclear layer, vice versa).

The center of core can also be or the ball of the hollow ball surrounded by one or more middle layer and/or tectum or liquid-fillings, or core can also comprise the solid by the elastomer material winding stretched or liquid center. Any around be configured in these selectable in layer in the heart can show the core hardness gradient (that is, " bearing " gradient) of the present invention. Tectum can be single layer or such as, is formed by multiple layers, such as inner covering layer and outer cover.

As sketched above, the core of the present invention can have such as undefined hardness gradient: this hardness gradient by core surface (or outer nuclear layer) and the hardness that the center of radial inwardly kernel (being generally 2-mm increment) measures define. Such as, refer to from (the outside surface of entity core the hardness value at the outside surface of measured composition at term used herein " bearing " and " just "; The outside surface of the kernel in double-core; The outside surface of the outer nuclear layer in double-core, etc.) such as, subtract the hardness value (kernel in the center of entity core or dual-core architecture of the inside part at measured composition; The internal surface of core layer; Etc.) after result. Such as, if the outside surface of entity core has hardness low compared with center (that is, surface is more soft-hearted than in), hardness gradient will be considered to be " bearing " gradient degree (numerical value of little numerical value-big=negative numerical value). The core of preferred the present invention has zero or negative hardness gradient, it is more preferable between zero (0) and-10, it is most preferred that between 0 and-5.

Preferably, core layer (kernel or outer nuclear layer) is prepared by composition, said composition comprises at least one heat-curable matrix rubber (baserubber), such as polybutadiene rubber, it is by least one superoxide and at least one reactive assistant (co-agent) solidification, and reactive assistant can be the metal-salt of unsaturated carboxylic acid (such as acrylic or methacrylic acid), non-metal auxiliary agent or their mixture. Preferably, composition also comprises suitable antioxidant. Core preparation can also comprise optional softening accelerator (softandfastagent) (being also cis-anticatalyzer sometimes), such as organosulfur or the organosulfur compound containing metal.

Can also using other composition well known by persons skilled in the art, these other compositions are to be understood that and include but not limited to Auto-regulating System of Density of Heavy Medium filler, processing aid, softening agent, foaming or whipping agent, sulphur promotor and/or non-peroxide radical source.Matrix thermoset rubber 130 can with other rubber and polymer blending, generally include natural or synthetic rubber. Preferred base rubber is 1,4-polyhutadiene, and its cis-structure is at least 40%, it is preferable that higher than 80%, and more preferably higher than 90%. The polybutadiene rubber example expected comprisesCB22 andCB23, CB1221, CB1220, CB24 and CB21, it can be purchased from LANXESSCorporation;360L and150L and UBEPOL-BR rubber, it can from UBEIndustries, Ltd, Tokyo, and Japan is purchased;7245��7265 and BUDENE1207 and 1208, it can be purchased from GoodyearofAkron, OH; SEBR-1220;BR40 and BR60, it can be purchased from PolimeriEuropa; And BR01, BR730, BR735, BR11 and BR51, it can be purchased from JapanSyntheticRubberCo.Ltd;BRNd-40; AndND40, ND50 and ND60, it can be purchased from Karbochem.

From LanxessCorporation, it is most preferred that be through the rank of neodymium and cobalt catalysis, but following all can use: BunaCB21; BunaCB22; BunaCB23; BunaCB24; BunaCB25; BunaCB29MES; BunaCBNd40; BunaCBNd40H; BunaCBNd60; BunaCB55NF; BunaCB60; BunaCB45B; BunaCB55B; BunaCB55H; BunaCB55L; BunaCB70B; BunaCB1220; BunaCB1221; BunaCB1203; BunaCB45. , it is possible to buy multiple applicable rubber from JSR (JapanSyntheticRubber), in addition the Ubepol that the UbeIndustriesInc of Japan sells, the BST that the BSTElastomers of Thailand sells; The IPCL that the IndianPetrochemicalLtd of India sells; The Nitsu that the KarbochemLtd in Karbochem or South Africa sells; And from the Petroflex of Brazil; The LG of Korea S; And the KuhmoPetrochemcial of Korea S buys multiple applicable rubber.

Base rubber can also comprise height or middle mooney viscosity rubber, or its blend. " Men Ni " unit is the unit of the plasticity for measuring crude rubber or unvulcanized rubber. Equal moment of torsion by the plasticity of " Men Ni " unit representation, with arbitrary unit, measuring containing rotating on the disk of the container of 100 DEG C of rubber and with every minute speed of 2 turns. The observed value of mooney viscosity is defined according to ASTMD-1646. Mooney viscosity scope is preferably greater than about 40, it is more preferable in the scope of about 40 to about 80, and the further preferred scope in about 40 to about 60. The polybutadiene rubber with relatively high Mooney viscosity can also be used, as long as the viscosity of polyhutadiene does not reach the level of the blocking of high viscosity polyhutadiene or other negative impact manufacturing machine. Expect to use viscosity to be less than the polyhutadiene of 65 Buddhist nuns in the present invention. In an embodiment of the invention, golf ball core by having-or the polyhutadiene material of height-mooney viscosity make, rebound resilience that its display improves (and, therefore distance) and the hardness of ball can not be improved. Such core is soft, and namely compression is less than about 60 and more specifically in the scope of about 50-55. The core with the compression of the scope in about 30 to about 50 is also in the scope of the preferred embodiment of the present invention.

In suitable-and comprising BayerAGCB23 (Nd-catalysis) to the commercial source of height-mooney viscosity polyhutadiene, it has the mooney viscosity of about 50 and is the polyhutadiene of highly linear, and CB1221 (Co-catalysis).If needed, polyhutadiene can also mix with other elastomerics known in the art, such as other polybutadiene rubber, natural rubber, styrene butadiene ribber and/or synthetic polyisoprene, further the character of core is carried out modification. When using the mixture of elastomerics, the content of other composition in core composition is usually based on total elastomer blends of 100 weight parts. In one preferred embodiment, base rubber comprises the polyhutadiene of Nd-catalysis, the polybutadiene rubber of rare earth element-catalysis, or their blend. If needed, polyhutadiene can mix with other elastomerics as known in the art, and such as natural rubber, polyisoprene rubber and/or styrene butadiene rubbers carry out modification with the character to core. Other suitable base rubber comprises thermosetting material, such as ethylene propylene diene monomer rubber, ethylene-propylene rubber(EPR), isoprene-isobutylene rubber, halogenated butyl rubber, hydrogenated nitrile-butadiene rubber, nitrile rubber and silicon rubber.

Thermoplastic elastomer (TPE) can also be used for the character to core layer and carry out modification, or by storing, with matrix thermoset rubber is blended, the core layer not solidified. These TPE comprise natural or synthetic gum (balata) or high trans-polyisoprene, high trans-polyhutadiene or any styrenic block copolymer, such as styrene ethylene butadiene styrene, styrene-isoprene-phenylethene etc., metallocene or other is through the polyolefine such as ethylene-octene copolymer of single site catalysed, or ethylene-butene copolymer, or thermoplastic polyurethane (TPU), comprise the multipolymer with silicone resin. Other suitable comprising for the TPE blended with the thermoset rubber of the present invention(thinking that it comprises polyether amide copolymer),(thinking that it comprises polyetherester copolymer), thermoplastic polyurethane, and(thinking that it comprises styrenic block polymer elastomer). Any above-mentioned TPE or TPU containing the functional group for grafting, can also comprise toxilic acid or maleic anhydride.

Extra polymkeric substance can also optionally be incorporated in base rubber. example includes but not limited to: thermo-setting elastomer, such as core abrasive material (coreregrind) again, thermoplastic elastomer sulfide (vulcanizate), the ionomer of copolymerization, three poly-ionomers, polycarbonate, polymeric amide, the polymeric amide of copolymerization, polyester, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polyarylester, polyacrylate(s), polyphenylene oxide (polyphenyleneether), impact-resistant modified polyphenylene oxide, high-impact polystyrene, Phthalic acid, diallyl ester polyester, SAN (SAN) (comprises olefin-modified SAN and acrylonitrile-styrene-acrylonitrile polymer), styrene-maleic anhydride copolymer, styrene copolymer, functionalized styrol copolymer, functionalized styrenic trimer, styrenic trimer, cellulose polymer compound, liquid crystalline polymers, ethylene vinyl acetate, polyureas, and polysiloxane, or the polymkeric substance of any metallocene catalysis of these materials.

In composition within the scope of the present invention, suitable polyamides class as extra polymkeric substance comprises the resin obtained in the following manner: (1) (a) di-carboxylic acid is such as oxalic acid, hexanodioic acid, sebacic acid, terephthalic acid, m-phthalic acid or 1,4-cyclohexane dicarboxylic acid and (b) diamine are such as the polycondensation of quadrol, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine or decamethylene diamine, 1,4-cyclohexane diamine or MXDP;(2) cyclic lactames is such as the ring-opening polymerization of ��-hexanolactam or ��-laurolactam; (3) aminocarboxylic acid, such as the polycondensation of 6-aminocaprolc acid, 9 aminononanoic acid, 11-amino undecanoic acid or 12 amino dodecanoic acid; Or the copolymerization of (4) cyclic lactames and di-carboxylic acid and diamine. The specific examples of suitable polymeric amide comprises NYLON, NYLONMXD6 and NYLON46 of NYLON6, NYLON66, NYLON610, NYLON11, NYLON12, copolymerization.

Suitable peroxide initiator comprises dicumyl peroxide; 2,5-dimethyl-2,5-two (t-butylperoxy) hexane; 2,5-dimethyl-2,5-two (t-butylperoxy) own alkynes; 2,5-dimethyl-2,5-two (benzoyl crosses oxygen base) hexane; 2,2 '-two (t-butylperoxy)-two-isopropyl benzene; 1,1-bis-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane; 4,4-bis-(t-butylperoxy) valeric acid n-butyl; T-butyl perbenzoate; Benzoyl peroxide; 4,4 '-two (butyl peroxy) valeric acid n-butyl; Ditertiary butyl peroxide; Or 2,5-bis--(t-butylperoxy)-2,5-dimethylhexane, lauryl peroxide, tert-butyl hydroperoxide, ��, ��-two (t-butylperoxy) diisopropyl benzene, two (2-tert butylperoxyisopropyl) benzene, two-t-amyl peroxy compound, ditertiary butyl peroxide. Preferably, this rubber combination comprises every 100 parts by weight of rubber (phr) of superoxide of about 0.25 to about 5.0 weight part, it is more preferable to 0.5phr to 3phr, it is most preferred that 0.5phr to 1.5phr. In the most preferred embodiment, this superoxide exists with the amount of about 0.8phr. These scopes of given superoxide assume that described superoxide is 100% activity, does not consider any carrier that may exist. Owing to many commercially available superoxide are sold together with carrier compound, therefore the physical presence amount of peroxide actives should be calculated. The peroxide initiator of commercially available acquisition comprises the DICUP of the dicumyl peroxide that can obtain from Crompton (GeoSpecialtyChemicals)^TMClass (comprises DICUP^TMR, DICUP^TM40C and DICUP^TM40KE). Similar initiator can obtain from AkroChem, Lanxess, Flexsys/Harwick and R.T.Vanderbilt. Other commercially available obtainable and preferred initiators have TRIGONOX^TM265-50B (from AkzoNobel), it is 1,1-bis-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane and the mixture of two (2-tert butylperoxyisopropyl) benzene. TRIGONOX^TMSuperoxide is sold usually on carrier compound.

Suitable reactive auxiliary reagent includes but not limited to be applicable to the metal-salt of the diacrylate salt of the present invention, dimethacrylate salt and monomethyl acrylate, and comprising wherein metal is those of zinc, manganese, calcium, barium, tin, aluminium, lithium, sodium, potassium, iron, zirconium and bismuth. Zinc dimethacrylate (ZDA) is preferred, but the present invention is not limited to this. ZDA provides the golf ball with high original speed. This ZDA can have various purity. Object for the present invention, the amount of the Zinic stearas existed in ZDA is more low, and the purity of ZDA is more high. It is preferred containing the ZDA being less than about 10% Zinic stearas. More preferably containing the ZDA of 4-8% Zinic stearas of having an appointment. Suitable, the dizinc acrylate resin of commercially available acquisition comprises from those of SartomerCo..The preferred concentration of the ZDA that can use is about 10phr to about 40phr, it is more preferable to 20phr to about 35phr, it is most preferred that 25phr to about 35phr. In particularly preferred embodiments, the amount of reactive auxiliary reagent is about 29phr to about 31phr.

The preferred coagent added can be used alone, it is also possible to combinationally uses with above-mentioned substance, but described coagent comprises and is not limited to trimethylolpropane trimethacrylate, Viscoat 295, etc. As well known to those skilled in the art, when coagent is at room temperature liquid, by contributing to, these compounds is scattered on suitable carrier, it is easy to it and is blended in rubber stock.

Oxidation inhibitor refers to those compounds suppressing or preventing elastomerics generation Oxidative demage and/or suppression or prevent the reaction caused by oxyradical. The example of the oxidation inhibitor that can use in the present invention includes but not limited to quinoline oxidation inhibitor, amine antioxidants and phenolic antioxidant. Preferred oxidation inhibitor is 2,2 '-methylene radical-bis-(4-methyl-6-tert butyl phenol), is called by being purchased the commodity of RT.Vanderbilt companyThe product of MBPC and obtain. Other Polyphenols oxidation inhibitor comprises:T��L��SKT��SWP��13��1290��

Preferred oxidation inhibitor comprises the cresols that alkylidene group-bis-alkyl replaces, such as: 4,4 '-methylene radical-bis-(2,5-xylenol); 4,4 '-ethylidene base-bis-(6-ethyl-m-methyl phenol); 4,4 '-Ding pitches base-bis-(the 6-tertiary butyl-m-methyl phenol); Pitch base-bis-(6-methyl-m-methyl phenol) 4,4 '-last of the ten Heavenly stems; 4,4 '-methylene radical-bis-(2-amyl group-m-methyl phenol); 4,4 '-propylidene base-bis-(the own base-m-methyl phenol of 5-); Pitch base-bis-(5-ethyl-p-menthan phenol) 3,3 '-last of the ten Heavenly stems; 2,2 '-Ding pitches base-bis-(the just own base-p-methyl phenol of 3-); 4,4 '-(2-fourth fork base)-bis-(the 6-tertiary butyl-m-methyl phenol); 3,3 '-(4-pitches base the last of the ten Heavenly stems)-bis-(5-ethyl-p-menthan phenol); (2,5-dimethyl-4-hydroxy phenyl) (2-hydroxyl-3,5-3,5-dimethylphenyl) methane; (2-methyl-4-hydroxyl-5-ethylphenyl) (2-ethyl-3-hydroxy-5-methyl base phenyl) methane; (3-methyl-5-hydroxyl-6-tert-butyl-phenyl) (2-hydroxy-4-methyl-5-decyl phenyl)-normal-butyl methane; (2-hydroxyl-4-ethyl-5-aminomethyl phenyl) (2-base in the last of the ten Heavenly stems-3-hydroxy-4-methyl phenyl) butyl amyl group methane; (3-ethyl-4-methyl-5-hydroxy phenyl) (2,3-dimethyl-3-hydroxy-pheny) nonyl methane; (3-methyl-2-hydroxyl-6-ethylphenyl) (2-sec.-propyl-3-hydroxy-5-methyl base-phenyl) cyclohexyl-methane; (2-methyl-4-hydroxy-5-methyl base phenyl) (2-hydroxy-3-methyl-5-ethylphenyl) dicyclohexyl methyl hydride; Deng, but it is not limited to described example.

Other suitable oxidation inhibitor comprises the phenols of replacement, such as: the 2-tertiary butyl-4-methoxyphenol; The 3-tertiary butyl-4-methoxyphenol; 3-tertiary octyl group-4-methoxyphenol; 2-methyl-4-methoxyphenol; 2-octadecyl-4-n-butyloxyphenol; The 3-tertiary butyl-4-octade-cyloxyphenol; 3-dodecyl-4-thanatol; 2,5-bis--tertiary butyl-4-methoxyphenol; 2-methyl-4-methoxyphenol; 2-(1-methyl cyclohexane base)-4-methoxyphenol; The 2-tertiary butyl-4-dodecane oxygen base phenol; 2-(1-methyl-benzyl)-4-methoxyphenol; 2-tertiary octyl group-4-methoxyphenol; Methyl gallate; N-Propyl gallate;N butyl gallate; Lauryl gallate; Gallic acid Semen Myristicae ester; Gallic acid stearyl; 2,4,5-trihydroxy-acetophenone; 2,4,5-trihydroxy-propyl group phenyl ketone; 2,4,5-trihydroxy-stearophenone; 2,6-bis--tertiary butyl-4-methylphenol; 2,6-bis--tertiary octyl group-4-methylphenol; 2,6-bis--tertiary butyl-4-octadecylphenol; 2-methyl-4-methyl-6-tert butyl phenol; 2,6-bis--octadecyl-4-methylphenol; 2,6-bis--dodecyl-4-methylphenol; 2,6-bis--n-octyl-4-methylphenol; 2,6-bis--n-hexadecyl-4-methylphenol; 2,6-bis--(1-methyl undecyl)-4-methylphenol; 2,6-bis--(1-methyl heptadecyl)-4-methylphenol; 2,6-bis--trimethyl-4-methylphenol; 2,6-bis--(1,1,3,3-tetramethyl-octyl group)-4-methylphenol; 2-dodecyl-6-the tertiary butyl-4-methylphenol; 2-dodecyl-6-(1-methyl undecyl)-4-methylphenol; 2-dodecyl-6-(1,1,3,3-tetramethyl-octyl group)-4-methylphenol; 2-dodecyl-6-Octadecane base-4-methylphenol; 2-dodecyl-6-n-octyl-4-methylphenol; 2-methyl-6-Octadecane base-4-methylphenol; 2-dodecyl-6-(1-methyl heptadecyl)-4-methylphenol; 2,6-bis-(1-methyl-benzyl)-4-methylphenol; 2,6-bis-(1-methyl cyclohexane base)-4-methylphenol; 2,6-(1-methyl cyclohexane base)-4-methylphenol; 2-(1-methyl-benzyl)-4-methylphenol; With relevant substituted phenol, but it is not limited to described example.

Preferred antioxidant packages contains alkylidene group diphenol, such as: 4,4 '-Ding pitches base-bis-(3 methy 6 tert butyl phenol); 2,2 '-Ding pitches base-bis-(4,6-xylenol); 2,2 '-Ding pitches base-bis-(4-methyl-6-tert butyl phenol); 2,2 '-Ding pitches base-bis-(the 4-tertiary butyl-6-methylphenol); 2,2 '-ethylidene base-bis-(4-methyl-6-tert butyl phenol); 2,2 '-methylene radical-bis-(4,6-xylenol); 2,2 '-methylene radical-bis-(4-methyl-6-tert butyl phenol); 2,2 '-methylene radical-bis-(4-ethyl-6-tert.-butyl phenol); 4,4 '-methylene radical-bis-(2,6 di t butyl phenol); 4,4 '-methylene radical-bis-(2-methyl-6-tert butyl phenol); 4,4 '-methylene radical-bis-(2,6-xylenol); 2,2 '-methylene radical-bis-(the 4-tertiary butyl-6-phenylphenol); 2,2 '-dihydroxyl-3,3 ', 5,5 '-tetramethyl-; 2,2 '-isopropylidene-bis-(4-methyl-6-tert butyl phenol); Ethylenebis (2-Naphthol); 1,5-dihydroxy naphthlene; 2,2 '-ethylidene-bis-(4-methyl-6-propylphenol); 4,4 '-methylene radical-bis-(2-propyl group-6-tert.-butyl phenol); 4,4 '-ethylidene-bis-(2-methyl-6-propylphenol); 2,2 '-methylene radical-bis-(5-methyl-6-tert butyl phenol); Pitch base-bis-(the 6-tertiary butyl-3-methylphenol) with 4,4 '-Ding, but it is not limited to described example.

Preferred oxidation inhibitor also comprises alkylidene group trisphenol, such as: 2,6-pair (2 '-hydroxyl-3 '-the tertiary butyl-5 '-methyl-benzyl)-4-methylphenol; 2,6-pair (2 '-hydroxyl-3 '-ethyl-5 '-t-butylbenzyl)-4-methylphenol; With 2,6-two (2 '-hydroxyl-3 '-the tertiary butyl-5 '-propyl group benzyl) 4-methylphenol, but it is not limited to described example.

The content of oxidation inhibitor is generally about 0.1phr��about 5phr, it is preferable that about 0.1phr��about 2phr, it is more preferable to about 0.1phr��about 1phr.In the especially preferred embodiments, the content of oxidation inhibitor is about 0.4phr. In other embodiments, the content of oxidation inhibitor is it should be ensured that the hardness gradient of core (core) of the present invention is negative. The amount of the oxidation inhibitor preferably added in core layer (inner nuclear layer and outer nuclear layer) component is about 0.2phr��about 1phr, it is more preferable to be about 0.3phr��about 0.8phr, it is most preferred that be about 0.4phr��about 0.7phr. In core component, preferably add the superoxide come in 100% activity of about 0.25phr��about 1.5phr, it is more preferable to be about 0.5phr��about 1.2phr, it is most preferred that be about 0.7phr��about 1.0phr. The amount that can adjust ZDA is to realize the compression required for the golf ball obtained, rotation and feel. Temperature during solidification is about 290 ��F��about 335 ��F, it is more preferable to be about 300 ��F��about 325 ��F, and stores at least about 10 minutes��30 minutes at the temperature of raw material (stock) selected by it.

The thermoset rubber composition of the present invention can also comprise optional containing softening accelerator (softandfastagent). " softening accelerator " means to make the core of manufacture to have any compound of following character or its blend or its arbitrary combination as used herein: compared with not using the core manufactured by softening accelerator, 1) more soft (low compression) when constant COR, or 2) there is higher COR under identical compression. The softening accelerator contained in the composition of preferred the present invention is about 0.05phr��about 10.0phr. In one embodiment, the amount of described softening accelerator is about 0.05phr��about 3.0phr, it is preferable to about 0.05phr��about 2.0phr, it is more preferable to be about 0.05phr��about 1.0phr. In another embodiment, the amount of described softening accelerator is about 2.0phr��about 5.0phr, it is preferable to about 2.35phr��about 4.0phr, it is more preferable to be about 2.35phr��about 3.0phr. In the enforcement mode of greater concn, the amount of described softening accelerator is about 5.0phr��about 10.0phr, it is more preferable to be about 6.0phr��about 9.0phr, it is most preferred that be about 7.0phr��about 8.0phr. In highly preferred enforcement mode, the amount of described softening accelerator is about 2.6phr.

Preferred softening accelerator includes but not limited to organosulfur compound or the organosulfur compound containing metal, and organosulfur compound (comprises list, two and polysulfide, mercaptan, sulfhydryl compound), inorganic sulfide compound, race's VIA compound, or its mixture. Softening accelerator component can also be the admixture of organosulfur compound and inorganic sulfide compound.

The present invention preferably softens accelerator and comprises the compound with following general formula, but is not limited thereto:

In formula, R₁��R₅Can any be sequentially: C₁��C₈Alkyl, halogen group, thiol group (-SH), carboxylicesters (salt) group, sulphonate (salt) group, and hydrogen, the present invention preferably softens accelerator: penta fluoro benzene thiophenol, 2-fluoro thiophenol, 3-fluoro thiophenol, 4-fluoro thiophenol, 2, 3-fluoro thiophenol, 2, 4-fluoro thiophenol, 3, 4-fluoro thiophenol, 3, 5-fluoro thiophenol, 2, 3, 4-fluoro thiophenol, 3, 4, 5-fluoro thiophenol, 2, 3, 4, 5-tetra fluoro benzene thiophenol, 2, 3, 5, 6-tetra fluoro benzene thiophenol, 4-chlorine tetra fluoro benzene thiophenol, reptazin, 2-chlorothio-phenol, 3-chlorothio-phenol, 4-chlorothio-phenol, 2, 3-chlorothio-phenol, 2, 4-chlorothio-phenol, 3, 4-chlorothio-phenol, 3, 5-chlorothio-phenol, 2, 3, 4-chlorothio-phenol, 3, 4, 5-chlorothio-phenol, 2, 3, 4, 5-tetrachlorobenzene thiophenol, 2, 3, 5, 6-tetrachlorobenzene thiophenol, pentabromobenzene thiophenol, 2-bromo thiophenol, 3-bromo thiophenol, 4-bromo thiophenol, 2, 3-bromo thiophenol, 2, 4-bromo thiophenol, 3, 4-bromo thiophenol, 3, 5-bromo thiophenol, 2, 3, 4-bromo thiophenol, 3, 4, 5-bromo thiophenol, 2, 3, 4, 5-tetrabromo-benzene thiophenol, 2, 3, 5, 6-tetrabromo-benzene thiophenol, five iodine thiophenols, 2-iodine thiophenol, 3-iodine thiophenol, 4-iodine thiophenol, 2, 3-iodine thiophenol, 2, 4-iodine thiophenol, 3, 4-iodine thiophenol, 3, 5-iodine thiophenol, 2, 3, 4-iodine thiophenol, 3, 4, 5-iodine thiophenol, 2, 3, 4, 5-tetraiodo thiophenol, 2, 3, 5, 6-tetraiodo thiophenol, and zinc salt.Preferred halogeno-benzene thiol compounds is reptazin, and it can be commercially available in a pure form, it is also possible to commercially available commodity are calledFinished product, these commodity be on clay medium carrier containing volume containing the sample be 45% reptazin (being equivalent to the PCTP of 2.4 parts).Can be commercially available from StruktolCompanyofAmericaofStow, OH company. PCTP can obtain its pure form from eChinachemofSanFrancisco, CA company, it is possible to obtains its salt form from eChinachemofSanFrancisco, CA company. Most preferably, halogeno-benzene thiol compounds is the zinc salt of reptazin, it is possible to commercially available from eChinachemofSanFrancisco, CA company.

As used herein, when relating to of the present invention, term " organosulfur compound " refers to any compound containing carbon, hydrogen and sulphur, and wherein sulphur is directly connected with at least one carbon atom. As used herein, term " sulphur compound " represents for elemental sulfur, polymerised sulphur or its combination. It is further understood that term " elemental sulfur " refers to S₈Ring structure, " polymerised sulphur " is the structure also comprising at least another sulphur except elemental sulfur.

Other suitable example that softening accelerator (is also considered as cis-to-anticatalyzer) include but not limited to 4,4 '-Diphenyl disulfide compound; 4,4 '-xylyl disulphide; 2,2 '-benzamido Diphenyl disulfide compound; Two (2-aminophenyl) disulphide; Two (4-aminophenyl) disulphide; Two (3-aminophenyl) disulphide; 2,2 '-two (4-amino naphthyl) disulphide; 2,2 '-two (3-amino naphthyl) disulphide; 2,2 '-two (4-amino naphthyl) disulphide; 2,2 '-two (5-amino naphthyl) disulphide; 2,2 '-two (6-amino naphthyl) disulphide; 2,2 '-two (7-amino naphthyl) disulphide; 2,2 '-two (8-amino naphthyl) disulphide; 1,1 '-two (2-amino naphthyl) disulphide; 1,1 '-two (3-amino naphthyl) disulphide; 1,1 '-two (3-amino naphthyl) disulphide; 1,1 '-two (4-amino naphthyl) disulphide; 1,1 '-two (5-amino naphthyl) disulphide; 1,1 '-two (6-amino naphthyl) disulphide; 1,1 '-two (7-amino naphthyl) disulphide; 1,1 '-two (8-amino naphthyl) disulphide; 1,2 '-diaminostilbene, 2 '-disulfide group two naphthalene; 2,3 '-diaminostilbene, 2 '-disulfide group two naphthalene; Two (4-chloro-phenyl-) disulphide; Two (2-chloro-phenyl-) disulphide; Two (3-chloro-phenyl-) disulphide; Two (4-bromophenyl) disulphide; Two (2-bromophenyl) disulphide; Two (3-bromophenyl) disulphide; Two (4-fluorophenyl) disulphide; Two (4-iodophenyl) disulphide; Two (2,5-dichlorophenyl) disulphide; Two (3,5-dichlorophenyl) disulphide; Two (2,5-dichlorophenyl) disulphide; Two (2,4 dichloro benzene base) disulphide; Two (2,6-dichlorophenyl) disulphide; Two (2,5-bis-bromochlorophene base) disulphide; Two (3,5-bis-bromochlorophene base) disulphide; Two (the chloro-5-bromophenyl of 2-) disulphide; Two (2,4,6-trichlorophenyl) disulphide; Two (2,3,4,5,6-five chlorophenyl) disulphide; Two (4-cyano-phenyl) disulphide; Two (2-cyano-phenyl) disulphide; Two (4-nitrophenyl) disulphide; Two (2-nitrophenyl) disulphide; 2,2 '-disulfido phenenyl ethyl formate;2,2 '-disulfido phenenyl methyl-formiate; 2,2 '-disulfido phenenyl formic acid; 4,4 '-disulfido phenenyl ethyl formate; Two (4-acetylphenyl) disulphide; Two (2-acetylphenyl) disulphide; Two (4-formyl radical phenyl) disulphide; Two (4-formamyl phenyl) disulphide; 1,1 '-dinaphthyl disulphide; 2,2 '-dinaphthyl disulphide; 1,2 '-dinaphthyl disulphide; 2,2 '-two (1-chlorine dinaphthyl) disulphide; 2,2 '-two (1-bromonaphthalene base) disulphide; 1,1 '-two (2-chloronaphthyl, methylnaphthyl) disulphide; 2,2 '-two (1-cyanonaphthyl) disulphide; 2,2 '-two (1-ethanoyl naphthyl) disulphide; Deng; Or its mixture. Preferred organic sulphur components comprises 4,4 '-Diphenyl disulfide compound; 4,4 '-ditolyl disulphide, or 2,2 '-benzamido Diphenyl disulfide compound, or its mixture. Preferred organic sulphur components comprises 4,4 '-xylyl disulphide. In another embodiment, the organic sulphur components containing metal can be used according to the present invention. Suitable include but not limited to the cadmium of diethyldithiocarbamate (salt), diamyl dithiocarbamate ester (salt) and dimethyldithiocarbamate (salt), copper, lead and tellurium analogue containing metal organic sulphur components, and mixture.

The suitable substituted or unsubstituted aromatic series organic composition not comprising sulphur or metal includes but not limited to 4,4 '-dibenzenyl, nitrogen benzide or its mixture. Aromatic series organic group preferred size is at C₆To C₂₀Scope, it is more preferable at C₆To C₁₀Scope. Suitable inorganic sulphide composition includes but not limited to titanium sulfide, manganese sulfide, and the sulfide analogue of iron, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, tin and bismuth.

Aromatic organic compounds that is that replace or that do not replace also is suitable as softening accelerator. Suitable substituted or unsubstituted aromatic series organic composition includes but not limited to have formula (R₁)_x-R₃-M-R₄-(R₂)_yComponent, wherein R₁And R₂It is hydrogen separately, or substituted or unsubstituted C_1-20The alkyl of straight chain, side chain or ring-type, alkoxyl group or alkyl sulfide base, or monocycle or many rings or condensed ring C₆-C₂₄Aromatic group; X and y is the integer of 0 to 5 separately; R₃And R₄It is selected from monocycle or many rings or condensed ring C separately₆-C₂₄Aromatic group; And M comprises azo group or metal ingredient. R₃And R₄It is preferably selected from C separately₆To C₁₀Aromatic group, it is more preferable to be selected from phenyl, benzyl, naphthyl, benzamido and benzothiazolyl. R₁And R₂That be preferably selected from replacement separately or do not replace C_1-10The alkyl of straight chain, side chain or ring-type, alkoxyl group or alkyl sulfide base, or C₆To C₁₀Aromatic group. Work as R₁��R₂��R₃Or R₄During for being substituted, replacement can comprise one or more substituents: hydroxyl and metal-salt thereof; Sulfydryl and metal-salt thereof; Halogen; Amino, nitro, cyano group and amide group; Carboxyl, comprises ester, acid and metal-salt thereof; Silylation; Acrylate group and metal-salt thereof; Alkylsulfonyl or sulfamyl; Bound phosphate groups and phosphite group. When M is metal ingredient, its any suitable metallic element that can be able to obtain for those of ordinary skill in the art. Generally speaking, metal can be transition metal, while it is preferred that it is tellurium or selenium. In one embodiment, aromatic organic compounds is not substantially containing metal, although in another embodiment, aromatic organic compounds is not completely containing metal.

This softening accelerator can also comprise Group VIA composition.Elemental sulfur and polymerised sulphur can be bought from Elastochem, Inc. (Chardon, OH) and obtain. Exemplary sulfur catalyst compound comprises PB (RM-S)-80 elemental sulfur and PB (CRST)-65 polymerised sulphur, can buy from Elastochem, Inc. respectively and obtain. Exemplary trade name isTellurium catalyzer and exemplary trade name beSelenium catalyzer respectively from RTVanderbilt buy obtain.

Other suitable softening accelerators include but not limited to hydroquinones, benzoquinones class, quinhydrone(s) class, catechol and Resorcinol class.

Suitable hydroquinone compound comprises the compound and hydrate thereof that are expressed from the next:

Wherein each R₁��R₂��R₃And R₃For hydrogen; Halogen; Alkyl; Carboxyl; Its metal-salt, and its ester; Acetate groups (acetate) and ester thereof; Formyl radical; Acyl group; Ethanoyl; Halo carbonyl; Sulfo group and ester thereof; Halogen is for alkylsulfonyl; Sulfino (sulfino); Alkylsulfinyl; Formamyl; Haloalkyl; Cyano group; Alkoxyl group; Hydroxyl and metal-salt thereof; Amino; Nitro; Aryl; Aryloxy; Arylalkyl; Nitroso-group; Kharophen; Or vinyl.

Other suitable hydroquinone compounds include but not limited to: quinhydrones; Four chlorohydroquinones; 2-chlorohydroquinone; 2-bromohydroquinone; 2,5-dichloro hydroquinone; 2,5-bis-bromohydroquinone; Four bromohydroquinones; 2-toluhydroquinone; TBHQ; 2,5 di tert amlyl hydroquinone; With 2-(2-chloro-phenyl-) quinhydrones hydrate.

More suitably hydroquinone compound comprises the compound and hydrate thereof that are expressed from the next:

Wherein each R₁��R₂��R₃And R₄For the metal-salt of carboxyl; Acetate groups and ester thereof; Hydroxyl; The metal-salt of hydroxyl; Amino; Nitro; Aryl; Aryloxy; Arylalkyl; Nitroso-group; Kharophen; Or vinyl.

Suitable benzoquinone compound comprises the compound and hydrate thereof that are expressed from the next:

Wherein each R₁��R₂��R₃And R₄For hydrogen; Halogen; Alkyl; Carboxyl; Its metal-salt, and its ester; Acetate groups (acetate) and ester thereof; Formyl radical; Acyl group; Ethanoyl; Halo carbonyl; Sulfo group and ester thereof; Halogen is for alkylsulfonyl; Sulfino (sulfino); Alkylsulfinyl; Formamyl; Haloalkyl; Cyano group; Alkoxyl group; Hydroxyl and metal-salt thereof; Amino; Nitro; Aryl; Aryloxy; Arylalkyl; Nitroso-group; Kharophen; Or vinyl.

Other suitable benzoquinone compounds comprise the one or more compound and hydrate thereof that are expressed from the next:

Wherein each R₁��R₂��R₃And R₄For the metal-salt of carboxyl; Acetate groups and ester thereof; Hydroxyl; The metal-salt of hydroxyl; Amino; Nitro; Aryl; Aryloxy; Arylalkyl; Nitroso-group; Kharophen; Or vinyl.

Suitable quinhydrone(s) class comprises the one or more compound and hydrate thereof that are expressed from the next:

Wherein each R₁��R₂��R₃��R₄��R₅��R₆��R₇And R₈For hydrogen; Halogen; Alkyl; Carboxyl; Its metal-salt, and its ester; Acetate groups (acetate) and ester thereof; Formyl radical; Acyl group; Ethanoyl; Halo carbonyl; Sulfo group and ester thereof; Halogen is for alkylsulfonyl; Sulfino (sulfino); Alkylsulfinyl; Formamyl; Haloalkyl; Cyano group; Alkoxyl group; Hydroxyl and metal-salt thereof; Amino; Nitro; Aryl; Aryloxy; Arylalkyl; Nitroso-group; Kharophen; Or vinyl.

Other suitable quinhydrone(s) classes comprise those compound with upper formula, wherein R₁��R₂��R₃��R₄��R₅��R₆��R₇And R₈It is the metal-salt of carboxyl separately; Acetate groups (acetate) and ester thereof;Hydroxyl; The metal-salt of hydroxyl; Amino; Nitro; Aryl; Aryloxy; Arylalkyl; Nitroso-group; Kharophen; Or vinyl.

Suitable catechol comprises the one or more compound and hydrate thereof that are expressed from the next:

Wherein each R1, R2, R3 and R4 are hydrogen; Halogen; Alkyl; Carboxyl; Its metal-salt and ester thereof; Acetate groups and its ester; Formyl radical; Acyl group; Ethanoyl; Halo carbonyl; Sulfo group and ester thereof; Halogen is for alkylsulfonyl; Sulfino (sulfino); Alkylsulfinyl; Formamyl; Haloalkyl; Cyano group; Alkoxyl group; Hydroxyl and metal-salt thereof; Amino; Nitro; Aryl; Aryloxy; Arylalkyl; Nitroso-group; Kharophen; Or vinyl.

Suitable Resorcinol comprises one or more compound and the hydrate thereof that following formula represents:

Wherein each R1, R2, R3 and R4 are hydrogen; Halogen; Alkyl; Carboxyl; Its metal-salt and ester thereof; Acetate groups and its ester; Formyl radical; Acyl group; Ethanoyl; Halo carbonyl; Sulfo group and ester thereof; Halogen is for alkylsulfonyl; Sulfino (sulfino); Alkylsulfinyl; Formamyl; Haloalkyl; Cyano group; Alkoxyl group; Hydroxyl and metal-salt thereof; Amino; Nitro; Aryl; Aryloxy; Arylalkyl; Nitroso-group; Kharophen; Or vinyl. Weighting material can be added the thermoset rubber composition of core, to regulate the density of said composition up or down. Usually, weighting material comprises such as following material: tungsten, zinc oxide, barium sulfate, silicon-dioxide, calcium carbonate, zinc carbonate, metal, metal oxide and salt, then the abrasive material (nuclear matter of recovery, usually about 30 object particles it are ground to), high Mooney (Mooney) bala gutta abrasive material again, trans grinds (trans-regrind) nuclear matter (nuclear matter of recovery, it comprises the trans-isomer(ide) of the polyhutadiene of a large amount) etc. again. When there is trans abrasive material again, the amount of trans-isomer(ide) is preferably about 10% to about 60%. In a preferred embodiment of the invention, this core comprises cis isomerism body burden and is greater than the polyhutadiene of about 95% and grinds nuclear matter (sulfuration (vulcanized)) again as the trans of weighting material. The trans nuclear matter that grinds again of any particle diameter is all sufficient, but it is preferably lower than about 125 ��m.

The weighting material adding the one or more part of this golf ball generally includes the processing material (processingaids) affecting rheology and mixed nature or compound, the weighting material of change density, tear strength or strengthening weighting material etc. Described weighting material is generally inorganics, and suitable weighting material comprises various metals or metal oxide, such as zinc oxide and stannic oxide and barium sulfate, zinc sulfate, calcium carbonate, barium carbonate, clay, tungsten, wolfram varbide, silicate series, and mixture. Weighting material also can comprise multiple whipping agent or pore forming material (blowingagent), and it can easily be selected by those skilled in the art. Weighting material can comprise entity or hollow, fill or unfilled polymkeric substance, pottery, metal and glass microsphere. Usually weighting material is added one or more parts of this golf ball, to change its density to meet the unified standard of golf ball. Weighting material also can be used for changing the weight of center weight or such as at least one extra play of Special ball (specialtyballs), and the ball for sportsmen's low weight of low pendulum speed is preferred.

Following material such as tungsten, zinc oxide, barium sulfate, silicon oxide, calcium carbonate, zinc carbonate, metal, metal oxide and salt and again abrasive material (nuclear matter of recovery, usually be ground to about 30 order particles), also it is suitable weighting material.

Polyhutadiene and/or any other base rubber (baserubber) or elastomerics system (elastomersystem), the microballoon that can also carry out foaming or maybe can expanding with tiny balloon is filled, and the described microballoon expanded is in the curing process in the low proportion level that the temperature expansion of setting is extremely any. Other compositions such as sulphur accelerator (such as two, three or tetramethylthiuram tetrasulfide (tetramethylthiuramdi, tri, tetrasulfide)) and/or the organic sulphur components containing metal also can be used according to the invention. The suitable organosulfur accelerator containing metal includes but not limited to: the N,N-Diethyldithiocarbamic Acid of cadmium, copper, lead and tellurium analogue, diamyl dithiocarbamate salt and dimethyl dithio carbamate, or its mixture. Other compositions, such as processing material (such as lipid acid and/or its metal-salt, process oil, dyestuff and pigment and other additives well known by persons skilled in the art, it is also possible to usually use the amount being reached object in the present invention to be enough to realizing it.

It is not limited to theory, it is believed that the per-cent of the double bond of transconfiguration manipulation can cause trans component gradient in the whole core containing at least one main chain unsaturated rubber (i.e. polyhutadiene), plastics or elastomerics. Trans gradient is affected up or down by changing the type of co-reagent (coagent) in cis to the type of the type of trans catalyzer (or softening accelerator (soft-and-fastagent)) and amount, superoxide and amount and formulation and amount. Such as, the formulation containing about 0.25phrZnPCTP can have the about 5% trans gradient through core, and the preparation containing about 2phrZnPCTP can have the trans gradient of about 10% or higher. Trans gradient also manipulates by set time and temperature. Think that lower temperature and shorter set time can produce lower trans gradient, although the combination of these factors multiple can produce and the gradient of the different and/or reverse direction using single factors to obtain.

In core, the per-cent of trans-isomer(ide) also manipulates by being added with organic sulfur compound (such as listed above) in core formulation, and described organosulfur compound includes but not limited to five chlorothio phenol, five chlorothio phenol zinc, xylyl disulphide (ditolyldisulfide) and Diphenyl disulfide compound. The amount of this organosulfur compound and the overall status of solidification affect in solidify reaction process the amount of the trans-isomer(ide) produced. Another kind of method increasing trans content in core introduces unsaturated rubber in core formulation, the trans-isomer(ide) (such as contain the polyhutadiene of high trans or contain the poly-octene (polyoctenamer) of high trans) of described unsaturated rubber contained high levels. High trans rubber can use when being with or without organic sulfur compound.

Usually, higher and/or faster curing degree tend to produce higher levels of trans component content, as the effect that ZDA concentration in the superoxide of greater concn, softening accelerator and certain degree produces. Even trans level can be had impact by the type of rubber, those by rare earth metal (such as Nd) catalysis are compared with those rubber formed by group VIII metal (such as Co, Ni and Li), it is possible to form higher levels of trans polybutadiene.

The measurement of the polyhutadiene trans-isomer content that the application refers to is, and can complete as follows. Calibration standard prepared by least two kind polybutadiene rubber samples (such as high and low-antiform per-cent polyhutadiene) known with trans content.These samples are used alone or mix with such form the trans polybutadiene content ladder producing at least about 1.5% to 50%, or (bracket) unknown amount drawn together by folder, thus the working curve of gained is containing the spaced points such as at least about 13.

Equipment is used to have the commercial FTIR spectrum instrument that can obtain of Photoacoustic (" PAS ") cell (cell), instrument parameter below is used to obtain the PAS spectrum of each standard: scanning speed 2.5KHZ (0.16cm/s optics speed), use 1.2KHz electronic filter, it is not enough in being 2 (before collection sample that sampling is set, the number that laser signal 0 passes through), altogether-add (co-add) minimum 128 scannings, at 375 to 4000cm^-1Scope intermediate-resolution be 4cm^-1, sensitivity is set to 1.

During PAS composes, cis, trans and vinyl-polyhutadiene peak see 600-1100cm^-1Between. Can area under each trans polybutadiene peak of integration. Determine the mark of each peak area relative to three isomer peak total areas, allow the working curve building the relatively actual trans polybutadiene content of trans polybutadiene peak area mark. Relation conefficient (the R of gained working curve²) must be minimum 0.95.

For the unknown nuclear matter at point (surface of such as core or center) place interested, by with the sample load PAS cell containing the untainted surface without allogenic material (the such as demoulding (moldrelease) etc.) just cut, it may also be useful to above-mentioned parameter obtains PAS spectrum. Analyze unknown trans polybutadiene area fraction to determine actual trans-isomer content from described working curve.

A kind of comprise barium sulfate known when, the aforesaid method detecting trans content may relatively out of true. Therefore, the other or optional test of the trans content of polyhutadiene is as follows. Calibration standard prepared by the polyhutadiene (such as high and low-antiform polyhutadiene per-cent) known with at least two kinds of trans component contents. These samples are used alone or mix to produce the ladder of the trans polybutadiene content of at least about 1.5% to 50% by this way, or unknown amount drawn together by folder, thus the working curve of gained is containing the spaced points such as at least 13.

Equipment is used to have the FT-Raman spectrograph of near-infrared laser, it may also be useful to instrument parameter below obtains StokesRaman spectrum from each standard substance: sufficient laser power (laserpower) (usual 400-800mW) does not cause excessive heating or fluorescence to obtain good signal to noise ratio; Resolving power 2cm^-1; At 400-4000cm^-1Raman shift in spectral limit (shiftspectralrange); Scan with common interpolation at least 300.

Stoechiometric process and software (such as from the PLSplus/IQ of GalacticIndustriesCorp) can be used to build working curve by the data produced above. The PLS-1 curve, mean center data encasement (meancenterdatapreparation) and the spectral limit that utilize this software application SNV (detrend) optical path length correction to produce are 1600-1700cm^-15-point SG bis-grades of derivatives (secondderivative), obtain acceptable standard. Relation conefficient (the R of gained working curve²) must be minimum 0.95.

Preferably, the geometric centre of core has about 1% to 10%, it is more preferable to 2% to 9%, and most preferably 4% to 8% trans component content. The outside surface of this core preferably has about 5% to 15%, it is more preferable to about 7% to 12%, and most preferably from about 8% to 10% trans content.In this core half-radius (half-radius) point preferably has about 5% to 16%, it is more preferable to about 6% to 14%, and most preferably from about 7% to 13% trans component content.

The core being most suitable for the golf ball of the present invention has outside surface and center, and is formed by uniform rubber combination substantially. middle layer (such as cap layer (interior cover)) is put around caryogamy, and tectum is formed around middle layer, coverture (cover) is usually formed by pourable polyureas or urethane and (namely refers to comprise pourable polyureas (100% urea connection base/connect base without carbamate), pourable urethane (100% carbamate connection base/connect base without urea), pourable assorted conjunction poly-(ammonia ester/urea) (prepolymer is all carbamate connection base and solidifies with amine), with the tectum of pourable assorted conjunction poly-(urea/ammonia ester) (prepolymer is all urea connection base and solidifies with polyvalent alcohol)). in a preferred embodiment, the outside surface of this core has the trans polybutadiene content of about 6% to 10%, the center of this core has the trans polybutadiene content of about 1% to 3%, and the trans component content of the outside surface of this core more than the trans component content at center about 6% or more, to determine that (namely the core of the contrary configuration that surperficial trans component content has trans component content higher than the trans component content in center is considered to have the trans component gradient of negativity (negativetransgradient) to pros-and-cons type component gradient (positivetransgradient) along nuclear radius, and also contain in this application).

The present invention preferably includes the core comprising at least one single layer, and this core has " soft gradient " formula and curing cycle, and it is defined as " LOG " core herein. This type of LOG core can have " just " Shore C hardness gradient (being defined as: core surface hardness subtracts the hardness of geometric centre) of about 1 Shore C to about 10 Shore C, it is more preferably about 2 Shore C to less than 8 Shore C, and the Shore C hardness gradient of most preferably about 2.5 Shore C to 7.5 Shore C. Wherein LOG core comprises more than one layer, such as by outer nuclear layer around center, any one or both of these layers can have low (or shallow) " just " hardness gradient.

The ball of the present invention preferably at least comprises LOG core and tectum. Optionally, there is one or more middle layer between core and tectum. More preferably, have about 1.45 to 1.62 inches, more preferably about 1.50 to 1.58 inches and most preferably the individual layer LOG core of diameter of about 1.51 to 1.55 inches encapsulated by two tectums. Inner covering layer is preferably made up of ionomer polymeric material (ionomericmaterial) (such as have about 60 Shore D or more the conventional ion cross-linked polymer of high rigidity or height/ionomer of neutralizing completely). Outer cover is preferably by having about 60 Shore D or the more urethane of soft, polyureas or its mixture, or its multipolymer or hybridization thing make. In this enforcement mode most preferably, described LOG core has the geometric centre hardness of about 70 to 80 Shore C, more preferably about 72 to 78 Shore C, and the surface hardness of about 71 to 88 Shore C, more preferably about 73 to 80 Shore C and more preferably about 74 to 78 Shore C. Described LOG core it is also preferred that ground have about 50 to 90, more preferably about 60 to 80 compression (Atti), and about 10% or lower surperficial trans-polybutadiene content and geometric centre about 8% or lower trans-polybutadiene content.

Optional middle layer may relatively hard (the Shore C hardness of at least about 85, preferably at least about 90; At least about 61, preferably at least about 63 Shore D hardness) or relatively soft (the Shore C hardness of about 85 or lower, preferably about 83 or lower, and the Shore D hardness of about 61 or lower, preferably about 57 or lower). Middle layer can comprise thermoplasticity or thermoset polymeric composition. Thermoset composition comprises the composition based on elastoprene, PBR, SBR, EPDM, NR etc. of such as superoxide or sulfur curable, or urethane, polyureas, ring oxygen, carbamate-acrylate etc. Thermoplastic material comprises ionomer, non-ionomer, polyester, polymeric amide, PEBAX or HYTRELTPE ' s and vinylbenzene-structure segmented copolymer (SBS, SEBS etc.).

Covering material can be the material identical with disclosed suitable intermediate layer material, and even can comprise LOG or zero-or low-hardness-gradient rubber compounding/solidification, but preferably includes ionomer, polyurethane(s), or polyureas. Described tectum can firmly can be soft, its hardness value is as described in above-mentioned middle layer.

Single (preferably), multilayer, or polylith core can have about 0.80 to 1.62 inch, preferably about 1.1 to 1.62 inches, more preferably about 1.2 to 1.60 inches and the most preferably diameter of about 1.3 to 1.58 inches. The combination in LOG core and middle layer preferably has about 1.0 to 1.66 inches, more preferably about 1.25 to 1.64 inches and the most preferably external diameter of about 1.40 to 1.62 inches. Tectum preferably has about 0.010 to 0.080 inch, more preferably about 0.015 to 0.060 inch and the most preferably thickness of about 0.020 to 0.040 inch.

Usually, when using harder tectum, usually it is combined with relative soft middle layer, rotate relatively low golf ball to produce. When using softer tectum, usually it is combined with relative hard middle layer, to produce than the golf ball using the same configuration of hard tectum to have higher speed of rotation. In another enforcement mode, hard tectum can use together with hard middle layer or soft tectum can use together with soft middle layer. It will be understood that term " firmly " refers to the Shore D hardness of 55 or higher, term " soft " refers to the Shore D hardness of 45 or lower; " common " hardness should be 45 to 55 Shore D.

Another preferred embodiment in, this golf ball comprises three layers. LOG core preferably has shallow " just " hardness gradient of about 1 to 5 Shore C, the diameter of about 1.55 inches, the compression of about 50 to 100, preferably 65 to 85, and the COR of about 0.800-0.815, preferably 0.800-0.810. Described middle layer is made up of the composition based on thermoplasticity ionomer with about 80 Shore C hardness and about 1.60 inch outer diameter. Single overburden layer is made up of the ionomer of about 0.040 inch thickness and about 66 Shore D hardness. The enforcement mode at another low compression center can comprise have about 1 to 50, the center of the compression of more preferably about 10 to 40, most preferably about 15 to 35.

The core of the present invention also can have lower than about 160, more preferably, about 40 to about 160 and more preferably, and about 60 to Yue120Ruan center tilt index (SoftCenterDeflectionIndex, " SCDI ") compresses.

The program that described SCDI is dynamic compressors (" DCM ") is changed, and it allows to measure the pound number needed for 10% that core deflects its diameter.Described DCM a kind of apply load to core or spheroid and measures core or the instrument of inch number that spheroid deflects under the load recorded. Obtain thick load/deflection curve, it is fit to described Atti and compresses yardstick, obtain representing the numerical value of Atti compression. Described DCM carries out through the load unit being connected to bottom hydro-cylinder, described hydro-cylinder with fixing speed (typically about 1.0ft/s) to fixing core pneumatic trigger. LVDT is connected to hydro-cylinder, and it measures the distance of hydraulic cylinder within the scope of the test duration. Logarithmic Algorithm based on software is guaranteed in the test initial stage, detects that at least 5 continuous print loads start to measure after increasing.

Described SCDI is the modification a little of this setting. Hardware is identical, but has changed software and output. Use described SCDI, concern be the power (in pound) of deflection needed for core x inch. Deflection amount is the 10% of described nuclear diameter. Triggering DCM, described hydro-cylinder makes core deflect the 10% of its diameter, simultaneously DCM return by needed for described core deflect amount power (in pound) (as the load unit that connects surveyed). Displayed value is in the single numerical value of pound.

Or, the LOG core of above-mentioned enforcement mode has the diameter of about 1.450 inches, and is loaded into the middle layer being made up of non-ionomer thermoplastic material (namely PEBAX type ester-acid amide builds block copolypeptide) with about 40 Shore D hardness and about 1.580 inch outer diameter. Preferred tectum is the ionomer tectum with about 68 Shore D hardness and about 0.050 inch thickness.

Another preferred embodiment in, this golf ball comprises four layers. Described core is made up of LOG as above formula and is had the external diameter of about 1.50 inches. This golf ball comprises two layers of middle layer, respectively has the thickness of about 0.060 inch. The middle layer of the inside preferably has the hardness of about 45 Shore D, and the middle layer of outside has the hardness of about 66 Shore D. Tectum has the thickness of about 0.030 inch, and is made up of thermoset, cast property urethane or polyureas, and has the hardness of about 53 Shore D.

The 4th preferred embodiment in, this golf ball comprises four layers. This core comprises LOG center and the outer nuclear layer that has about 1.0 inch diameters. Described outer core layer has the external diameter of about 1.540 inches and the surface hardness of about 89 to 92 Shore C. Described outer nuclear layer by " conventional " polybutadiene rubber formula but not LOG formula make. Described middle layer is made up of the material based on ionomer and is had the external diameter of about 1.62 inches and the hardness of about 67 Shore D. Described tectum is made up of urethane that casting or polyureas and is had the hardness of about 45 Shore D.

The hardness of the outside surface of described core can lower than the hardness of geometric centre, to limit the negative hardness gradient of about-1 to about-15, more preferably about-5 to-10. The outside surface of described core can have the hardness of about 68 to about 80 Shore C, and described geometric centre has the hardness of about 68 to 80 Shore C. The hardness recorded at the outside surface of core also can be greater than the hardness at core center, to limit the positive hardness gradient of about 0 to 5, more preferably about 2 to 5. This core preferably has about 1.5 inches to 1.59 inches, more preferably about 1.51 to 1.57 inch, most preferably about 1.51 inches to 1.55 inches, the diameter that specifically comprises 1.51 inches, 1.53 inches or 1.55 inches.

Above-mentioned enforcement mode can be customized to meet default capabilities. Such as, another enforcement mode comprises those with kernel, and described kernel has about 0.250 inch to about 1.550 inches, preferably about 0.500 inch to about 1.500 inches and the more preferably external diameter of about 0.750 inch to about 1.400 inches.In a preferred embodiment, described kernel has the external diameter of about 1.000 inches, 1.200 inches or 1.300 inches, and external diameter most preferably is 1.130 inches. Described outer nuclear layer should have about 1.30 inches to about 1.620 inches, preferably 1.400 inches to about 1.600 inches and the more preferably external diameter (whole two-layer core) of about 1.500 inches to about 1.590 inches. In a preferred embodiment, described outer nuclear layer has about 1.510 inches, 1.530 inches or the most preferably external diameter of 1.550 inches.

Much core is formed, and described core hardness value is as shown in table 2 below according to the formula described in following table 1 and curing cycle.

Table 1

Formula (phr)	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2	Comparative example 3
							SR-526+	34.0	34.0	31.2	29.0	29.0	29.0
ZnO	5	5	5	5	5	5
							BaSO4	11.2	11.2	16.1	13.8	13.8	13.8
VANOX MBPC*	0.40	0.40	0.40	-	0.50	-
							TRIGONOX-265-50B**	1.4	1.4	1.6	-	-	0.8
PERKADOX BC-FF***	-	-	-	1.0	1.6	-
							Polyhutadiene	100	100	100	100	100	100
ZnPCTP	2.35	2.35	2.60	2.35	2.35	2.35
							Grind again	-	-	17	17	-	-
The ratio of antioxidant/initiator	0.57	0.57	0.50		0.31	-
							Solidification value (��F)	305	315	320	350	335	335
Set time (min)	14	11	16	11	11	11
Characteristic
							Diameter (in)	1.530	1.530	1.530	1.530	1.530	1.530
Atti compresses	69	63	70	69	47	-
							COR125ft/s	0.808	0.806	0.804	0.804	-	-

^*VanoxMBPC:2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol), can from R.T.VanderbiltCompanyInc;^**The mixture of Trigonox265-50B:1,1-bis-(t-butyl peroxy)-3,3,5-trimethyl-cyclohexane and two (2-tert-butylperoxyiso-propyl) benzene, 50% is active, on a inert carrier, can from AkzoNobel;^***PerkadoxBC-FF: dicumyl peroxide (99%-100% is active), can from AkzoNobel; And⁺SR-526:ZDA, can from Sartomer

Table 2

Prepare multiple core, and carry out the hardness measurement across core. The core being hereafter called example 1-4 in table 3 all has the external diameter of 1.53 inches. Shore C hardness is measured in the multiple positions across core cross section according to ASTMD-2240. Hereafter by geometric centre, outside surface and from the geometric centre of core radially outward 2mm, 4mm, 6mm, 8mm, 10mm, 12mm, 14mm, 16mm and 18mm position hardness result tabulation. General purpose core formula comprises >=85phrCB1221 polybutadiene rubber ,��15phrCB23 polybutadiene rubber, about 35phr dizinc acrylate resin (zincdiacrylate), about 1phr superoxide, about 0.5phrVANOXMBPC, about 5phrZnO, about 0.5phrZnPCTP, about 1phrAFLUX16, about 13phrPOLYWATE325 and about 15phr abrasive material again. Adjust curing cycle when necessary to change the hardness gradient through core. Temperature/time standard changes between about 330 ��F/20min, 335 ��F/18min, 340 �� P/16min and 345 ��F/14min.

Table 3

The hardness gradient scope seen in table 3 above is 1.5 to 4.3 Shore C. These are shallow positive gradients, and the hardness subtracting geometric centre place by the hardness of core surface is determined.

Also the core formed from same general formula mentioned above is tested % cis-polybutadine, % trans-polyhutadiene and % vinyl-polyhutadiene. Hereafter table 4 presents result.

Table 4

Core	% is trans	% vinyl	% cis
				Example E outside surface	7.6	2.7	89.6
Example E half radius	7.8	2.8	89.4
				Example E center	7.4	2.8	89.7
				Example F outside surface	9.2	2.7	88.4
Example F half radius	13.2	2.6	85.4
				Example F center	8.5	2.9	88.6
				Example G outside surface	8.7	2.8	88.5
Example G half radius	12.6	2.6	85.7
				Example G center	7.3	2.6	90.1

Above the core E-G in table 3 represent core center to surface shallow trans-polyhutadiene gradient.

The surface hardness of core is that the mean value from the repetitive measurement of the opposite hemispheres to core obtains, and carefully avoids measuring on the parting line of core or in surface imperfection (such as hole or projection). Hardness measurement carries out according to ASTMD-2240 " by the penetration hardness (IndentationHardnessofRubberandPlasticbyMeansofaDurometer) of the rubber of Durometer measurements and plastics ".Due to the curved surface of core, it is necessary to carefully guarantee the pronucleus obtaining surface hardness reading under sclerometer pressure head placed in the middle. Use and carry out all hardness measurements through the digital durometer that calibrate, 0.1 stiffness units can be read, and hardness reading when being arranged to after acquirement obtains maximum reading 1 second. Digital durometer must be connected to the base portion of automatic platform and make its base parallel with the base portion of automatic platform so that weight and impact speed on sclerometer meet ASTMD-2240.

In order to prepare gently core to be pressed into the hemisphere clamper that internal diameter is roughly smaller than the diameter of core so that core is fixed in the hemispherical portion of clamper for the core that hardness gradient is measured, make the geometric centre plane of core expose simultaneously. Core is fixed in clamper by frictional force so that it can not cutting and grinding steps during move, but frictional force and unduly, the natural shape of core can not be caused to be out of shape. Core is fixing, so that the parting line of core is roughly parallel with the top of clamper. Before fixing, to be orientated to, with this, the diameter that 90 degree are measured core. Measure and also proceed to core top to provide the reference point of following calculating from clamp base. Band saw or other suitable parting tools is used to carry out rough cutting above the geometric centre that core exposes is omited, it is ensured that core does not move in clamper in this step. Still the residue part of the core in clamper, is fixed on the substrate of surface grinding machine. " coarse " core exposed surface mill is made as smooth flat surface, expose the geometric centre of core, it is verified by measuring the height on the surface that clamp base exposes to core, it is ensured that removed the just half of as above measured core original height to �� 0.004 inch.

Being stayed by core in clamper, find the center of core with center square, and carefully mark, Bing Gai center mark measures hardness. The hardness measurement of distance core center any distance by marking radially outward setting-out from center, and measure and mark the distance from center, is usually spaced apart 2mm, measures. All hardness measurements to carrying out through the plane of geometric centre carry out when described core is thrown away in clamper, do not upset its orientation, so that test surfaces is always parallel with clamp base. Difference of hardness from any predetermined position of core is calculated as the hardness that average surface hardness subtracts suitable reference point, such as, single, the center of entity core, so that the core surface softer than its center can have negative hardness gradient.

With reference to table 1-2, in embodiment 1, surface 10 Shore Cs lower than core rigidities, and than in core the low 12 Shore C of most hard spot. In embodiment 3, surface 5 Shore Cs lower than core rigidities, and than in core the low 8 Shore C of most hard spot. In example 2, center and surface hardness are equal, and the most low 10 Shore C of soft spots specific surface in core.

In the embodiments of the invention presented in Table 1, solidification value is variation from 305 ��F to 320 ��F, and set time was from variation in 11 to 16 minutes. The core composition of embodiment 1 and 2 is identical, only curing cycle change. In embodiment 3, amount and the embodiment 1 of antioxidant are identical with in 2, but other compositions and curing cycle have variation. In addition, the ratio of initiator is changed to 0.57 from 0.50 by antioxidant from embodiment 1 and 2 to embodiment 3.

The ratio of initiator is the factor of a control core surface hardness by antioxidant. The data display hardness gradient being shown in table 2 is at least but is not limited to the amount of antioxidant and superoxide, the function of its ratio and curing cycle.Should point out that higher antioxidant also needs higher peroxide initiator to maintain required compression.

The core of comparative example 1, its composition is shown in table 1, is use conventional curing cycle solidification, and solidification value is 350 ��F and set time is 11 minutes. The core of the present invention uses 305 ��F to carry out 14 minutes, and 315 ��F carry out 11 minutes, and 320 ��F of curing cycles carrying out 16 minutes produce. Measure the hardness gradient of these cores and carry out following observation. For the core in comparative example, as expected, obviously conventional as seen crust is to the gradient at soft center. The gradient of the core of the present invention follows same shape substantially each other.

In all preferred embodiments of the present invention, the hardness of core on surface at most about equals or is significantly less than the hardness at He center. In addition, the core rigidities of core may not be point the hardest in core, but in all cases, it is preferable that its at least equal or specific surface harder. In some embodiments, lowest hardness value occurs in the surperficial 6mm in the outer part of about core. But, the lowest hardness value in core can occur in any point on distance surface, but does not comprise center, as long as surface hardness is still equal to or less than core rigidities. Should pointing out in the present invention, in core and core layer, formula is identical, and core does not impose surface treatment to obtain preferred surface hardness.

Although the golf ball of the present invention can be formed by multiple difference and conventional covering material (middle layer and outer cover), it is preferable that covering material include but not limited to:

(1) urethane, such as those are from polyvalent alcohol or polyamines and vulcabond or polyisocyanates and/or prepared by its prepolymer, and those are disclosed in U.S. Patent No. 5,334,673 and 6,506,851;

(2) polyureas, such as those are disclosed in U.S. Patent No. 5,484,870 and 6,835,794; And

(3) the polyurethane-urea hybridization thing of carbamate or urea segment, blend or multipolymer is comprised.

Suitable polyurethane composition comprises at least one polyisocyanates and the reaction product of at least one solidifying agent. Solidifying agent can comprise such as one or more polyamines, one or more polyvalent alcohols or their combination. Polyisocyanates and one or more polyvalent alcohols can be combined to form prepolymer, then this prepolymer and at least one solidifying agent be combined. So, polyvalent alcohol described herein be adapted at polyurethane material two kinds of compositions one or both in use (namely as a part for prepolymer or in solidifying agent use). Suitable urethane is recorded in U.S. Patent Application Publication text No.2005/0176523, it complete is included by addressing.

The available any polyisocyanates of those of ordinary skill in the art is applicable to using according to the present invention. Exemplary polyisocyanates includes but not limited to 4,4 '-diphenylmethanediisocyanate (MDI); Polymeric MDI; The liquid MDI of carbodiimide modified; 4,4 '-dicyclohexyl methane diisocyanate (H12MDI); P-phenylene vulcabond (PPDI); M-phenylene vulcabond (MPDI); Tolylene diisocyanate (TDI); 3,3 '-dimethyl-4,4 '-diphenylene vulcabond; Isophorone diisocyanate; 1,6-hexamethylene diisocyanate (HDI); Naphthalene diisocyanate; Xylene Diisocyanate; P-tetramethylxylene diisocyanate; M-tetramethylxylene diisocyanate; Ethylidene diisocyanate;Propylidene-1,2-vulcabond; Tetramethylene-1,4-vulcabond; Cyclohexyl diisocyanate; Dodecane-1,12-vulcabond; Tetramethylene-1,3-vulcabond; Hexanaphthene-1,3-vulcabond; Hexanaphthene-1,4-vulcabond; 1-isocyanate group-3,3,5-trimethylammonium-5-isocyanatomethyl hexanaphthene; Methyl cyclohexylene diisocyanate; The triisocyanate of HDI; The triisocyanate of 2,4,4-trimethylammonium-1,6-hexane diisocyanate; Tetracene vulcabond (tetracenediisocyanate); Naphthalene two isocyanic acid; Anthracene two isocyanic acid; The different cyanogen urea of toluene diisocynate; The uretdione of hexa-methylene two isocyanic acid; And mixture. Those of ordinary skill in the art know that polyisocyanates has more than an isocyanate groups, such as di-isocyanate, tri-isocyanate and four-isocyanic ester. Preferably, polyisocyanates comprises MDI, PPDI, TDI or its mixture, and more preferably, polyisocyanates comprises MDI. It is to be understood that, as used in this article, term MDI comprises 4, the liquid MDI of 4 '-diphenylmethanediisocyanate, polymeric MDI, carbodiimide modified and their mixture, and, in addition, the vulcabond of employing can be " low free monomer ", those of ordinary skill in the art are interpreted as " dissociating " the monomeric diisocyanate group with lower level, usually less than about 0.1% free monomeric isocyanates group. The example of " low free monomer " vulcabond includes but not limited to low free monomer MDI, low free monomer TDI and low free monomer PPDI. Described at least one polyisocyanates should have less than about 14% unreacted NCO group. Preferably, described at least one polyisocyanates has not more than about 8.0%NCO, it is more preferable to not more than about 7.8%, and most preferably not more than about 7.5%NCO, normally used NCO level is the NCO of about 7.2% or 7.0% or 6.5%.

The available any polyvalent alcohol of those of ordinary skill in the art is applicable to using according to the present invention. Exemplary polyvalent alcohol includes but not limited to polyether glycol, hydroxy-end capped polyhutadiene (comprising part/complete all hydrogenated derivative), polyester polyol, polycaprolactone polyol and polycarbonate polyol. In a preferred embodiment, polyvalent alcohol comprises polyether glycol. Example includes but not limited to polytetramethylene ether diol (PTMEG), polyoxyethylene glycol propylene glycol, poly-oxygen trimethylene glycol and mixture thereof. Aromatic series that is that hydrocarbon chain can have saturated or unsaturated key and replacement or that do not replace and cyclic group. Preferably, the polyvalent alcohol of the present invention comprises PTMEG.

In another embodiment, polyurethane material comprises polyester polyol. Suitable polyester polyol includes but not limited to polyethylene glycol adipate glycol; Polybutylene glyool adipate; Polyethylene glycol adipate propylene glycol ester glycol; O-phthalate-1,6-HD; Poly-(hexanodioic acid hexylene glycol ester) glycol; And mixture. Aromatic series that is that hydrocarbon chain can have saturated or unsaturated key or replacement or that do not replace and cyclic group.

In another embodiment, the material of the present invention comprises polycaprolactone polyol. Suitable polycaprolactone polyol includes but not limited to 1, polycaprolactone, the polycaprolactone of TriMethylolPropane(TMP) initiation, the polycaprolactone of dimethyltrimethylene glycol initiation, the polycaprolactone of 1,4-butyleneglycol initiation and the mixture thereof that the polycaprolactone of 6-hexylene glycol initiation, glycol ether cause.Aromatic series that is that hydrocarbon chain can have saturated or unsaturated key or replacement or that do not replace and cyclic group.

Also having in an embodiment, the polyurethane material of the present invention comprises polycarbonate polyol. Suitable polycarbonate includes but not limited to poly-carbonic acid O-phthalic ester and poly-(carbonic acid hexylene glycol ester) glycol. Aromatic series that is that hydrocarbon chain can have saturated or unsaturated key or replacement or that do not replace and cyclic group. In one embodiment, the molecular weight of polyvalent alcohol is about 200 to about 4000.

Polyamine curing agent is also adapted in the polyurethane composition of the present invention to use, and has been found that cutting resistance, the shear resistant and shock resistance that improve gained ball. Preferred polyamine curing agent includes but not limited to 3,5-dimethyl sulphide base-2,4-tolylene diamine and isomer thereof; 3,5-diethyl toluene-2,4-diamines and isomer thereof, such as 3,5-diethyl toluene-2,6-diamines; 4,4 '-two-(second month in a season-butylamino)-ditan; 1,4-bis--(second month in a season-butylamino) and-benzene, 4,4 '-methylene radical-two-(2-chloroaniline); 4,4 '-methylene radical-two-(chloro-2,6-Diethyl Aniline of 3-); Polytetramethylene oxygen-two-p-benzaminic acid; N, N '-dialkyl diamines ditan; P, p '-methylene dianiline (MDA); M-phenylenediamine; 4,4 '-methylene radical-two-(2-chloroaniline); 4,4 '-methylene radical-two-(2,6-Diethyl Aniline); 4,4 '-methylene radical-two-(2,3-dichlorphenamide bulk powder); 4,4 '-diamino-3,3 '-diethyl-5,5 '-dimethyl diphenylmethane; 2,2 ', 3,3 '-tetrachloro diaminodiphenyl-methane; Trimethylene two-p-aminobenzoic acid esters; And mixture. Preferably, the solidifying agent of the present invention comprises 3,5-dimethyl sulphide base-2,4-tolylene diamine and isomer thereof, such as300, can purchased from AlbermarleCorporation (BatonRouge, LA). Suitable polyamines (comprising primary amine and secondary amine) solidifying agent preferably has the molecular weight of scope about 64 to about 2000.

At least one in glycol, triol, four alcohol or hydroxy-end capped solidifying agent can be added into polyurethane composition mentioned above. Suitable glycol, triol and four alcohol groups comprise ethylene glycol; Diethylene Glycol; Polyoxyethylene glycol; Propylene glycol; Polypropylene glycol; Lower molecular weight polytetramethylene ether diol; 1,3-bis-(2-hydroxyl-oxethyl] benzene; 1,3-bis--[2-(2-hydroxyl-oxethyl) oxyethyl group] benzene; 1,3-bis--{ 2-[2-(2-hydroxyl-oxethyl) oxyethyl group] oxyethyl group } benzene; 1,4-butyleneglycol; 1,5-pentanediol; 1,6-HD; Resorcinol-two-(beta-hydroxy ethyl) ether; Quinhydrones-two-(beta-hydroxy ethyl) ether; And mixture. Preferably hydroxy-end capped solidifying agent comprises 1,3-bis-(2-hydroxyl-oxethyl) benzene; 1,3-bis--[2-(2-hydroxyl-oxethyl) oxyethyl group] benzene; 1,3-bis--{ 2-[2-(2-hydroxyl-oxethyl) oxyethyl group] oxyethyl group } benzene; 1,4-butyleneglycol, and mixture. Preferably, hydroxy-end capped solidifying agent has the molecular weight that scope is about 48 to 2000. It is to be understood that as used in this article, molecular weight is absolute weight molecular-weight average, can understand as those of ordinary skill in the art.

Hydroxy-end capped solidifying agent and amine hardener all can comprise the group of one or more saturated, unsaturated, aromatic and ring-type. In addition, hydroxy-end capped solidifying agent and amine hardener can comprise one or more halogen group.Polyurethane composition can be formed with the mixture of several solidifying agent or adulterant. But, when needed, it is possible to form polyurethane composition with single curing agent.

In a preferred embodiment of the invention, it may also be useful to saturated urethane forms one or more tectum, it is preferable that outer cover, and pourable thermoset and thermoplastic polyurethane can be selected from. In this embodiment, the saturated urethane of the present invention there is no aromatic group or part. The saturated urethane being applicable to using in the present invention is the product of the reaction between the solidifying agent that at least one polyurethane prepolymer and at least one are saturated. Polyurethane prepolymer is the product that the reaction between the vulcabond that the polyvalent alcohol saturated by least one and at least one are saturated is formed. As is well known the art, it is possible to adopt catalyzer to promote solidifying agent and isocyanic ester and polyvalent alcohol, or the reaction between solidifying agent and prepolymer.

The saturated vulcabond that can use includes but not limited to ethylidene diisocyanate; Propylidene-1,2-vulcabond; Tetramethylene-1,4-vulcabond; 1,6-hexamethylene diisocyanate (HDI); 2,2,4-trimethyl hexamethylene diisocyanate; 2,4,4-trimethyl hexamethylene diisocyanate; Dodecane-1,12-vulcabond; Dicyclohexyl methane diisocyanate; Tetramethylene-1,3-vulcabond; Hexanaphthene-1,3-vulcabond; Hexanaphthene-1,4-vulcabond; 1-isocyanate group-3,3,5-trimethylammonium-5-isocyanatomethyl hexanaphthene; Different Buddhist ear ketone vulcabond; Methyl cyclohexylene diisocyanate; The triisocyanate of HDI; The triisocyanate of 2,2,4-trimethylammonium-1,6-hexane diisocyanate. Saturated vulcabond most preferably is 4,4 '-dicyclohexyl methane diisocyanate and different Buddhist ear ketone vulcabond.

The saturated polyvalent alcohol being applicable to using in the present invention includes but not limited to polyether glycol such as polytetramethylene ether diol and poly-(oxygen propylidene) glycol. Suitable saturated polyester polyol comprises the poly-oxygen trimethylene glycol of polyethylene glycol adipate glycol, polyethylene glycol adipate propylene glycol ester glycol, polybutylene glyool adipate, polycarbonate polyol and oxyethane envelope lid. Saturated polycaprolactone polyol useful in the present invention comprise glycol ether cause polycaprolactone, 1,4-butyleneglycol cause polycaprolactone, 1,6-HD cause polycaprolactone; The polycaprolactone that polycaprolactone, the polycaprolactone of dimethyltrimethylene glycol initiation and the polytetramethylene ether diol that TriMethylolPropane(TMP) causes causes. Saturated polyvalent alcohol most preferably is the polycaprolactone that polytetramethylene ether diol and PTMEG cause.

Suitable saturated solidifying agent comprises 1,4-butyleneglycol, ethylene glycol, glycol ether, polytetramethylene ether diol, propylene glycol; Trihydroxymethyl propane; Four-(2-hydroxypropyl) quadrols; The isomer of cyclohexyl dimethanol and isomer mixture, the isomer of hexanaphthene two (methylamine) and isomer mixture; Tri-isopropanolamine; Quadrol; Diethylenetriamine; Triethylenetetramine (TETA); Tetren; 4,4 '-dicyclohexyl first diamines; 2,2,4-trimethylammonium-1,6-hexanediamine; 2,4,4-trimethylammonium-1,6-hexanediamine; Glycol ether two-(aminopropyl) ether; 4,4 '-two-(second month in a season-butylamino)-dicyclohexyl methyl hydride;1,2-bis--(second month in a season-butylamino) hexanaphthene; 1,4-bis--(second month in a season-butylamino) hexanaphthene; Different Buddhist ear ketone diamines; Hexamethylene-diamine; Propylene diamine; 1-methyl-2,4-cyclohexyl diamines; 1-methyl-2,6-cyclohexyl diamines; 1,3-diamino propane; Dimethylamino propylamine; Diethyl amino propylamine; Imino--two-propylamine; The isomer of diamino-cyclohexane and isomer mixture; Monoethanolamine; Diethanolamine; Trolamine; Monoisopropanolamine; And diisopropanolamine (DIPA). Saturated solidifying agent most preferably is 1,4-butyleneglycol, 1,4-cyclohexyl dimethanol and 4,4 '-two-(second month in a season-butylamino)-dicyclohexyl methyl hydride.

Or, other suitable polymkeric substance comprise the polymkeric substance of the ionomer, metallocene or other single site catalysed that partially or completely neutralize, polyester, polymeric amide, nonionic cross-linked polymer thermoplastic elastomer, copolymerization ether-ester, copolymerization ether-amide, polycarbonate, polyhutadiene, polyisoprene, polystyrene block copolymer (such as styrene-butadiene-styrene), styrene-ethylene-propylene-styrene, styrene-ethylene-butylene-styrene, etc. and their mixture. Heat-curable urethane or polyureas are suitable for the outer cover of the golf ball of the present invention.

In addition, urethane can with polyurea materials replace or blended with polyurea materials. Polyureas and polyurethane composition are completely different, but the aerodynamics also causing expecting when using in golf ball composition and aesthetic features. Composition based on polyureas is preferably saturated in character.

Not being bound to any particular theory, present phase credit long-chain polyamines oligopolymer soft chain segment substitutes the long-chain polyhydric alcohol segment in polyurethane prepolymer and improves the property sheared, cutting and rebound resilience, and the adhesivity to other composition. So, it is possible to by forming the polyurea composition of the present invention by the reaction product of the crosslinked isocyanic ester of solidifying agent and polyamines prepolymer. Such as, it is possible to prepare the composition of the present invention based on polyureas from least one isocyanic ester, at least one polyetheramine and at least one two polyol curing agent or at least one diamine curing agent.

The available any polyamines of those of ordinary skill in the art is adapted in polyureas prepolymer to use. Polyetheramine is particularly suitable in prepolymer to use. As used in this article, " polyetheramine " at least refers to the poly-oxygen alkylene amine containing the primary amino being attached to polyether backbone end. But, due to isocyanic ester and the rapid reaction of amine and the insoluble of many urea products, the selection of diamines and polyetheramine is limited to those and allows and successfully form polyureas prepolymer. In one embodiment, polyether backbone is based on tetramethylene, propylene, ethene, trihydroxymethyl propane, glycerine and mixture thereof.

Suitable polyetheramine includes but not limited to methyldiethanolamine; Polyoxy alkylidene diamines such as polytetramethylene ether diamine, poly-oxygen propylidene triamine and poly-oxygen trimethylene diamine; Gather (the oxygen propylidene that oxyethane adds cap) ether diamine; Based on the triamine of propylene oxide; Triethylene glycol diamines; Based on the triamine of trihydroxymethyl propane; Based on the triamine of glycerine; And their mixture. In one embodiment, polyetheramine for the formation of prepolymer isD2000 (HuntsmanChemicalCo., Austin, TX).

The molecular weight ranges of the polyetheramine used in polyureas prepolymer can be about 100 to about 5000. In one embodiment, polyetheramine molecular weight is about 200 or bigger, it is preferable that about 230 or bigger.In another embodiment, the molecular weight of polyetheramine is about 4000 or less. In still another embodiment, the molecular weight of polyetheramine is about 600 or bigger. Also having in an embodiment, the molecular weight of polyetheramine is about 3000 or less. Also having in an embodiment, the molecular weight of polyetheramine between about 1000 and about 3000, and more preferably between about 1500 to about 2500. Because the polyetheramine of lower molecular weight can tend to form solid polyureas, it is advantageous to the oligopolymer of higher molecular weight, such asD2000��

Such as brief discussion above, some amine may be unsuitable for and isocyanate reaction, because rapid reaction occurs in this Liang Zhongcheng branch. Specifically, relatively can there is rapid reaction in the amine of short chain. But, in one embodiment, the secondary diamine being obstructed is applicable in prepolymer. It is reluctant to arrest in any concrete theory, it is believed that the amine with high-level steric hindrance (stearichindrance) (tertiary butyl groups on such as nitrogen-atoms) is slower than not having the amine of steric hindrance or have the speed of reaction of the amine of low-level steric hindrance. Citing, 4,4 '-two-(s-butylamino)-dicyclohexyl methyl hydride (1000) can be suitable for combining with isocyanic ester to form polyureas prepolymer.

The isocyanic ester that any those of ordinary skill in the art can use is applicable to polyureas prepolymer. The compound that every molecule has the aliphatics of two or more isocyanate group (NCO) group, Zhi Huan race, araliphatic, aromatics is comprised for the isocyanic ester of the present invention, and any derivative, and the combination of these compounds. Described isocyanic ester can be the prepolymer of organic multiple isocyanate for end. Described containing isocyanic ester also can comprise any isocyanate functional monomer, dipolymer, trimer or its many polyadduct by reacted constituent, prepolymer, quasi-prepolymer (quasi-prepolymer), or its mixture. Isocyanate functional compound can comprise monoisocyanates or polyisocyanates, and the latter comprises two or more any isocyanate functional groups.

Suitable comprises the vulcabond with following formula containing isocyanate prepolymer composition: O=C=N-R-N=C=O, and wherein R is preferably the hydrocarbyl portion of ring-type, aromatics or straight chain or branching, comprises about 1 to about 20 carbon atom. Described vulcabond also can comprise one or more cyclic group or one or more phenyl group. When there is multiple ring-type or aromatic group, comprise about 1 to about 10 straight chain of carbon atom and/or the alkyl of branching can be used as spacer groups (spacer) and is present between described ring-type or aromatic group. In some cases, described ring-type or aromatic group can distinguish 2-, 3-and/or 4-position, or ortho position, a position and/or contraposition are replaced. Substituted radical can include but not limited to halogen, primary, uncle or secondary hydrocarbyl groups, or its combination.

The example of vulcabond used in the present invention includes but not limited to: the mixture with different structure of replacement, comprise 2,2 '-and, 2,4 '-and 4,4 '-diphenylmethanediisocyanate; 3,3 '-dimethyl-4,4 '-xenyl vulcabond; Tolylene diisocyanate; Polymeric MDI; The liquid state 4,4 '-diphenylmethanediisocyanate of carbodiimide modified; PPDI; M-benzene diisocyanate; Triphenyl methane-4,4 '-and triphenyl methane-4,4 ' triisocyanate; Naphthalene-1,5-vulcabond; 2,4 '-, 4,4 '-and 2,2 '-diphenyl diisocyanate;Polyphenyl polymethylene polyisocyanates; The mixture of MID and PMDI; The mixture of PMDI and TDI; Ethylidene diisocyanate; Propylidene-1,2-vulcabond; Tetramethylene-1,2-vulcabond; Tetramethylene-1,3-vulcabond; Tetramethylene-1,4-vulcabond; 1,6-hexamethylene diisocyanate; Eight methylene diisocyanates; Decamethylene vulcabond; 2,2,4-trimethyl hexamethylene diisocyanate; 2,4,4-trimethyl hexamethylene diisocyanate; Dodecyl-1,12-vulcabond; Tetramethylene-1,3-vulcabond; Hexanaphthene-1,2-vulcabond; Hexanaphthene 1,3-vulcabond; Hexanaphthene-1,4-vulcabond; Methyl-cyclohexylene diisocyanate; 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4 '-dicyclohexyl vulcabond; 2,4 '-dicyclohexyl vulcabond; 1,3,5-hexanaphthene triisocyanate; Isocyanatomethyl hexanaphthene isocyanic ester; 1-isocyanate group-3,3,5-trimethylammonium-5-isocyanatomethyl hexanaphthene; Isocyanatoethyl hexanaphthene isocyanic ester; Two (isocyanatomethyl)-cyclohexyl diisocyanates; 4,4 '-two (isocyanatomethyl) bicyclohexane; 2,4 '-two (isocyanatomethyl) bicyclohexane; Isophorone diisocyanate; The triisocyanate of HDI; The triisocyanate of 2,2,4-trimethylammonium-1,6-hexane diisocyanate; 4,4 '-dicyclohexyl methane diisocyanate; 2,4-six hydrogen tolylene diisocyanate; 2,6-six hydrogen tolylene diisocyanate; 1,2-, 1,3-and 1,4-phenylene vulcabond; Aromatics aliphatic isocyanate, such as 1,2-, 1,3-and 1,4-Xylene Diisocyanate; M-tetramethylxylene diisocyanate; P-tetramethylxylene diisocyanate; The isocyanuric acid ester of the trimerizing of any polyisocyanates is such as the isocyanuric acid ester of tolylene diisocyanate, the trimer of diphenylmethanediisocyanate, the trimer of tetramethylxylene diisocyanate, the isocyanuric acid ester of hexamethylene diisocyanate, the isocyanuric acid ester of isophorone diisocyanate, and mixture. The dimerization uretdione of any polyisocyanates, such as tolylene diisocyanate, the uretdione of hexamethylene diisocyanate, and mixture; Derive from the polyisocyanates of the modification of above-mentioned isocyanic ester and polyisocyanates; And mixture.

The example of saturated vulcabond used in the present invention includes but not limited to: ethylidene diisocyanate; Propylidene-1,2-vulcabond; Tetramethylene diisocyanate; Tetramethylene-1,4-vulcabond; 1,6-hexamethylene diisocyanate; Eight methylene diisocyanates; Decamethylene vulcabond 2,2,4-trimethyl hexamethylene diisocyanate; 2,4,4-trimethyl hexamethylene diisocyanate; Dodecane-1,12-vulcabond; Tetramethylene-1,3-vulcabond; Hexanaphthene-1,2-vulcabond; Hexanaphthene-1,3-vulcabond; Hexanaphthene-1,4-vulcabond; Methyl-cyclohexylene diisocyanate; 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4 '-dicyclohexyl vulcabond; 2,4 '-dicyclohexyl vulcabond; 1,3,5-hexanaphthene triisocyanate;Isocyanatomethyl hexanaphthene isocyanic ester; 1-isocyanate group-3,3,5-trimethylammonium-5-isocyanatomethyl hexanaphthene; Isocyanatoethyl hexanaphthene isocyanic ester; Two (isocyanatomethyl)-cyclohexyl diisocyanates; 4,4 '-two (isocyanatomethyl) bicyclohexane; 2,4 '-two (isocyanatomethyl) bicyclohexane; Isophorone diisocyanate; The triisocyanate of HDI; The triisocyanate of 2,2,4-trimethylammonium-1,6-hexane diisocyanate; 4,4 '-dicyclohexyl methane diisocyanate; 2,4-six hydrogen tolylene diisocyanate; 2,6-six hydrogen tolylene diisocyanate; And mixture. Aromatics aliphatic isocyanate also can be used for forming light stable material. The example of this type of vulcabond comprises 1,2-, 1,3-and 1,4-Xylene Diisocyanate; M-tetramethylxylene diisocyanate; P-tetramethylxylene diisocyanate; Three poly-isocyanurates of any polyisocyanates are such as the isocyanuric acid ester of tolylene diisocyanate, the trimer of diphenylmethanediisocyanate, the trimer of tetramethylxylene diisocyanate, the isocyanuric acid ester of hexamethylene diisocyanate, the isocyanuric acid ester of isophorone diisocyanate, and mixture; The dimerization uretdione of any polyisocyanates, such as the uretdione of tolylene diisocyanate, the uretdione of hexamethylene diisocyanate, and mixture; Derive from the modified polyisocyanate of above-mentioned isocyanic ester and polyisocyanates; And mixture. , for the purposes of the present invention, in addition described aromatics aliphatic isocyanate can mix with any saturated isocyanic ester listed above.

Unreacted NCO group number can be changed in the polyureas prepolymer of isocyanic ester and polyetheramine to control such as factors such as speed of response, the composition hardness of gained. Citing, the unreacted NCO group number in the polyureas prepolymer and polyetheramine of isocyanic ester can be less than about 14%. In one embodiment, described polyureas prepolymer has the unreacted NCO group of about 5% to about 11%, and even more preferably has the unreacted NCO group of about 6% to about 9.5%. In one embodiment, the per-cent of unreacted NCO group is about 3% to about 9%. Or, the per-cent of the unreacted NCO group in polyureas prepolymer can be about 7.5% or less, and more preferably, about 7% or less. In another embodiment, unreacted NCO content is about 2.5% to about 7.5%, and is more preferably about 4% to about 6.5%.

When formed, polyureas prepolymer can comprise the free isocyanate monomer of about 10% to about 20% accounting for described prepolymer be weight. In one embodiment, therefore, described polyureas prepolymer can eliminate free isocyanate-monomer. Such as, after getting rid of, prepolymer can comprise about 1% or less free isocyanate-monomer. In another embodiment, described prepolymer comprises be weight about 0.5% or less free isocyanate monomer.

Described polyetheramine can mix to prepare multipolymer with other polyvalent alcohols, reacts multipolymer and excess isocyanate to form polyureas prepolymer. In one embodiment, by by copolymer weight less than about 30% polyvalent alcohol mix with saturated polyetheramine. In another embodiment, by by copolymer weight less than about 20% polyvalent alcohol, it is preferable that by copolymer weight less than about 15%, mix with described polyetheramine.Polyvalent alcohol listed above is relative to polyurethane prepolymer, and such as polyether glycol, polycaprolactone polyol, polyester polyol, polycarbonate polyol, hydrocarbon polyvalent alcohol, other polyvalent alcohols, and mixture, be also suitable for mixing with described polyetheramine. The molecular weight of these polymkeric substance can be about 200 to about 4000, but also can be about 1000 to about 3000, and is more preferably about 1500 to about 2500.

Described polyurea composition is made by polyureas prepolymer and single solidifying agent or curing agent mixture being cross-linked. The solidifying agent of the present invention is preferably the solidifying agent (amine-terminatedcuringagent) of amine end-blocking, it is more preferable to be secondary diamine solidifying agent so that composition only comprises urea and connects base. In one embodiment, the solidifying agent of described amine end-blocking can have the molecular weight of about 64 or bigger. In another embodiment, the molecular weight of described amine hardener is about 2000 or less. As discussed above, the solidifying agent of some amine end-blocking can carry out modification with the mixture of compatible amine end-blocking freezing point inhibitor (amine-terminatedfreezingpointdepressingagent) or compatible freezing point inhibitor.

Suitable amine end-blocking solidifying agent includes but not limited to, quadrol; Hexamethylene-diamine; 1-methyl-2,6-cyclohexyl diamines; Tetrahydroxy propylidene quadrol; 2,2,4-and 2,4,4-trimethylammonium-1,6-hexane diamines; 4,4 '-two-(s-butylamino)-dicyclohexyl methyl hydride; 1,4-bis--(s-butylamino)-hexanaphthene; 1,2-bis--(s-butylamino)-hexanaphthene; The derivative of 4,4-bis--(s-butylamino)-dicyclohexyl methyl hydride; 4,4 '-dicyclohexyl methyl hydride diamines; 1,4-hexanaphthene-two-(first amine); 1,3-hexanaphthene-two-(first amine); Diethylene Glycol two-(aminopropyl) ether; 2-methyl five methylene radical-diamines; Diamino-cyclohexane; Diethylenetriamine; Triethylenetetramine (TETA); Tetren; Trimethylene diamine; 1,3-diamino propane; Dimethylamino propylamine; Diethyl amino propylamine; Dipropylenetriamine; Imido grpup-two-propylamine; Monoethanolamine, diethanolamine; Trolamine; Single Isopropylamine, Diisopropylamine; Isophorone diamine; 4,4 '-methylene radical, two-(2-chloroaniline); 3,5-dimethyl sulphur-based-2,4-tolylene diamine; 3,5-dimethyl sulphur-based-2,6-tolylene diamine; 3,5-diethyl sulfide base-2,4-tolylene diamine; 3,5-diethyl sulfide base-2,6-tolylene diamine; 4,4 '-two-(s-butylamino)-ditane and derivative thereof; 1,4-bis--(s-butylamino)-benzene; 1,2-bis--(s-butylamino)-benzene; N, N '-dialkyl amido-ditane; N, N, N ', N '-four (2-hydroxypropyl) ethylene diamine; Trimethylene-two-P aminobenzoates; Tetrahydrofuran (THF)-two-P aminobenzoates; 4,4 '-methylene radical, two-(the chloro-2,6-diethylidene aniline of 3-); 4,4 '-methylene radical, two-(2,6-Diethyl Aniline); M-phenylenediamine; P-pHENYLENE dI AMINE; And mixture. In one embodiment, the solidifying agent of described amine end-blocking is 4,4 '-two-(s-butylamino)-dicyclohexyl methyl hydride.

Suitable saturated amine end solidifying agent includes but not limited to: quadrol; Hexamethylene-diamine; 1-methyl-2,6-cyclohexyl diamines; Tetrahydroxy propylidene quadrol; 2,2,4-and 2,4,4-trimethylammonium-1,6-hexanediamine; 4,4 '-two-(s-butylamino)-dicyclohexyl methyl hydride;1,4-bis--(s-butylamino)-hexanaphthene; 1,2-bis--(s-butylamino)-hexanaphthene; The derivative of 4,4 '-two-(s-butylamino)-dicyclohexyl methyl hydride; 4,4 '-dicyclohexyl methyl hydride diamines; 4,4 '-methylene radical, two-(2,6-diethylamino hexanaphthene); 1,4-hexanaphthene-two-(first amine); 1,3-hexanaphthene-two-(first amine); Diethylene Glycol two-(aminopropyl) ether; 2-methyl pentamethylene diamine; Diamino-cyclohexane; Diethylenetriamine; Triethylenetetramine (TETA); Tetren; Trimethylene diamine; 1,3-diamino propane; Dimethylamino propylamine; Diethyl amino propylamine; Imido grpup-two-propylamine; Monoethanolamine, diethanolamine; Trolamine; Monoisopropanolamine, diisopropanolamine (DIPA); Isophorone diamine; Tri-isopropanolamine; And mixture. In addition, any polyetheramine listed above can be used as solidifying agent and the reaction of polyureas prepolymer.

The tectum of golf ball of the present invention also can be made from the ionomer (HNP) of ionomer preferred heights neutralization. In a preferred embodiment, at least one middle layer of described golf ball is made from the mixture of HNP material or HNP material. The acidic moiety of HNP, is generally the ionomer based on ethylidene, it is preferable that is neutralized and is greater than about 70%, it is more preferable to be greater than about 90%, and most preferably at least about 100%. HNP also can mix with the 2nd polymeric constituent, if described component is containing acid groups, available usual manner neutralizes, and is neutralized by the organic aliphatic acid of the present invention, or both are all. Described 2nd polymeric constituent can partially or completely neutralize, it is preferable that comprises multipolymer and the trimer of ionomer polymerization, ionomer precursor, thermoplastics, polymeric amide, polycarbonate, polyester, urethane, polyureas, thermoplastic elastomer, polybutadiene rubber, balata (balata), the polymkeric substance of metallocene catalysis (grafting with non-grafted), unit point polymkeric substance, the acid polymer of high crystallization, cationic ion cross-linked polymer etc. HNP polymkeric substance has the material hardness of about 20 to about 80 Shore D usually, and the modulus in flexure of about 3000psi to about 200000psi.

In one embodiment of the invention, HNP is ionomer, and/or its acid precursor, it is preferable that neutralize wholly or in part through organic acid multipolymer or its salt. Described acid copolymer is preferably alpha-olefin, such as ethene, and C_3-8��, ��-ethylenic unsaturated carboxylic acid, such as vinylformic acid and Sipacril 2739OF. It can preferably comprise softening comonomer, and such as alkyl acrylate and alkyl methacrylate, wherein said alkyl group has 1 to 8 carbon atom.

Described acid copolymer can be described as e/x/y copolymer, and wherein E is ethene, and X is ��, ��-ethylenic unsaturated carboxylic acid, and Y is softening comonomer. In a preferred embodiment, X is acrylic or methacrylic acid, and Y is vinylformic acid C_1-8Alkyl ester or methacrylic acid C_1-8Alkyl ester. X preferably exists with the amount of the weight percent of polymkeric substance about 1 to about 35, it is more preferable to is the weight percent of about 5 to about 30 of polymkeric substance, and most preferably is the weight percent of about 10 to about 20 of polymkeric substance. Y preferably exists with the amount of the weight percent of polymkeric substance about 0 to about 50, it is more preferable to is the weight percent of about 5 to about 25 of polymkeric substance, and most preferably is the weight percent of about 10 to about 20 of polymkeric substance.

The concrete ethylene copolymer containing acid includes but not limited to, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/n-butyl acrylate, ethylene/methacrylic acid/isobutyl acrylate, ethylene/acrylic acid/isobutyl acrylate, ethylene/methacrylic acid/n-BMA, ethylene/acrylic acid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl methacrylate and ethylene/acrylic acid/n-BMA.The preferred ethylene copolymer containing acid comprises ethylene/methacrylic acid/n-butyl acrylate, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/acrylic acid/ethyl propenoate, ethylene/methacrylic acid/ethyl propenoate and ethylene/acrylic acid/methyl acrylate copolymer. The ethylene copolymer containing acid most preferably is ethene/(methyl) vinylformic acid/n-butyl acrylate, ethene/(methyl) vinylformic acid/ethyl propenoate and ethene/(methyl) vinylformic acid/methyl acrylate copolymer.

Usually with metallic cation such as Li, Na, Mg, K, Ca, or ionomer neutralizes by Zn. However, it has been found that by by enough organic acids or organic acid salt, together with suitable alkali, adding described acid copolymer or ionomer to, this ionomer can be neutralized to for level much bigger metallic cation, and does not lose processibility. Preferably, the neutralization of this acid moieties is greater than about 80%, it is preferable that 90-100%, it is most preferred that 100%, and does not lose processibility. This is with melt blending ethylene-alpha, ��-ethylenic copolymers of unsaturated carboxylic acids is (such as, with organic acid or organic acid salt copolymerization), and add the cationic source enough measured the neutralization levels of all acid moieties (be included in acid copolymer and in organic acid those) to be increased to and be greater than 90%, (being preferably greater than 100%).

The organic acid of the present invention is aliphatics, single-or many-sense (saturated, unsaturated, or how unsaturated) organic acid. Also these organic acid salt can be used. The organic acid salt of the present invention comprises barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, caesium, iron, nickel, silver, the salt of aluminium, tin, or calcium, the salt of the derivative of the salt of lipid acid, particularly stearic acid, behenic acid, sinapinic acid, oleic acid, linolic acid or its dimerization. Preferably this organic acid is relative non-migrating (they do not move on the surface of polymkeric substance at ambient temperature) and non-volatile (they do not volatilize at the temperature needed for melt blending) with the salt of the present invention.

The ionomer of the present invention also can be more conventional ionomer, that is, with metallic cation part neutralization. By cat ions if lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminium or its mixture are by the acid moieties in this acid copolymer and about 1 to about 90%, preferred at least about 20 to about 75%, more preferably at least about 40 to about 70%, thus form ionomer.

In a preferred embodiment, the individual layer core of the present invention is encapsulated with two tectums, wherein the thickness of inner cover is about 0.01 inch to about 0.06 inch, more specifically about 0.015 inch to about 0.040 inch, most preferably from about 0.02 inch to about 0.035 inch, formed by the ionomer of part-or all neutralizations with described inner cover, the Shore D hardness of described part-or all ionomer of neutralization is for being greater than about 55, more preferably greater than about 60, and most preferably it is greater than about 65. In this embodiment, the thickness of outer cover should be about 0.015 inch to about 0.055 inch, more preferably from about 0.02 inch to about 0.04 inch, most preferably from about 0.025 inch to about 0.035 inch, it is about Shore D 60 or less with hardness, more preferably 55 or less, and most preferably from about 52 or less.Described inner cover should be harder than described outer cover. In this embodiment, outer cover comprises part-or the ionomer of completely-neutralization, urethane, polyureas, or its blend. Outer cover most preferably can pour into a mould or can the urethane of reaction injection moulding, polyureas or its multipolymer or mixture, its Shore D hardness is about 40 to about 50. Inner cover material most preferably is the ionomer of part neutralization, and it contains zinc, and the ionomer of sodium or lithium neutralization is such as8940,8945,9910,7930,7940, or its Shore D hardness is the mixture of about 63 to about 68.

In another multilayer tectum, single core enforcement mode, outer cover and inner cover material and thickness are identical, but durometer level is contrary, that is, outer cover is harder than inner cover.

Alternative preferred embodiment in, golf ball is the golf ball of monoblock, it has the surface (dimpledsurface) of depression, and has the surface hardness (that is, negative hardness gradient) equal or less with core rigidities. The diameter of the ball of this monoblock is preferably about 1.680 inches to about 1.690 inches, and weight is that about 1.620oz, Atti compression is about 40 to 120, and COR is about 0.750 to 0.825.

In preferred two pieces-ball enforcement mode, the individual layer core individual layer covering material with negative hardness gradient is coated, the Shore D hardness of this covering material is about 20 to about 80, more preferably from about 40 to about 75, most preferably from about 45 to about 70, and comprise thermoplasticity or heat-curable urethane, polyureas, polymeric amide, polyester, polyester elastomer, polyether-amide or polyester-amides, the ionomer partly or completely neutralized, polyolefine is polyethylene such as, polypropylene, polyethylene and ethylene copolymers such as Ethylene-butyl acrylate or ethylene-methyl acrylate, poly-(ethylene-methyl methacrylate) multipolymer-and terpolymer, metallocene-catalyzed polyolefine and the functionalized polyolefine of polar group and blend thereof. in two pieces of enforcement modes, preferred covering material is ionomer (is conventional or HNP), and its hardness is about 50 to about 70 Shore D. in two pieces of enforcement modes, another preferred covering material is thermoplasticity or heat-curable urethane or polyureas. preferred ionomer is high acid ionomer, and it comprises ethene and methacrylic acid or acrylic acid multipolymer, and acid content is at least 16 to about 25wt%. in this case, the antigradient core (spin-increasingnegativegradientcore) rotated by increasing by the rotation (reducedspin) of the reduction of the high acid ionomer contribution of relative rigidity is offset to a certain extent. the diameter of this core can be about 1.0 inches to about 1.64 inches, it is preferable that about 1.30 inches to about 1.620, and more preferably from about 1.40 inches to about 1.60 inches.

Another preferred covering material comprises can be poured into a mould or the urethane of reaction injection moulding, the multipolymer of polyureas or polyurethane/polyurea or mixture. Effectively, this tectum is thermoset, but can be thermoplasticity, and Shore D hardness is about 20 to about 70, it is more preferable to about 30 to about 65, it is most preferred that about 35 to about 60. Wetting vapour blocking layer optionally is used (to be such as disclosed in United States Patent (USP) 6,632,147 between this tectum and core; 6,932,720;7,004,854; In 7,182,702, by whole contents of all these documents by reference to being incorporated to the application).

Although any enforcement mode of the application all can have any known depression number and pattern, but preferred depression number is 252 to 456, it is more preferable to be 330 to 392. This depression number can comprise in prior art any width, the degree of depth and rib corner degree (edgeangle) that disclose, and this pattern can comprise multiple depression with different in width, the degree of depth and rib corner degree. The separation line configuration of described pattern can be straight line or staggered wave separation line (SWPL). Most preferably this depression number is 330,332, or 392, and comprise 5 to 7 depression sizes, and separation line is SWPL.

In these enforcement modes any, this individual layer core can replace with the core of 2 or more layers, and wherein at least one core layer has negative hardness gradient. Different from operation embodiment, or unless specifically indicated otherwise, otherwise, all numerical ranges, amount, value has term " about " to modify with percentage before for those read likes of material with the amount of other things in specification sheets similarly being, even if this term " about " may occur together with this value, amount or scope indefinitely. Therefore, unless the contrary indicated otherwise, numerical parameter listed in specification sheets and appended claim is approximate, the character of its expectation that can obtain desired by the present invention and change. At least, and not attempting, by the scope that should be used for limiting claim of identical instruction, each numerical parameter should at least be explained according to given significant figure with by applying the common technology of rounding up. Although the wide in range numerical range enclosed providing the present invention and parameter are approximate, but the numerical value provided in specific embodiment as far as possible accurately provides. But some error that any numerical value itself must cause containing the standard deviation owing to existing in their each measurement means. In addition, when the application provides various numerical range, any combination (comprising described value) of these values any can be used. Although the illustrated embodiment of the present invention that the application discloses meets above-described object clearly, it should be understood that it may occur to persons skilled in the art that many improvement and other enforcement mode. Improve and the mode of enforcement therefore, it is to be understood that appended claim intention covers within the spirit and scope of the present invention all these.

Claims (13)

1. a golf ball, comprises:

Single core, it has outside surface and geometric centre, and is formed by uniform rubber combination substantially;

Inner covering layer, it is put around described caryogamy, and described interior covering comprises ionomer material, and has the material hardness of 60 Shore D or bigger; With

Outer cover, it configures around described inner covering layer, and described outer covering comprises casting type polyureas or casting PU and has the material hardness of 60 Shore D or less;

Wherein said outside surface has the hardness of 12% or less trans component content and 71 to 88 Shore C, described geometric centre has the hardness of 10% or less trans component content and 70 to 80 Shore C, and core surface hardness is greater than geometric centre hardness 1 to 10 Shore C to limit shallow positive hardness gradient.

2. the golf ball of claim 1, wherein said positive hardness gradient is 2 to 8 Shore C.

3. the golf ball of claim 2, wherein said positive hardness gradient is 2.5 to 7 Shore C.

4. the golf ball of claim 1, wherein said core has the external diameter of 1.45 to 1.62 inches.

5. the golf ball of claim 4, wherein said core has the external diameter of 1.50 to 1.58 inches.

6. the golf ball of claim 1, the hardness at wherein said Nuclear goemetry center is 72 to 78 Shore C.

7. the golf ball of claim 1, the hardness on wherein said core surface is 73 to 80 Shore C.

8. the golf ball of claim 7, its center surface hardness is 74 to 78 Shore C.

9. the golf ball of claim 1, wherein said outside surface has 10% or less trans component content, and geometric centre has 8% or less trans component content.

10. a golf ball, comprises:

Single core, has the external diameter of 1.5 to 1.55 inches, outside surface and geometric centre, and is formed by uniform rubber combination substantially;

Inner covering layer, it is put around caryogamy, and described interior covering comprises thermoplasticity ionomer material, and described material has the material hardness of 66 to 80 Shore D; With

Outer cover, it configures around described inner covering layer, and described outer covering has the thickness of 0.04 inch, and comprises the ionomer that material hardness is 64 to 68 Shore D, or has the thermoset casting PU of 51 to 55 Shore D;

Wherein said outside surface has the hardness of 12% or less trans component content and 74 to 78 Shore C, described geometric centre has the hardness of 10% or less trans component content and 72 to 78 Shore C, and described core surface hardness is greater than geometric centre hardness 1 to 5 Shore C to limit shallow positive hardness gradient, described core has the Atti compression of 50 to 70.

The golf ball of 11. claims 10, wherein said golf ball also comprises the middle layer being configured between inner covering layer and core, and described middle layer has the thickness of 0.06 inch and the hardness of 43 to 47 Shore D.

The golf ball of 12. claims 11, wherein said interior covering hardness is 66 Shore D, and described middle layer hardness is 45 Shore D, and outer cover hardness is 53 Shore D.

13. 1 kinds of golf ball, comprise:

Single core, has the external diameter of 1.45 inches, outside surface, and geometric centre, and is formed by uniform rubber combination substantially;

Inner covering layer, it is put around caryogamy, and described interior covering has the external diameter of 1.58 inches, and comprises thermoplasticity nonionic crosslinked polymeric materials, and described material has the material hardness of 38 to 42 Shore D; With

Outer cover, it configures around described inner covering layer, and described outer covering has the thickness of 0.05 inch and comprises the ionomer with 66 to 70 Shore D material hardnesses;

Wherein said outside surface has the hardness of 12% or less trans component content and 74 to 78 Shore C, described geometric centre has the hardness of 10% or less trans component content and 72 to 78 Shore C, and described core surface hardness is greater than geometric centre hardness 1 to 5 Shore C to limit shallow positive hardness gradient.