CN102526994A

CN102526994A - Multi-piece golf ball comprising low hardness gradient core

Info

Publication number: CN102526994A
Application number: CN2011104102068A
Authority: CN
Inventors: B.科莫; M.J.沙利文; D.E.琼斯; D.A.拉德
Original assignee: Acushnet Co
Current assignee: Acushnet Co
Priority date: 2010-12-09
Filing date: 2011-12-09
Publication date: 2012-07-04
Anticipated expiration: 2031-12-09
Also published as: JP5468055B2; CN105833483A; JP2012120846A; CN105833483B; CN102526994B

Abstract

A golf ball includes a single core formed from a substantially homogenous rubber composition, an inner cover disposed about the core, and an outer cover. The inner cover includes an ionomeric material and has a hardness of about 60 Shore D or greater. The outer cover layer is disposed about the inner cover layer, is formed from a castable polyurea or polyurethane, and has a material hardness of about 60 Shore D or less. The outer surface of the core has a trans content of about 12% or less and a hardness of about 71 to 88 Shore C, the geometric center of the core has a trans content of about 10% or less and a hardness of about 70 to 80 Shore C, and the core surface hardness is greater than the geometric center hardness by about 1 to 10 Shore C to define a shallow positive hardness gradient.

Description

The multi-piece golf ball that comprises soft gradient nuclear

Cross reference

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

Invention field

The present invention normally relates to the golf with the nuclear that contains one or more layers, and any layer all has the hardness gradient of ' bearing ' or ' just ', trans component gradient (trans gradient), or both.More particularly, golf has one or more layers nuclear, and wherein (solid) nuclear of at least one layer, preferred single entity has low ' just ' hardness gradient and comprises the trans polybutadiene gradient simultaneously.

Background technology

Entity golf coats entity nuclear by lining cap rock (cover) usually and processes, and both all can have a plurality of layers cover layer and nuclear, and for example double-core has entity center and outside stratum nucleare, and perhaps multilayer coatingn has inside.In general, golf ball and/or center are formed by thermoset rubber, normally based on the composition of polybutadiene.Usually nuclear is heated and make it crosslinked producing specific character, for example higher or lower compression, it can influence the rotary speed of ball and/or better " sensation " is provided.Like this and other character can be adapted to have the golf player's of different abilities needs.Angle from the golf producer; The nuclear of desired display wide region character; These character are resilience, durability, rotation and " sensation " for example, because can make manufacturer make and sell the golf of the number of different types that is suitable for different ability levels like this.

Up to the present, most of single core golf balls nuclears have traditional surface from nuclear to the center of nuclear by hard to soft hardness gradient, this also be considered to " positive hardness gradient ".But these gradients are bigger usually, up to 15 Xiao's formula C hardness, and 20 Xiao's formula C hardness, even up to 25 Xiao's formula C hardness or higher.Patent documentation comprises a large amount of lists of references, in addition, its discussed across the golf ball from firmly-surface is to the hardness gradient at soft-center.

People's such as Molitor United States Patent(USP) No. 4; 650; 193 disclose the hardness gradient in the superficial layer of examining prevailingly, and it forms as follows: utilize and solidify the material piece that changes agent (cure-altering agent) processing curable elastomer and will expect that subsequently formation of lots is a nuclear.As stated; Such processing has produced has the nuclear of forming two different zones, first be nuclear hard, elastic mid portion is arranged, this part remains and is not processed; And second portion is soft, the variable skin of nuclear, and this part is handled through solidify changing agent.It is whole that two " layers " of this nuclear or zone become each other, can obtain thus from pressure release surface to hard center such gradient.

People's such as Berman United States Patent(USP) No. 3,784,209 discloses soft to hard hardness gradient prevailingly.This patent discloses has the heterogeneous of " mixing " elastomer core, the golf of moulding.The center spheroid of uncured elastomer material is surrounded by compatible but different uncured elastomer.When elastomeric two-layer when being exposed to curing agent simultaneously, they can form integral body each other, thereby have formed the nuclear that mixes.The center of this nuclear has first elastomeric material of higher concentration, and it is harder than skin.A shortcoming of this manufacturing approach is to make first elastomer, and making second elastomer then and then they being shaped to one is a time-consuming procedure.

Thereby other patent has been discussed and nuclear is carried out surface treatment has been made it have soft " skin (skin) ".But because the interior section of these nuclears is unprocessed, so they have the gradient of similar crust to soft center, and are the same with traditional nuclear.For example, people's such as Nesbitt United States Patent(USP) No. 6,113, the 831 independent moccasin skin that discloses traditional nuclear prevailingly and surrounded this nuclear.Prepare this moccasin skin through following process: in forming process, preformed material piece is exposed under the steam (steam), thereby makes maximum forming temperature surpass steam cure point (steam set point), and the temperature of control thermoforming in forming process.This skin comprises into 1/4 inch of radial outermost 1/32 inch～spherical nuclei.People's such as Nesbitt United States Patent(USP) No. 5,976,443 and No.5,733,206 disclose all that the outer surface to the material piece adds water smoke before the moulding, and form the moccasin skin thus.As stated, through hindering crosslinked on the nuclear surface, water softening the compression of nuclear, thereby made the softer moccasin skin that surrounds hard mid portion.

In addition, a plurality of patents disclose multi-layer golf ball nuclear, and wherein each stratum nucleare has different hardness, have produced the hardness gradient from the stratum nucleare to the stratum nucleare thus.

Yet, still have following demand: with regard to multi-layer golf ball with individual layer nuclear (its have more shallow from the surface to the center firmly to soft (" just ") hardness gradient) with regard to, obtain making the cheapness and the effective method of such nuclear.

Summary of the invention

The present invention relates to comprise single nuclear and two obducent golf.This single nuclear has outer surface and geometric center, and its by basically uniformly rubber compsn form.This pair covering comprises inner covering layer and outer cover.Inner covering layer, it is put around said caryogamy, and it is formed by ionomer material.Inner covering layer has about 60 Shore D or bigger material hardness.It disposes outer cover around inner covering layer, and it is formed by casting type (castable) polyureas or casting type polyurethane usually.This layer has about 60 Shore D or littler material hardness.One preferred embodiment in; The outer surface of nuclear has about 12% or the hardness of trans component content still less (trans content) and about 71 to 88 Shore C; Geometric center has about 10% or the hardness of trans component content still less and about 70 to 80 Shore C, and the nuclear case hardness than about 1 to the 10 Shore C of geometric center hardness to limit shallow positive hardness gradient.

In one embodiment, said positive hardness gradient is about 2 to 8 Shore C, more preferably about 2.5 to 7 Shore C.Nuclear preferably has about 1.45 to about 1.62 inches external diameter, more preferably has about 1.50 to about 1.58 inches external diameter.The hardness of nuclear geometric center is generally about 72 to 78 Shore C, and the hardness on nuclear surface is generally about 73 to 80 Shore C, more preferably from about 74 to 78 Shore C.Another preferred embodiment in, the outer surface of nuclear has about 10% or trans composition still less, and the geometric center of nuclear has about 8% or trans composition still less.

The invention still further relates to golf, it is become by the single karyomorphism with about 1.5 to 1.55 inches external diameter.This nuclear usually by basically uniformly rubber compsn form.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 is around the inner covering layer configuration, and it has about 0.04 inch thickness.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 thermosetting casting type polyurethane with about 51 to 55 Shore D hardness.Preferably; The outer surface of nuclear has about 12% or the hardness of trans component content still less and about 74 to 78 Shore C; Geometric center has about 10% or the hardness of trans component content still less and about 72 to 78 Shore C; And to limit shallow positive hardness gradient, nuclear has about 50 to 70 Atti compression (Atti comprission) to the nuclear case hardness than about 1 to the 5 Shore C of geometric center case hardness.

In one embodiment, golf also comprises the intermediate layer that is disposed between inner covering layer and the nuclear, and this intermediate layer has the hardness of about 0.06 inch thickness and about 43 to 47 Shore D.Usually covering hardness in is about 66 Shore D, and intermediate layer hardness is about 45 Shore D, and outer cover hardness is about 53 Shore D.

The invention still further relates to the golf that comprises single nuclear, this single nuclear has about 1.45 inches external diameter, outer surface, and geometric center, and be by basically uniformly rubber compsn form.Inner covering layer is put around caryogamy.The interior covering has about 1.58 inches external diameter, and formed by the thermoplasticity nonionic crosslinked polymeric materials of the material hardness with about 38 to 42 Shore D.Outer cover is around said inner covering layer configuration.Outer covering has about 0.05 inch thickness and is formed by the ionomer with about 66 to 70 Shore D material hardnesses.Preferably; The outer surface of nuclear has about 12% or the hardness of trans component content still less and about 74 to 78 Shore C; Geometric center has about 10% or the hardness of trans component content still less and about 72 to 78 Shore C, and the nuclear case hardness than about 1 to the 5 Shore C of geometric center hardness to limit shallow positive hardness gradient.

Detailed Description Of The Invention

Golf of the present invention can comprise simple layer () golf; And multi-layer golf ball; The obducent golf that for example has nuclear and encloses core, but preferably by the nuclear of entity center (being also referred to as kernel) and outer nuclear layer, inner covering layer and outer cover form.Certainly, any nuclear and/or cover layer can comprise more than one deck.In preferred embodiment; Nuclear is formed by kernel and outer nuclear layer; Wherein kernel and outer nuclear layer all have from the outer surface of a composition to its penetrale (promptly; The center of kernel or the inner surface of outer nuclear layer) hardness gradient (" bearing " hardness gradient) of radial inside " soft " to hard, but also can expect other embodiment, wherein relate to the hardness gradient between the nuclear composition variation direction and combination (for example; In " bearing " gradient at center and " just " gradient coupling at outer nuclear layer, vice versa).

The center of nuclear can also be or by one or the hollow ball of more intermediate layers and/or cover encloses or the ball of liquid-filling, perhaps nuclear can also comprise the solid or the liquid center of being twined by the elastomeric material that stretches.Anyly can show nuclear hardness gradient of the present invention (that is, " bearing " gradient) around being configured in these selectable supercentral layers.Cover layer can be a simple layer or for example, forms by a plurality of layers, for example inner covering layer and outer cover.

Like top summary, of the present invention endorsing to have the hardness gradient as giving a definition: this hardness gradient is by defining at core surface (or outer nuclear layer) and the radial hardness of inwardly measuring towards the center of kernel (being generally the 2-mm increment).Employed in this article term " is born " and " just " is meant from (for example, the outer surface of entity nuclear the hardness number of the outer surface of measured composition; The outer surface of the kernel in double-core; The outer surface of the outer nuclear layer in double-core, or the like) deduct hardness number (for example, the center of entity nuclear or the kernel in the dual-core architecture in the inside of measured composition part; The inner surface of stratum nucleare; Or the like) after the result.For example, have the low hardness (that is, soft-hearted in the surface ratio) of comparing with the center like the outer surface of sporocarp nuclear, hardness gradient will be considered to be " bearing " gradient degree (little numerical value-big numerical value=negative numerical value).Preferred nuclear of the present invention has zero or negative hardness gradient, more preferably between zero (0) and-10, most preferably between 0 and-5.

Preferably; Stratum nucleare (kernel or outer nuclear layer) is by preparation of compositions; Said composition comprises at least a heat-curable matrix rubber (base rubber); Polybutadiene rubber for example, it solidifies through at least a peroxide and at least a reactive auxiliary agent (co-agent), and reactive auxiliary agent can be slaine, non--metal promoter or their mixture of unsaturated carboxylic acid (for example acrylic or methacrylic acid).Preferably, composition also comprises suitable anti-oxidant.Nuclear can also comprise optional softening accelerator (soft and fast agent) (also being suitable-anticatalyst sometimes) in the preparation, for example organic sulfur or contain the organosulfur compound of metal.

Can also use other composition well known by persons skilled in the art, these other compositions are to be understood that Auto-regulating System of Density of Heavy Medium filler, processing aid, plasticizer, foaming or blowing agent, sulphur promoter and/or the non--peroxide radical source of including but not limited to.Matrix thermoset rubber 130 can with other rubber and polyblend, generally include natural or synthetic rubber.Preferred base rubber is 1, the 4-polybutadiene, and its cis-structure is at least 40%, preferably is higher than 80%, and more preferably is higher than 90%.The polybutadiene rubber instance of expectation comprises

CB 22 and

CB 23, CB 1221, CB 1220, CB 24 and CB21, and it can be purchased from LANXESS Corporation;

360L and

150L and UBEPOL-BR rubber; It can be from UBE Industries; Ltd; Tokyo, Japan is purchased;

7245,

7265 and BUDENE 1207 and 1208; It can be from Goodyear of Akron, and OH is purchased; SE BR-1220; BR 40 and BR 60, it can be purchased from Polimeri Europa; And BR 01, BR 730, BR 735, BR 11 and BR51, it can be purchased from Japan Synthetic Rubber Co.Ltd;

BRNd-40; And ND 40, ND 50 and ND 60, it can be purchased from Karbochem.

From Lanxess Corporation, most preferably through the rank of neodymium and cobalt catalysis, but following all can use: Buna CB 21; Buna CB 22; Buna CB 23; Buna CB 24; Buna CB25; Buna CB 29MES; Buna CB Nd 40; Buna CB Nd 40H; Buna CB Nd 60; Buna CB 55NF; Buna CB 60; Buna CB 45B; Buna CB 55B; Buna CB 55H; Buna CB 55L; Buna CB 70B; Buna CB 1220; Buna CB 1221; Buna CB 1203; Buna CB 45.In addition, can buy multiple suitable rubber, the Ubepol that the Ube Industries Inc of Japan sells, the BST that the BST Elastomers of Thailand sells from JSR (Japan Synthetic Rubber); The IPCL that the Indian Petrochemical Ltd of India sells; The Nitsu that the Karbochem Ltd in Karbochem or South Africa sells; And from the Petroflex of Brazil; The LG of Korea S; And the Kuhmo Petrochemcial of Korea S buys multiple suitable rubber.

Base rubber can also comprise height or middle Mooney viscosity rubber, or its blend." Mooney " unit is the unit that is used to measure the plasticity of crude rubber or half finished rubber.Equal moment of torsion with the plasticity of " Mooney " unit representation, with arbitrary unit, at the speed wheel measuring that contains on the disk of the container of 100 ℃ of rubber and change with per minute 2.Measured value according to ASTM D-1646 definition Mooney viscosity.It is about 40 that the Mooney viscosity scope is preferably greater than, more preferably in about 40 to about 80 scope, and further preferably in about 40 to about 60 scope.Can also use the polybutadiene rubber that has than high Mooney viscosity, the high viscosity polybutadiene stops up or the level of other negative effect manufacturing machine gets final product so long as the viscosity of polybutadiene does not reach.Expectation can be used the polybutadiene of viscosity less than 65 Mooneys in the present invention.In an embodiment of the invention, the golf ball through in having-or the polybutadiene material of height-Mooney viscosity process its resilience that show to improve (and, therefore distance) and the hardness of ball of can not improving.Such nuclear is soft, promptly compresses less than about 60 with more specifically in the scope of about 50-55.Have in the nuclear of about 30 to about 50 scope compression also scope in the preferred embodiment of the present invention.

In suitable-and the commercial source of paramount-Mooney viscosity polybutadiene comprises Bayer AG CB23 (Nd-catalysis), it has about 50 Mooney viscosity and is the polybutadiene of highly linear, and CB1221 (Co-catalysis).If desired, polybutadiene can also mix with other elastomer known in the art, and for example other polybutadiene rubber, natural rubber, styrene butadiene ribber and/or isoprene rubber are further to carry out modification to the character of nuclear.When using elastomeric mixture, the content of other composition during nuclear is formed is usually based on the proof resilience body mixture of 100 weight portions.One preferred embodiment in, base rubber comprises the polybutadiene of Nd-catalysis, the polybutadiene rubber of rare earth element-catalysis, or their blend.If desired, polybutadiene can mix with other elastomer as known in the art, and for example natural rubber, polyisoprene rubber and/or SBR styrene butadiene rubbers are to carry out modification to the character of nuclear.Other suitable base rubber comprises thermosets, for example ethylene propylene diene monomer rubber, EP rubbers, butyl rubber, halogenated butyl rubber, hydrogenated nitrile-butadiene rubber, nitrile rubber and silicon rubber.

Thermoplastic elastomer (TPE) (TPE) also can be used for the character of stratum nucleare is carried out modification, perhaps through storing uncured stratum nucleare with the blend of matrix thermoset rubber.These TPE comprise natural or paragutta (balata) or high trans-polyisoprene, high trans-polybutadiene or any SBC; For example styrene ethylene butadiene styrene, styrene-isoprene-phenylethene etc.; Metallocene or other are through the polyolefin of single site catalysed ethylene-octene copolymer for example; Or ethylene-butene copolymer, or thermoplastic polyurethane (TPU), comprise copolymer with silicones.Other is suitable is used for comprising

(thinking that it comprises polyether amide copolymer),

(thinking that it comprises polyetherester copolymer) with the TPE of thermoset rubber blend of the present invention; Thermoplastic polyurethane, and

(thinking that it comprises the styrenic block polymer elastomer).Any above-mentioned TPE or TPU can also contain the functional group that is useful on grafting, comprise maleic acid or maleic anhydride.

Extra polymer can also be chosen wantonly and be incorporated in the base rubber.Instance includes but not limited to: thermo-setting elastomer, as examine again abrasive material (core regrind), thermoplastic rubber sulfide (vulcanizate), the ionomer of copolymerization; The ionomer of trimerization, Merlon, polyamide, the polyamide of copolymerization; Polyester, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polyarylate, polyacrylate, polyphenylene oxide (polyphenylene ether); Impact-resistant modified polyphenylene oxide, high impact polystyrene, diallyl phthalate polyester, SAN (SAN) (comprising olefin-modified SAN and acrylonitrile-styrene-acrylonitrile polymer); Styrene-maleic anhydride copolymer, styrene copolymer, functionalized styrol copolymer, functionalized phenylethylene trimer; The phenylethylene trimer, cellulosic polymer, liquid crystal polymer, vinyl-vinyl-acetic ester copolymer; Polyureas, and polysiloxanes, or the polymer of any metallocene catalysis of these materials.

In the composition within the scope of the present invention; Suitable polyamides class as extra polymer comprises the resin that obtains in the following manner: (1) is dicarboxylic acids such as oxalic acid, adipic acid, decanedioic acid, terephthalic acid (TPA), M-phthalic acid or 1 (a); 4-cyclohexane dicarboxylic acid and (b) diamine such as ethylenediamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine or decamethylene diamine, 1, the polycondensation of 4-cyclohexane diamine or MXDP; (2) ring-opening polymerisation of cyclic lactames such as ∈-caprolactam or Ω-lauric lactam; (3) amino carboxylic acid is like the polycondensation of 6-aminocaprolc acid, 9 aminononanoic acid, the amino hendecanoic acid of 11-or 12 amino dodecanoic acid; Or the copolymerization of (4) cyclic lactames and dicarboxylic acids and diamine.The instantiation of suitable polyamide comprises NYLON, NYLON MXD6 and the NYLON 46 of NYLON 6, NYLON 66, NYLON 610, NYLON 11, NYLON 12, copolymerization.

Suitable peroxide initiator comprises cumyl peroxide; 2,5-dimethyl-2,5-two (t-butylperoxy) hexane; 2,5-dimethyl-2,5-two (t-butylperoxy) hexin; 2,5-dimethyl-2,5-two (benzoyl peroxy) hexane; 2,2 '-two (t-butylperoxy)-two-cumenes; 1,1-two (t-butylperoxy)-3,3,5-trimethyl-cyclohexane; 4,4-two (t-butylperoxy) valeric acid n-butyl; T-butyl perbenzoate; Benzoyl peroxide; 4,4 '-two (butyl peroxy) valeric acid n-butyl; Di-tert-butyl peroxide; Or 2,5-two-(t-butylperoxy)-2,5-dimethylhexane, lauryl peroxide; Tert-butyl hydroperoxide, α, α-two (t-butylperoxy) diisopropyl benzene; Two (2-t-butylperoxy isopropyl) benzene, two-t-amyl peroxy thing, di-tert-butyl peroxide.Preferably, this rubber compsn comprises about 0.25 to per 100 parts by weight of rubber of the peroxide of about 5.0 weight portions (phr), more preferably 0.5phr to 3phr, most preferably 0.5phr to 1.5phr.In most preferred embodiment, this peroxide exists with the amount of about 0.8phr.These scopes of given peroxide are that the said peroxide of hypothesis is 100% activity, do not consider any carrier that possibly exist.Because many commercially available peroxide are sold with carrier compound, therefore should calculate the physical presence amount of peroxide actives.The peroxide initiator of commercially available acquisition comprises the DICUP of the cumyl peroxide that can obtain from Crompton (Geo SpecialtyChemicals) ^TMClass (comprises DICUP ^TMR, DICUP ^TM40C and DICUP ^TM40KE).Similarly initator can be from AkroChem, Lanxess, and Flexsys/Harwick and R.T.Vanderbilt obtain.Other commercially available obtainable and preferred initators have TRIGONOX ^TM265-50B (from Akzo Nobel), it is 1,1-two (t-butylperoxy)-3,3, the mixture of 5-trimethyl-cyclohexane and two (2-t-butylperoxy isopropyl) benzene.TRIGONOX ^TMPeroxide is sold on carrier compound usually.

Suitable reactive auxiliary reagent includes but not limited to be applicable to the slaine of diacrylate of the present invention, dimethacrylate and monomethyl acrylates, comprises that metal wherein 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 with high initial velocity.This ZDA can have various purity.For the object of the invention, the amount of the zinc stearate that in ZDA, exists is low more, and the purity of ZDA is high more.The ZDA that contains less than about 10% zinc stearate is preferred.The ZDA that more preferably contains the 4-8% zinc stearate of having an appointment.Suitable, the dizinc acrylate resin of commercially available acquisition comprises from those of Sartomer Co..The preferred concentration of operable ZDA is extremely about 40phr of about 10phr, and more preferably 20phr is to about 35phr, and most preferably 25phr is to about 35phr.In particularly preferred embodiments, the amount of reactive auxiliary reagent is that about 29phr is to about 31phr.

The preferred coagent that appends can use separately, also can use with above-mentioned substance combination, but said coagent comprise and be not limited to trimethylol-propane trimethacrylate, trimethylolpropane triacrylate, etc.As well known to those skilled in the art, when coagent at room temperature is liquid, will help these compounds are scattered on the appropriate carriers, be easy to it and be blended in the rubber composition.

Antioxidant is meant those inhibition or prevents that elastomer generation oxidation from destroying and/or suppress or the compound of the reaction that prevents to be caused by oxygen radical.The instance of operable antioxidant includes but not limited to quinolines antioxidant, amine antioxidants and phenolic antioxidant among the present invention.Preferred antioxidant is 2; 2 '-methylene-two (4-methyl-6-tert butyl phenol), the product that can be called MBPC through the commodity that are purchased RT.Vanderbilt company obtains.Other polyphenolic antioxidants include:

T, L,

SKT,

SWP,

13,

1290.

Preferred antioxidant comprises alkylidene-substituted cresols of two alkyl, for example: 4,4 '-methylene-two (2, the 5-xylenol); 4,4 '-ethidine-two (6-ethyl-m-methyl phenol); 4,4 '-Ding fork base-two (the 6-tert-butyl group-m-methyl phenols); 4, pitch base-two (6-methyl-m-methyl phenols) 4 '-last of the ten Heavenly stems; 4,4 '-methylene-two (2-amyl group-m-methyl phenol); 4,4 '-propylidene base-two (5-hexyl-m-methyl phenol); 3, pitch base-two (5-ethyl-p-methyl phenols) 3 '-last of the ten Heavenly stems; 2,2 '-Ding fork base-two (3-n-hexyl-p-methyl phenols); 4,4 '-(2-fourth fork base)-two (the 6-tert-butyl group-m-methyl phenols); 3,3 '-(4-pitches basic the last of the ten Heavenly stems)-two (5-ethyl-p-methyl phenols); (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-decyl-3-hydroxy-4-methyl phenyl) butyl amyl group methane; (3-ethyl-4-methyl-5-hydroxy phenyl) (2,3-dimethyl-3-hydroxyl-phenyl) nonyl methane; (3-methyl-2-hydroxyl-6-ethylphenyl) (2-isopropyl-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 be not limited to said example.

Other suitable antioxidant comprises substituted phenols, for example: the 2-tert-butyl group-4-metoxyphenol; The 3-tert-butyl group-4-metoxyphenol; Uncle's 3-octyl group-4-metoxyphenol; 2-methyl-4-metoxyphenol; 2-octadecyl-4-n-butoxy phenol; The 3-tert-butyl group-4-octadecane oxygen base phenol; 3-dodecyl-4-thanatol; 2,5-two-tert-butyl group-4-metoxyphenol; 2-methyl-4-metoxyphenol; 2-(1-methylcyclohexyl)-4-metoxyphenol; The 2-tert-butyl group-4-dodecyloxy phenol; 2-(1-methyl-benzyl)-4-metoxyphenol; Uncle's 2-octyl group-4-metoxyphenol; Gallicin; The gallic acid n-propyl; The positive butyl ester of gallic acid; Lauryl gallate; The gallic acid myristin; The gallic acid stearyl; 2,4, the 5-trihydroxy-acetophenone; 2,4,5-trihydroxy butyrophenone; 2,4,5-trihydroxy stearophenone; 2,6-two-tert-butyl group-4-methylphenol; 2,6-two-uncle octyl group-4-methylphenol; 2,6-two-tert-butyl group-4-octadecyl phenol; 2-methyl-4-methyl-6-tert butyl phenol; 2,6-two-octadecyl-4-methylphenol; 2,6-two-dodecyl-4-methylphenol; 2,6-two-n-octyl-4-methylphenol; 2,6-two-n-hexadecyl-4-methylphenol; 2,6-two-(1-methyl undecyl)-4-methylphenol; 2,6-two-(1-methyl heptadecyl)-4-methylphenol; 2,6-two-trimethyl hexyl-4-methylphenol; 2,6-two-(1,1,3,3-tetramethyl octyl group)-4-methylphenol; 2-dodecyl-6-the tert-butyl group-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-n-octadecane base-4-methylphenol; 2-dodecyl-6-n-octyl-4-methylphenol; 2-methyl-6-n-octadecane base-4-methylphenol; 2-dodecyl-6-(1-methyl heptadecyl)-4-methylphenol; 2,6-two (1-methyl-benzyl)-4-methylphenol; 2,6-two (1-methylcyclohexyl)-4-methylphenol; 2,6-(1-methylcyclohexyl)-4-methylphenol; 2-(1-methyl-benzyl)-4-methylphenol; With relevant substituted phenol, but be not limited to said example.

Preferred antioxidant comprises the alkylidene diphenol, for example: 4,4 '-Ding fork base-two (3 methy 6 tert butyl phenols); 2,2 '-Ding fork base-two (4, the 6-xylenol); 2,2 '-Ding fork base-two (4-methyl-6-tert butyl phenol); 2,2 '-Ding fork base-two (4-tert-butyl groups-6-methylphenol); 2,2 '-ethidine-two (4-methyl-6-tert butyl phenol); 2,2 '-methylene-two (4, the 6-xylenol); 2,2 '-methylene-two (4-methyl-6-tert butyl phenol); 2,2 '-methylene-two (4-ethyl-6-tert-butyl phenol); 4,4 '-methylene-two (2, the 6-DI-tert-butylphenol compounds); 4,4 '-methylene-two (2-methyl-6-tert butyl phenol); 4,4 '-methylene-two (2, the 6-xylenol); 2,2 '-methylene-two (the 4-tert-butyl group-6-phenylphenol); 2,2 '-dihydroxy-3,3 ', 5,5 '-tetramethyl Stilbene; 2,2 '-isopropylidene-two (4-methyl-6-tert butyl phenol); Ethylenebis (betanaphthol); 1, the 5-dihydroxy naphthlene; 2,2 '-ethylidene-two (4-methyl-6-propylphenol); 4,4 '-methylene-two (2-propyl group-6-tert-butyl phenol); 4,4 '-ethylidene-two (2-methyl-6-propylphenol); 2,2 '-methylene-two (5-methyl-6-tert butyl phenol); With 4,4 '-Ding fork base-two (6-tert-butyl groups-3-methylphenol), but be not limited to said example.

Preferred antioxidant also comprises the alkylidene trisphenol, for example: 2, two (2 '-hydroxyl-the 3 '-tert-butyl group-5 '-the methyl-benzyl)-4-methylphenols of 6-; 2, two (2 '-hydroxyl-3 '-ethyl-5 '-tert-butyl group benzyl)-4-methylphenols of 6-; With 2, two (2 '-hydroxyl-the 3 '-tert-butyl group-5 '-propyl group benzyl) the 4-methylphenols of 6-, but be not limited to said example.

The content of antioxidant is generally about 0.1phr～about 5phr, preferably about 0.1phr～about 2phr, more preferably from about 0.1phr～about 1phr.In special preferred embodiment, the content of antioxidant is about 0.4phr.In other embodiments, the content of antioxidant should guarantee that the hardness gradient of nuclear of the present invention (core) bears.The amount of the antioxidant that preferably in stratum nucleare (inner nuclear layer and outer nuclear layer) component, adds is about 0.2phr～about 1phr, and more preferably about 0.3phr～about 0.8phr most preferably is about 0.4phr～about 0.7phr.Preferably in nuclear consitution, add the peroxide that comes in 100% activity of about 0.25phr～about 1.5phr, more preferably about 0.5phr～about 1.2phr most preferably is about 0.7phr～about 1.0phr.Can adjust golf desired compression, rotation and the feel of amount of ZDA to realize obtaining.Temperature during curing is about 290 ° of F～about 335 ° of F, more preferably about 300 ° of F～about 325 ° of F, and raw material (stock) stores at least about 10 minutes～30 minutes under its selected temperature.

Can also comprise the optional softening accelerator (soft and fast agent) that contains in the thermoset rubber composition of the present invention." softening accelerator " in this use means any compound or its blend or its combination in any that the nuclear that makes manufacturing has property: with the nuclear phase ratio that does not use softening accelerator manufacturing; 1) more soft under constant COR condition (low compression), or 2) under identical compression, have a higher COR.The softening accelerator that contains in the preferred composition of the present invention is about 0.05phr～about 10.0phr.In one embodiment, the amount of said softening accelerator is about 0.05phr～about 3.0phr, is preferably about 0.05phr～about 2.0phr, more preferably about 0.05phr～about 1.0phr.In another embodiment, the amount of said softening accelerator is about 2.0phr～about 5.0phr, is preferably about 2.35phr～about 4.0phr, more preferably about 2.35phr～about 3.0phr.In the embodiment of higher concentration, the amount of said softening accelerator is about 5.0phr～about 10.0phr, and more preferably about 6.0phr～about 9.0phr most preferably is about 7.0phr～about 8.0phr.In highly preferred embodiment, the amount of said softening accelerator is about 2.6phr.

Preferred softening accelerator includes but not limited to organosulfur compound or metallic organosulfur compound, organosulfur compound (comprising list, two and polysulfide, mercaptan, sulfhydryl compound), inorganic sulfide compound, the VIA of family compound, or its mixture.Softening accelerator component also can be the admixture of organosulfur compound and inorganic sulfide compound.

The preferably softening accelerator of the present invention comprises the compound with formula, but is not limited thereto:

In the formula, R ₁～R ₅Can anyly sequentially be: C ₁～C ₈Alkyl, halogen group, mercapto (SH), carboxylate (salt) group, sulphonic acid ester (salt) group, and hydrogen, the preferably softening accelerator of the present invention also can be: phenyl-pentafluoride 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-phenyl tetrafluoride thiophenol, 2,3,5,6-phenyl tetrafluoride thiophenol, 4-chlorine phenyl tetrafluoride thiophenol, reptazin, 2-chlorothio-phenol, 3-chlorothio-phenol, 4-chlorothio-phenol, 2,3-chlorothio-phenol, 2; The 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, phenyl-pentabromide thiophenol, 2-bromo thiophenol, 3-bromo thiophenol, 4-bromo thiophenol, 2; The 3-bromo thiophenol, 2,4-bromo thiophenol, 3,4-bromo thiophenol, 3,5-bromo thiophenol, 2,3,4-bromo thiophenol, 3,4; The 5-bromo thiophenol, 2,3,4,5-tetrabromo-benzene thiophenol, 2,3,5,6-tetrabromo-benzene thiophenol, pentaiodobenzene thiophenol, 2-iodobenzene thiophenol, 3-iodobenzene thiophenol; 4-iodobenzene thiophenol, 2,3-iodobenzene thiophenol, 2,4-iodobenzene thiophenol, 3,4-iodobenzene thiophenol, 3,5-iodobenzene thiophenol, 2,3,4-iodobenzene thiophenol; 3,4,5-iodobenzene thiophenol, 2,3,4,5-tetraiodo-benzene thiophenol, 2,3,5,6-tetraiodo-benzene thiophenol, and zinc salt.Preferred halogeno-benzene thiol compounds is a reptazin; It can be purchased acquisition with pure form; Also can be purchased the finished product that obtains commodity

by name, these commodity are that on the clay medium carrier, to contain volume containing the sample be 45% reptazin (being equivalent to 2.4 parts PCTP).

can be from Struktol Company ofAmerica of Stow, and OH company is purchased acquisition.PCTP can be from eChinachem of San Francisco, and CA company obtains its pure form, can be from eChinachem of San Francisco, and CA company obtains its salt form.Most preferably, the halogeno-benzene thiol compounds is the zinc salt of reptazin, can be from eChinachem of San Francisco, and CA company is purchased acquisition.

As used herein, when relating to when of the present invention, term " organosulfur compound " is meant the compound of any carbon containing, hydrogen and sulphur, and wherein sulphur directly is connected with at least one carbon atom.As used herein, term " sulphur compound " is expressed as elemental sulfur, polymerised sulphur or its combination.Should be understood that further that term " elemental sulfur " is meant S ₈Ring structure, " polymerised sulphur " is for also comprising the structure of another sulphur at least except that elemental sulfur.

Other suitable example of softening accelerator (also be considered to suitable-to-anticatalyst) include but not limited to 4,4 '-diphenyl disulphide; 4,4 '-xylyl disulphide; 2,2 '-benzamido diphenyl disulphide; Two (2-aminophenyl) disulphide; Two (4-aminophenyl) disulphide; Two (3-aminophenyl) disulphide; 2,2 '-two (the amino naphthyl of 4-) disulphide; 2,2 '-two (the amino naphthyl of 3-) disulphide; 2,2 '-two (the amino naphthyl of 4-) disulphide; 2,2 '-two (the amino naphthyl of 5-) disulphide; 2,2 '-two (the amino naphthyl of 6-) disulphide; 2,2 '-two (the amino naphthyl of 7-) disulphide; 2,2 '-two (the amino naphthyl of 8-) disulphide; 1,1 '-two (the amino naphthyl of 2-) disulphide; 1,1 '-two (the amino naphthyl of 3-) disulphide; 1,1 '-two (the amino naphthyl of 3-) disulphide; 1,1 '-two (the amino naphthyl of 4-) disulphide; 1,1 '-two (the amino naphthyl of 5-) disulphide; 1,1 '-two (the amino naphthyl of 6-) disulphide; 1,1 '-two (the amino naphthyl of 7-) disulphide; 1,1 '-two (the amino naphthyl of 8-) disulphide; 1,2 '-diaminostilbene, 2 '-disulfide group dinaphthyl; 2,3 '-diaminostilbene, 2 '-disulfide group dinaphthyl; Two (4-chlorphenyl) disulphide; Two (2-chlorphenyl) disulphide; Two (3-chlorphenyl) disulphide; Two (4-bromophenyl) disulphide; Two (2-bromophenyl) disulphide; Two (3-bromophenyl) disulphide; Two (4-fluorophenyl) disulphide; Two (4-iodophenyl) disulphide; Two (2, the 5-dichlorophenyl) disulphide; Two (3, the 5-dichlorophenyl) disulphide; Two (2, the 5-dichlorophenyl) disulphide; Two (2, the 4-dichlorophenyl) disulphide; Two (2, the 6-dichlorophenyl) disulphide; Two (2,5-dibromo chlorphenyl) disulphide; Two (3,5-dibromo chlorphenyl) disulphide; Two (2-chloro-5-bromophenyl) disulphide; Two (2,4, the 6-trichlorophenyl) disulphide; Two (2,3,4,5, the 6-five chlorophenyl) disulphide; Two (4-cyano-phenyl) disulphide; Two (2-cyano-phenyl) disulphide; Two (4-nitrobenzophenone) disulphide; Two (2-nitrobenzophenone) disulphide; 2,2 '-disulfido phenenyl Ethyl formate; 2,2 '-disulfido phenenyl methyl formate; 2,2 '-disulfido phenenyl formic acid; 4,4 '-disulfido phenenyl Ethyl formate; Two (4-acetylphenyl) disulphide; Two (2-acetylphenyl) disulphide; Two (4-formoxyl phenyl) disulphide; Two (4-carbamoyl 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-cyanic acid naphthyl) disulphide; 2,2 '-two (1-acetyl group naphthyl) disulphide; Deng; Or its mixture.Preferred organic sulfur composition comprises 4,4 '-diphenyl disulphide; 4,4 '-ditolyl disulphide, or 2,2 '-benzamido diphenyl disulphide, or its mixture.Preferred organic sulfur composition comprises 4,4 '-xylyl disulphide.In another embodiment, can use metallic organic sulfur composition according to the present invention.Suitable containing metal organic sulfur composition includes but not limited to cadmium, copper, lead and the tellurium analog of DDC (salt), diamyl dithiocarbamate ester (salt) and dimethyldithiocarbamate (salt), and composition thereof.

Suitable replacement that does not comprise sulphur or metal or unsubstituted aromatic series organic principle include but not limited to 4,4 '-dibenzenyl, azobenzene or its mixture.Aromatic series organic group preferred size is at C ₆To C ₂₀Scope, more preferably at C ₆To C ₁₀Scope.Suitable inorganic sulphide composition includes but not limited to the sulfide analog of titanium sulfide, manganese sulfide and iron, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, tin and bismuth.

Substituted or unsubstituted aromatic organic compounds also is suitable as softening accelerator.Suitable replacement or unsubstituted aromatic series organic principle include but not limited to have formula (R ₁) _x-R ₃-M-R ₄-(R ₂) _yComponent, R wherein ₁And R ₂Hydrogen, perhaps replacement or unsubstituted C respectively do for oneself _1-20The alkyl of straight chain, side chain or ring-type, alkoxyl or alkyl sulfenyl, perhaps monocycle or encircle or condensed ring C more ₆-C ₂₄Aromatic group; Respectively do for oneself 0 to 5 integer of x and y; R ₃And R ₄Be selected from monocycle separately or encircle or condensed ring C more ₆-C ₂₄Aromatic group; And M comprises azo group or metal ingredient.R ₃And R ₄Be preferably selected from C separately ₆To C ₁₀Aromatic group more preferably is selected from phenyl, benzyl, naphthyl, benzamido and benzothiazolyl.R ₁And R ₂Be preferably selected from substituted or unsubstituted C separately _1-10The alkyl of straight chain, side chain or ring-type, alkoxyl or alkyl sulfenyl, perhaps C ₆To C ₁₀Aromatic group.Work as R ₁, R ₂, R ₃Or R ₄For when replacing, replacement can comprise one or more following substituting groups: hydroxyl and slaine thereof; Sulfydryl and slaine thereof; Halogen; Amino, nitro, cyanic acid and amide groups; Carboxyl comprises ester, acid and slaine thereof; Siloyl group; Acrylate group and slaine thereof; Sulfonyl or sulfamoyl; Bound phosphate groups and phosphite ester group.When M is metal ingredient, any suitable metallic element that it can obtain for those of ordinary skills.Generally speaking, metal can be transition metal, although be preferably tellurium or selenium.In one embodiment, aromatic organic compounds is containing metal not basically, although in another embodiment, aromatic organic compounds is containing metal not fully.

Should can also comprise VIA family composition by softening accelerator.Elemental sulfur and polymerised sulphur can be from Elastochem, and (Chardon OH) buys acquisition to Inc..Exemplary sulfur catalyst compound comprises PB (RM-S)-80 elemental sulfur and PB (CRST)-65 polymerised sulphur, respectively can be from Elastochem, and Inc. buys acquisition.Exemplary trade name

Te exemplary catalyst and the product name

selenium catalyst respectively, from RT? Vanderbilt purchase.

Other suitable softening accelerators include but not limited to hydroquinones, benzoquinones class, quinhydrone class, catechol and resorcinol class.

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

Each R wherein ₁, R ₂, R ₃And R ₃Be hydrogen; Halogen; Alkyl; Carboxyl; Its slaine and its ester; Acetate group (acetate) and ester thereof; Formoxyl; Acyl group; Acetyl group; Halo carbonyl; Sulfo group and ester thereof; Halosulfonyl groups; Sulfino (sulfino); The alkyl sulfinyl; Carbamoyl; Haloalkyl; Cyanic acid; Alkoxyl; Hydroxyl and slaine thereof; Amino; Nitro; Aryl; Aryloxy; Aryl alkyl; Nitroso; Acetylamino; Or vinyl.

Other suitable hydroquinone compounds include but not limited to: quinhydrones; The tetrachloro quinhydrones; The 2-chlorohydroquinone; The 2-bromohydroquinone; 2, the 5-dichloro hydroquinone; 2,5-two bromohydroquinones; The tetrabromo quinhydrones; The 2-methylnaphthohydroquinone; The 2-tertiary butylated hydroquinone; 2,5-two amyl hydroquinone; And 2-(2-chlorphenyl) quinhydrones hydrate.

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

Each R wherein ₁, R ₂, R ₃And R ₄Slaine for carboxyl; Acetate group and ester thereof; Hydroxyl; The slaine of hydroxyl; Amino; Nitro; Aryl; Aryloxy; Aryl alkyl; Nitroso; Acetylamino; Or vinyl.

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

Each R wherein ₁, R ₂, R ₃And R ₄Be hydrogen; Halogen; Alkyl; Carboxyl; Its slaine and its ester; Acetate group (acetate) and ester thereof; Formoxyl; Acyl group; Acetyl group; Halo carbonyl; Sulfo group and ester thereof; Halosulfonyl groups; Sulfino (sulfino); The alkyl sulfinyl; Carbamoyl; Haloalkyl; Cyanic acid; Alkoxyl; Hydroxyl and slaine thereof; Amino; Nitro; Aryl; Aryloxy; Aryl alkyl; Nitroso; Acetylamino; Or vinyl.

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

Suitable quinhydrone class comprises one or more compounds and the hydrate thereof that is expressed from the next:

Each R wherein ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇And R ₈Be hydrogen; Halogen; Alkyl; Carboxyl; Its slaine and its ester; Acetate group (acetate) and ester thereof; Formoxyl; Acyl group; Acetyl group; Halo carbonyl; Sulfo group and ester thereof; Halosulfonyl groups; Sulfino (sulfino); The alkyl sulfinyl; Carbamoyl; Haloalkyl; Cyanic acid; Alkoxyl; Hydroxyl and slaine thereof; Amino; Nitro; Aryl; Aryloxy; Aryl alkyl; Nitroso; Acetylamino; Or vinyl.

Other suitable quinhydrone classes comprise that those have the compound of following formula, wherein R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇And R ₈Respectively the do for oneself slaine of carboxyl; Acetate group (acetate) and ester thereof; Hydroxyl; The slaine of hydroxyl; Amino; Nitro; Aryl; Aryloxy; Aryl alkyl; Nitroso; Acetylamino; Or vinyl.

Suitable catechol comprises one or more compounds and the hydrate thereof that is expressed from the next:

Wherein each R1, R2, R3 and R4 are hydrogen; Halogen; Alkyl; Carboxyl; Its slaine and ester thereof; Acetate group and its ester; Formoxyl; Acyl group; Acetyl group; Halo carbonyl; Sulfo group and ester thereof; Halosulfonyl groups; Sulfino (sulfino); The alkyl sulfinyl; Carbamoyl; Haloalkyl; Cyanic acid; Alkoxyl; Hydroxyl and slaine thereof; Amino; Nitro; Aryl; Aryloxy; Aryl alkyl; Nitroso; Acetylamino; Or vinyl.

Suitable resorcinol comprises one or more compounds and the hydrate thereof that following formula is represented:

Each R1 wherein, R2, R3 and R4 are hydrogen; Halogen; Alkyl; Carboxyl; Its slaine and ester thereof; Acetate group and its ester; Formoxyl; Acyl group; Acetyl group; Halo carbonyl; Sulfo group and ester thereof; Halosulfonyl groups; Sulfino (sulfino); The alkyl sulfinyl; Carbamoyl; Haloalkyl; Cyanic acid; Alkoxyl; Hydroxyl and slaine thereof; Amino; Nitro; Aryl; Aryloxy; Aryl alkyl; Nitroso; Acetylamino; Or vinyl.The thermoset rubber composition that can filler be added nuclear is to regulate the density of said composition up or down.Usually, the material below filler for example comprises: tungsten, zinc oxide, barium sulfate; Silica, calcium carbonate, zinc carbonate, metal; Metal oxide and salt, abrasive material (nuclear material of recovery is ground to about 30 purpose particles usually) again; High Mooney (Mooney) bala gutta is abrasive material again, trans (trans-regrind) nuclear material (nuclear material of recovery, it comprises the transisomer of the polybutadiene of a large amount) etc. that grinds again.When having trans abrasive material again, the amount of transisomer is preferably about 10% to about 60%.In a preferred embodiment of the invention, this nuclear comprises the syn-isomerism body burden greater than about 95% polybutadiene and as the trans nuclear material (vulcanizing (vulcanized)) that grinds again of filler.The trans nuclear material that grinds again of any particle diameter all is fully, but it preferably is lower than about 125 μ m.

The filler that adds the one or more parts of this golf generally includes filler, the tearing strength of the processing aid (processing aids) that influences rheology and mixed nature or compound, change density or strengthens filler etc.Said filler is generally inorganic matter, and suitable filler comprises multiple metal or metal oxide, for example zinc oxide and tin oxide and barium sulfate, zinc sulfate, calcium carbonate, brium carbonate, clay, tungsten, tungsten carbide, silicate series, and composition thereof.Filler also can comprise multiple blowing agent or foaming agent (blowing agent), and it can easily be selected by those skilled in the art.Filler can comprise entity or hollow, filling or unfilled polymer, pottery, metal and glass microsphere.Usually the one or more parts that filler added this golf are to change its density to meet the unified standard of golf.Filler also can be used for changing the weight of at least one extra play of center weight or for example special-purpose ball (specialty balls), is preferred for the ball of sportsman's low weight of low slew rate.

Following material for example tungsten, zinc oxide, barium sulfate, silica, calcium carbonate, zinc carbonate, metal, metal oxide and salt and again abrasive material (nuclear material of recovery, usually be ground to about 30 order particles), also be suitable filler.

Polybutadiene and/or any other base rubber (base rubber) or elastomer system (elastomer system); Can also foam or fill with tiny balloon or expandable microballoon, said expandable microballoon in solidification process in the temperature expansion of setting to any low-gravity level.Other compositions for example the sulphur accelerator (for example two, three or tetramethylthiuram tetrasulfide (tetramethylthiuram di, tri, tetrasulfide)) and/or metallic organic sulfur composition also can be used according to the invention.Suitable metallic organic sulfur accelerator includes but not limited to: the DECTC of cadmium, copper, lead and tellurium analog, diamyl dithiocarbamate salt and dimethyl dithio carbamate, or its mixture.Other compositions, for example (for example aliphatic acid and/or its slaine, processing also can be to be enough to realizing that the amount of purpose that its use is usually reached is used for the present invention with oil, dyestuff and pigment and other additives well known by persons skilled in the art for processing aid.

Be not limited to theory, think anti-configuration two keys percentage can whole contain to control at least one main chain unsaturated rubber (being polybutadiene), plastics or the elastomeric nuclear cause trans component gradient.The type of co-reagent (coagent) and amount in the type of type that can be through changing cis to trans catalyst (or softening accelerator (soft-and-fast agent)) and amount, peroxide and amount and the formulation and influence trans gradient up or down.For example, the formulation that contains about 0.25phr ZnPCTP can have the about 5% trans gradient of passing nuclear, and the preparation that contains about 2phr ZnPCTP can have about 10% or higher trans gradient.Trans gradient also can be controlled through hardening time and temperature.Think lower temperature and short hardening time can produce lower trans gradient, although the combination of a plurality of these factors can produce and use the resulting different and/or rightabout gradient of single factors.

The percentage of transisomer also can be controlled through in the nuclear formulation, adding organosulfur compound (cited for example) in the nuclear, and said organosulfur compound includes but not limited to pentachloro-thiophenol, pentachloro-thiophenol zinc, xylyl disulphide (ditolyl disulfide) and diphenyl disulphide.The amount of this organosulfur compound and the overall status of curing influence the amount of the transisomer that produces in the solidify reaction process.The another kind of method that in nuclear, increases trans content is in the nuclear formulation, to introduce unsaturated rubber, the transisomer of said unsaturated rubber contained high levels (what for example contain the polybutadiene of high trans or contain high trans gathers octene (polyoctenamer)).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 peroxide of higher concentration, softening accelerator and the effect that produced of ZDA concentration in a way.Even the type of rubber can have influence to trans level, and those and those rubber phase ratios that formed by VIII family metal (for example Co, Ni and Li) by rare earth metal (for example Nd) catalysis can form higher levels of trans polybutadiene.

The measurement of the polybutadiene trans-isomer content of the application's indication is, and can accomplishes as follows.Prepare calibration standard with at least two kinds of known polybutadiene rubber samples of trans content (for example high and low-antiform percentage polybutadiene).These samples use separately or mix to produce the trans polybutadiene content ladder at least about 1.5% to 50% with such form, and perhaps folder is drawn together (bracket) unknown amount, thereby the calibration curve of gained contains at least about 13 equally spaced points.

Use is equipped with the commercial available FTIR spectrometer of Photoacoustic (" PAS ") cell (cell); Instrument parameter below using obtains the PAS spectrum of each standard: sweep speed 2.5KHZ (0.16cm/s optics speed); Use the 1.2KHz electronic filter, it is 2 (before collecting sample, the number that laser signal 0 passes through) that the undersampling ratio is set; Altogether-add (co-add) minimum 128 scannings, 375 to 4000cm ^-1The scope intermediate-resolution be 4cm ^-1, sensitivity is set to 1.

Cis in the PAS spectrum, trans and vinyl-polybutadiene peak are shown in 600-1100cm ^-1Between.Area under each trans polybutadiene peak of integrable.Confirm the mark of each peak area, allow to make up the calibration curve of the actual relatively trans polybutadiene content of trans polybutadiene peak area mark with respect to three isomers peak gross areas.Gained correlation coefficient of calibration curve (R ²) must be minimum 0.95.

The unknown nuclear material of locating for interested point (for example nuclear surface or center); Sample through with the untainted surface of containing the no allogenic material (the for example demoulding (mold release) etc.) that has just downcut is filled the PAS cell, uses above-mentioned parameter to obtain the PAS spectrum.Analyze unknown trans polybutadiene area fraction to confirm actual trans-isomer content from said calibration curve.

Under a kind of known situation that comprises barium sulfate, the said method that detects trans content maybe be than inaccuracy.Therefore, the other or optional test of the trans content of polybutadiene is following.Prepare calibration standard with at least two kinds of known polybutadiene (for example high and low-antiform polybutadiene percentage) of trans component content.These samples use separately or mix by this way to produce the ladder at least about 1.5% to 50% trans polybutadiene content, and perhaps folder is drawn together unknown amount, thereby the calibration curve of gained contains at least 13 equally spaced points.

Use is equipped with the FT-Raman spectrometer of near-infrared laser, and the instrument parameter below using obtains Stokes Raman spectrum from each reference material: sufficient laser power (laser power) (400-800mW usually) does not cause excessive heating or fluorescence to obtain good signal-to-noise; Resolution ratio 2cm ^-1At 400-4000cm ^-1Raman shift in the spectral limit (shift spectral range); With interpolation at least 300 scannings altogether.

Can use stoechiometric process and software (for example from Galactic Industries Corp PLSplus/IQ) to make up calibration curve through the data of top generation.Utilize this software to use PLS-1 curve, average centre data preparation (mean center data preparation) and the spectral limit of the generation of SNV (detrend) optical path length correction to be 1600-1700cm ^-15-point SG secondary derivative (second derivative), obtain acceptable standard.Gained correlation coefficient of calibration curve (R ²) must be minimum 0.95.

Preferably, it is about 1% to 10% that the geometric center of nuclear has, and more preferably 2% to 9%, and 4% to 8% trans component content most preferably.It is about 5% to 15% that the outer surface of this nuclear preferably has, and more preferably from about 7% to 12%, and 8% to 10% trans content most preferably from about.It is about 5% to 16% that half-radius in this nuclear (half-radius) point preferably has, and more preferably from about 6% to 14%, and 7% to 13% trans component content most preferably from about.

The nuclear that is suitable for most golf of the present invention has outer surface and center, and by basically uniformly rubber compsn form.Put around caryogamy in intermediate layer (for example cover layer (inner cover)); And cover layer forms around in the intermediate layer, and covering (cover) is formed by pourable polyureas or polyurethane usually and (promptly refers to comprise pourable polyureas (100% urea connects base/no carbamate and connects base), pourable polyurethane (100% carbamate connects base/no urea and connects basic), pourable heterozygosis and gather (ammonia ester/urea) (prepolymer all is that the carbamate connection is basic and solidify with amine); The cover layer that gathers (urea/ammonia ester) (prepolymer all is that urea is connected base and solidifies with polyalcohol) with pourable heterozygosis).In a preferred embodiment; The outer surface of this nuclear has about 6% to 10% trans polybutadiene content; The center of this nuclear has about 1% to 3% trans polybutadiene content; And the trans component content of the outer surface that should examine Duos about 6% or more than the trans component content at center; To confirm pros-and-cons type component gradient (positive trans gradient) (be that surperficial trans component content is higher than the trans component content in center---the nuclear with opposite configuration of trans component content is considered to have the trans component gradient of negativity (negative trans gradient), and also contains in this application) along nuclear radius.

The present invention preferably includes the nuclear that comprises at least one simple layer, and this nuclear has " soft gradient " prescription and cure cycle, and it is defined as " LOG " nuclear in this article.This type of LOG endorses has " just " Shore C hardness gradient (be defined as: nuclear case hardness deduct the hardness of geometric center) of about 1 Shore C to about 10 Shore C; More preferably for about 2 Shore C to being 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 nuclear comprises more than one deck, the center that for example centers on by outer nuclear layer, and any one of these layers or both can have low (or shallow) " just " hardness gradient.

Ball of the present invention preferably comprises LOG nuclear and cover layer at least.Randomly, there are one or more intermediate layers between nuclear and the cover layer.More preferably, have about 1.45 to 1.62 inches, more preferably the individual layer LOG nuclear of about 1.50 to 1.58 inches and most preferably about 1.51 to 1.55 inches diameter is by two cover encloses.Inner covering layer preferably by ionomer polymeric material (ionomeric material) (for example have about 60 Shore D or more high rigidity the conventional ion cross-linked polymer or the height/fully the neutralization ionomer) process.Outer cover is preferably by having about 60 Shore D or more polyurethane, polyureas or its mixture of soft, or its copolymer or hybridization thing are processed.In this most preferred embodiment; Said LOG nuclear has about 70 to 80 Shore C, the more preferably geometric center hardness of about 72 to 78 Shore C, and about 71 to 88 Shore C, the case hardness of about 73 to 80 Shore C and more preferably about 74 to 78 Shore C more preferably.About 50 to 90, more preferably about compression of 60 to 80 (Atti) that said LOG nuclear also preferably has, and about 10% or lower surperficial trans-polybutadiene content and in geometric center about 8% or lower trans-polybutadiene content.

Optional intermediate layer is maybe be relatively hard (at least about 85, preferably at least about 90 Shore C hardness; With at least about 61, preferably at least about 63 Shore D hardness) or softer relatively (about 85 or lower, preferably about 83 or lower Shore C hardness and about 61 or lower, preferably about 57 or lower Shore D hardness).The intermediate layer can comprise thermoplasticity or thermosetting polymeric compositions.Thermoset composition comprises the composition based on diene rubber, the for example PBR of peroxide or sulfur curable, SBR, EPDM, NR etc., or polyurethane, polyureas, epoxy, carbamate-acrylic acid ester etc.Thermoplastic comprises ionomer, non--ionomer, polyester, polyamide, PEBAX or HYTREL TPE ' s and styrene-structure block copolymer (SBS, SEBS etc.).

Cladding material can be with disclosed suitable intermediate layer material identical materials and even can comprise LOG or zero-or low-hardness-gradient rubber compounding/curing, but preferably include ionomer, polyurethanes, or polyureas.Said cover layer can firmly can be soft, and its hardness number such as above-mentioned intermediate layer are said.

Single (preferably), multilayer, or polylith endorse 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 most preferably about 1.3 to 1.58 inches diameter.The combination in LOG nuclear and intermediate layer preferably has about 1.0 to 1.66 inches, more preferably about 1.25 to 1.64 inches and most preferably about 1.40 to 1.62 inches external diameter.Cover layer preferably has about 0.010 to 0.080 inch, more preferably about 0.015 to 0.060 inch and most preferably about 0.020 to 0.040 inch thickness.

Normally, when using harder cover layer, usually it is combined with soft relatively intermediate layer, to produce the low relatively golf of rotation.When using softer cover layer, usually it is combined with hard relatively intermediate layer, have the more golf of high slew rate to produce than to use hard tectal same configuration.In another embodiment, hard cover layer can use or soft cover layer can use with soft intermediate layer with hard intermediate layer.Should be understood that term " firmly " is meant 55 or higher Shore D hardness, term " soft " is meant 45 or lower Shore D hardness; " common " hardness should be 45 to 55 Shore D.

Another preferred embodiment in, this golf comprises three layers.LOG nuclear preferably has shallow " just " hardness gradient of about 1 to 5 Shore C, about 1.55 inches diameter, about compression of 50 to 100, preferably 65 to 85 and about 0.800-0.815, the COR of 0.800-0.810 preferably.Said intermediate layer is processed by the composition based on the thermoplasticity ionomer with about 80 Shore C hardness and about 1.60 inches external diameters.Single cover layer is processed by the ionomer of about 0.040 inch thickness and about 66 Shore D hardness.The embodiment at another low compression center can comprise having about 1 to 50, about 10 to 40, the center of about compression of 15 to 35 most preferably more preferably.

Nuclear of the present invention also can have and is lower than approximately 160, more preferably, and about 40 to about 160 and more preferably, about 60 to about 120 soft center tilt index (Soft Center Deflection Index, " SCDI ") compression.

Said SCDI is the program change of dynamic compressors (" DCM "), and it allow to measure the 10% required poundage that will examine its diameter of deflection.Said DCM be a kind of to nuclear or spheroid apply load and measure nuclear or spheroid at the instrument of the inch number of the load deflect that records.Obtain thick load/deflection curve, it is fit to said Atti compression yardstick, obtain representing the numerical value of Atti compression.Said DCM carries out through the load unit that is connected to the hydraulic cylinder bottom, and said hydraulic cylinder pneumatically triggers to fixing nuclear with fixing speed (typically about 1.0ft/s).LVDT is connected to hydraulic cylinder, and it measures the distance of hydraulic cylinder motion in the testing time scope.Guarantee in the test incipient stage based on the Logarithmic Algorithm of software, detect and begin to measure after at least 5 continuous loads increase.

Said SCDI is the modification a little of this setting.Hardware is identical, but has changed software and output.Use said SCDI, concern be the required power (in pound) of deflection nuclear x inch.Amount of deflection is 10% of a said nuclear diameter.Trigger DCM, said hydraulic cylinder makes 10% of its diameter of nuclear deflection, the power (in pound) (load unit as connecting is surveyed) that DCM repayment simultaneously is required with the said amount of said nuclear deflection.Show value is the single numerical value in pound.

Perhaps; The LOG of above-mentioned embodiment nuclear has about 1.450 inches diameter, and is loaded into the intermediate layer of being processed by non--ionomer thermoplastic (being that PEBAX type ester-acid amide makes up block copolypeptide) with about 40 Shore D hardness and about 1.580 inches external diameters.Preferred cover layer is the ionomer cover layer with about 68 Shore D hardness and about 0.050 inch thickness.

Another preferred embodiment in, this golf comprises four layers.Said nuclear is processed by aforesaid LOG prescription and is had about 1.50 inches external diameter.This golf comprises two-layer intermediate layer, respectively has about 0.060 inch thickness.Innermost intermediate layer preferably has the hardness of about 45 Shore D, and outmost intermediate layer has the hardness of about 66 Shore D.Cover layer has about 0.030 inch thickness, and is processed by thermosetting, cast based polyurethane or polyureas, and has the hardness of about 53 Shore D.

The 4th preferred embodiment in, this golf comprises four layers.This nuclear comprises a LOG center and an outer nuclear layer with about 1.0 inch diameters.Said outer stratum nucleare has the case hardness of about 1.540 inches external diameter and about 89 to 92 Shore C.Said outer nuclear layer by " conventional " polybutadiene rubber prescription but not the LOG prescription process.Said intermediate layer is by the hardness of processing and have about 1.62 inches external diameter and about 67 Shore D based on the material of ionomer.The hardness that about 45 Shore D were processed and had to said cover layer by the polyurethane or the polyureas of casting.

The hardness of the outer surface of said nuclear can be lower than the hardness of geometric center, with limit approximately-1 to approximately-15, about-5 to-10 negative hardness gradient more preferably.The outer surface of said nuclear can have about 68 hardness to about 80 Shore C, and said geometric center has the hardness of about 68 to 80 Shore C.Also can be in the hardness that records of outer surface of nuclear greater than the hardness at nuclear center,, more preferably about 2 to 5 positive hardness gradient about 0 to 5 to limit.This nuclear preferably has about 1.5 inches to 1.59 inches, more preferably about 1.51 to 1.57 inches, most preferably about 1.51 inches to 1.55 inches, specifically comprises the diameter of 1.51 inches, 1.53 inches or 1.55 inches.

Customizable above-mentioned embodiment is to satisfy default capabilities.For example, another embodiment comprises those with kernel, said kernel have about 0.250 inch to about 1.550 inches, preferably about 0.500 inch to about 1.500 inches and more preferably about 0.750 inch to about 1.400 inches external diameter.In preferred embodiment, said kernel has the external diameter of about 1.000 inches, 1.200 inches or 1.300 inches, and most preferred external diameter is 1.130 inches.Said outer nuclear layer should have about 1.30 inches to about 1.620 inches, preferably 1.400 inches to about 1.600 inches and more preferably about 1.500 inches to about 1.590 inches external diameter (whole two-layer core).In preferred embodiment, said outer nuclear layer has about 1.510 inches, 1.530 inches or 1.550 inches external diameter most preferably.

Form many nuclears according to prescription described in the following table 1 and cure cycle, and said nuclear hardness number is as shown in table 2 below.

Table 1

Prescription (phr)	Instance 1	Instance 2	Instance 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
							BaSO ₄	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	-
							Polybutadiene	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 anti-oxidant/initator	0.57	0.57	0.50		0.31	-
							Solidification temperature (° F)	305	315	320	350	335	335
Hardening time (min)	14	11	16	11	11	11

Characteristic
							Diameter (in)	1.530	1.530	1.530	1.530	1.530	1.530
The Atti compression	69	63	70	69	47	-
							COR125ft/s	0.808	0.806	0.804	0.804	-	-

^*Vanox MBPC:2,2 '-methylene-two-(4-methyl-6-tert butyl phenol), can derive from R.T.Vanderbilt Company Inc; ^*Trigonox 265-50B:1,1-two (t-butyl peroxy)-3,3, the mixture of 5-trimethyl-cyclohexane and two (2-t-butyl peroxy isopropyl) benzene, 50% activity on inert carrier, can derive from Akzo Nobel; ^{* *}Perkadox BC-FF: dicumyl peroxide (99%-100% is active) can derive from Akzo Nobel; And ⁺SR-526:ZDA can derive from Sartomer

Table 2

Prepare multiple nuclear, and carried out striding the hardness measurement of nuclear.The nuclear that is called instance 1-4 in the hereinafter table 3 all has 1.53 inches external diameter.Measured Shore C hardness according to ASTM D-2240 in a plurality of positions of striding the nuclear cross section.Hereinafter is with geometric center, outer surface, and from the geometric center hardness result tabulation of 2mm, 4mm, 6mm, 8mm, 10mm, 12mm, 14mm, 16mm and 18mm position radially outward of nuclear.The general purpose core prescription comprises>=85phr CB1221 polybutadiene rubber ,≤abrasive material again of 15phr CB23 polybutadiene rubber, about 35phr dizinc acrylate resin (zinc diacrylate), about 1phr peroxide, about 0.5phrVANOX MBPC, about 5phr ZnO, about 0.5phr ZnPCTP, about 1phrAFLUX 16, about 13phrPOLYWATE 325 and about 15phr.Adjust cure cycle passes nuclear with change hardness gradient where necessary.Temperature/time standard changes between about 330 ° of F/20min, 335 ° of F/18min, 340 ° of P/16min and 345 ° of F/14min.

Table 3

The hardness gradient scope of in preceding text table 3, seeing is 1.5 to 4.3 Shore C.These are shallow positive gradients, and are that hardness through the nuclear surface deducts the hardness at geometric center place and definite.

Also to the nuclear that forms from same general prescription mentioned above tested % cis-polybutadiene, % trans-polybutadiene and % vinyl-polybutadiene.Presented the result in the hereinafter table 4.

Table 4

Nuclear	% is trans	The % vinyl	The % cis
				Instance E outer surface	7.6	2.7	89.6
Instance E half radius	7.8	2.8	89.4
				Instance E center	7.4	2.8	89.7

				Instance F outer surface	9.2	2.7	88.4
Instance F half radius	13.2	2.6	85.4
				Instance F center	8.5	2.9	88.6

				Instance G outer surface	8.7	2.8	88.5
Instance G half radius	12.6	2.6	85.7
				Instance G center	7.3	2.6	90.1

Nuclear E-G in the preceding text table 3 represents the shallow trans-polybutadiene gradient of nuclear center to the surface.

The case hardness of nuclear is to obtain from the mean value of repeatedly measuring to the relative hemisphere of nuclear, carefully avoids on the die parting line of nuclear or on blemish (such as hole or projection), measures.Hardness measurement is to carry out according to ASTM D-2240 " rubber of measuring through hardometer and the identation hardness (Indentation Hardness of Rubber and Plastic by Means of a Duromete r) of plastics ".Because the curved surface of nuclear is taken every caution against error and is guaranteed that nuclear is placed in the middle under penetrator before obtaining the case hardness reading.Use through digital hardometer calibration, that can read 0.1 stiffness units and carry out all hardness measurements, and be arranged to obtain the hardness reading of acquisition full-scale reading in the time of 1 second afterwards.The numeral hardometer must be connected to the base portion of automatic station and make its base parallel with the base portion of automatic station, makes that weight and the impact speed on the hardometer meets ASTM D-2240.

In order to prepare to be used for the nuclear that hardness gradient is measured, lightly nuclear is pressed into internal diameter roughly than the smaller hemisphere clamper of diameter of nuclear, make nuclear be fixed in the hemispherical portion of clamper, make the geometric center plane of nuclear expose simultaneously.Nuclear is fixed in the clamper through frictional force, make it can during cutting and grinding steps, not move, but frictional force is inexcessive, can not cause the natural shape distortion of examining.Nuclear is fixed, thereby makes that the die parting line of nuclear is roughly parallel with the top of clamper.Before fixing, to be orientated to the diameter that 90 degree are measured nuclear with this.Also measure and proceed to the nuclear top so that the following reference point that calculates to be provided from clamp base.Use band saw or other suitable cutting tools above the geometric center that nuclear exposes is omited, to carry out rough cutting, guarantee in clamper, not move at this step center.The remainder of the nuclear in clamper still is fixed in the substrate of surface grinding machine.It is the smooth surface of putting down that " coarse " nuclear surface that exposes is ground; The geometric center of exposing nuclear; It can be verified through measuring clamp base to the surface height that nuclear exposes, and guarantees to remove the just in time half the to ± 0.004 inch of as above measured nuclear original height.

Nuclear is stayed in the clamper, found the center of nuclear, and mark carefully, and measure hardness at this centre mark place with centre square.Apart from the hardness measurement of any distance in nuclear center can through from centre mark setting-out radially outward and measure and mark from the distance at center, be spaced apart 2mm usually, measure.All hardness measurements that the plane of passing geometric center is carried out are carried out when said nuclear is thrown away in clamper, do not upset its orientation, thereby make test surfaces always parallel with clamp base.Difference of hardness from any precalculated position of nuclear is calculated as the hardness that average surface hardness deducts suitable reference point, and is for example single, the center of entity nuclear, thus make that the nuclear surface softer than its center can have negative hardness gradient.

With reference to table 1-2, in embodiment 1, the surface ratio core rigidities hang down 10 Shore C, and hangs down 12 Shore C than hard spot in the nuclear.In embodiment 3, the surface ratio core rigidities hangs down 5 Shore C, and than the low 8 Shore C of hard spot in the nuclear.In embodiment 2, center and case hardness equate, and the low 10 Shore C of soft spots specific surface in the nuclear.

In the embodiments of the invention that in table 1, appear, solidification temperature changes from 305 ° of F to 320 ° of F, and change from 11 to 16 minutes hardening times.It is identical that embodiment 1 forms with 2 nuclear, and only cure cycle changes.In embodiment 3, identical in the amount of anti-oxidant and embodiment 1 and 2, but other compositions and cure cycle have change.In addition, anti-oxidant changes to 0.57 from 0.50 from embodiment 1 and 2 to embodiment 3 ratio of initator.

Anti-oxidant is the factor of a control nuclear case hardness to the ratio of initator.The data that are shown in table 2 show that hardness gradient is at least but is not limited to the amount of anti-oxidant and peroxide, the function of its ratio and cure cycle.Should point out that higher anti-oxidant also needs higher peroxide initiator to keep required compression.

The nuclear of comparative example 1, its composition is shown in table 1, is to use conventional cure cycle to solidify, and solidification temperature is 350 ° of F and be 11 minutes hardening time.Nuclear of the present invention is to use 305 ° of F to carry out 14 minutes, and the cure cycle that 315 ° of F carried out 11 minutes and 320 ° of F carried out 16 minutes produces.Measure the hardness gradient of these nuclears and carried out observation.For the nuclear in the comparative example, like expection, obviously visible conventional crust arrives the gradient at soft center.The gradient of nuclear of the present invention is followed identical shaped basically each other.

In all embodiment preferred of the present invention, the hardness of nuclear on the surface approximates at most or is remarkable in the hardness of nuclear at the center.In addition, the core rigidities of nuclear possibly not be the hardest point in the nuclear, but in all cases, be preferably equal at least or specific surface harder.In some embodiments, the lowest hardness value betides among about nuclear surface 6mm in the outer part.Yet the lowest hardness value in the nuclear can betide any point on distance surface, but does not comprise the center, as long as case hardness still is equal to or less than core rigidities.Should point out that in the present invention prescription is identical in nuclear and stratum nucleare, and nuclear is not imposed surface treatment to obtain preferred case hardness.

Although golf of the present invention can be formed by multiple difference and conventional cladding material (intermediate layer and outer cover), preferred cladding material includes but not limited to:

(1) polyurethane, from polyalcohol or polyamines and vulcabond or polyisocyanates and/or the preparation of its prepolymer, and those are disclosed in United States Patent(USP) No. 5,334 such as those, 673 and 6,506,851;

(2) polyureas is disclosed in United States Patent(USP) No. 5,484 such as those, 870 and 6,835,794; And

(3) comprise polyurethane-urea hybridization thing, blend or the copolymer of carbamate or urea segment.

Suitable urethane composition comprises the product of at least a polyisocyanates and at least a curing agent.Curing agent can comprise for example one or more polyamines, one or more polyalcohols or their combination.Can polyisocyanates and one or more polyalcohols be made up to form prepolymer, then with this prepolymer and the combination of at least a curing agent.So, polyalcohol described herein is adapted at using in one or both of two kinds of compositions of polyurethane material (promptly as the part of prepolymer or in curing agent, use).Suitable polyurethane is recorded in the open text No.2005/0176523 of U.S. Patent application, through addressing its complete including.

Any polyisocyanates that those of ordinary skills can get is fit to use according to the present invention.The polyisocyanates of exemplary includes but not limited to 4,4 '-methyl diphenylene diisocyanate (MDI); Polymeric MDI; The liquid MDI of carbodiimide modified; 4,4 '-dicyclohexyl methyl hydride diisocyanate (H12MDI); Right-phenylene vulcabond (PPDI); Between-phenylene vulcabond (MPDI); Toluene di-isocyanate(TDI) (TDI); 3,3 '-dimethyl-4,4 '-diphenylene vulcabond; IPDI; 1,6-hexamethylene diisocyanate (HDI); Naphthalene diisocyanate; XDI; Right-tetramethylxylene diisocyanate; Between-tetramethylxylene diisocyanate; Ethylidene diisocyanate; Propylidene-1, the 2-vulcabond; Tetramethylene-1, the 4-vulcabond; Cyclohexyl diisocyanate; Dodecane-1, the 12-vulcabond; Cyclobutane-1, the 3-vulcabond; Cyclohexane-1, the 3-vulcabond; Cyclohexane-1, the 4-vulcabond; 1-NCO-3,3,5-trimethyl-5-NCO hexahydrotoluene; Methyl cyclohexylidene vulcabond; The triisocyanate of HDI; 2,4,4-trimethyl-1, the triisocyanate of 6-hexane diisocyanate; Aphthacene vulcabond (tetracene diisocyanate); Naphthalene two isocyanic acids; Anthracene two isocyanic acids; The isocyanide urea of toluene diisocynate; The uretdione of hexa-methylene two isocyanic acids; And composition thereof.Those of ordinary skills know that polyisocyanates has an isocyanate groups, for example di-isocyanate, tri-isocyanate and the four-isocyanates of surpassing.Preferably, polyisocyanates comprises MDI, PPDI, TDI or its mixture, and more preferably, polyisocyanates comprises MDI.Should be appreciated that term MDI comprises 4 like what use among this paper; The liquid MDI of 4 '-methyl diphenylene diisocyanate, polymeric MDI, carbodiimide modified, and their mixture; And in addition, the vulcabond of employing can be " low free monomer "; Those of ordinary skills are interpreted as " dissociating " the monomeric diisocyanate group with reduced levels, are less than about 0.1% free monomer isocyanate groups usually.The instance of " low free monomer " vulcabond includes but not limited to low free monomer MDI, low free monomer TDI and low free monomer PPDI.Said at least a polyisocyanates should have and is less than about 14% unreacted NCO group.Preferably, said at least a polyisocyanates has no more than about 8.0%NCO, and more preferably no more than about 7.8% and most preferably no more than about 7.5%NCO, normally used NCO level is about 7.2% or 7.0% or 6.5% NCO.

Any polyalcohol that those of ordinary skills can get is fit to use according to the present invention.The polyalcohol of exemplary includes but not limited to PPG, hydroxyl terminated poly-butadiene (derivative that comprises part/complete hydrogenation), PEPA, polycaprolactone polyol and polycarbonate polyol.In a preferred embodiment, polyalcohol comprises PPG.Instance include but not limited to polytetramethylene ether diol (PTMEG), polyethylene glycol propane diols, polyoxy trimethylene glycol, and composition thereof.Hydrocarbon chain can have saturated or unsaturated key and substituted or unsubstituted aromatic series and cyclic group.Preferably, polyalcohol of the present invention comprises PTMEG.

In another embodiment, comprise PEPA in the polyurethane material.Suitable PEPA includes but not limited to the polyethylene glycol adipate glycol; The poly adipate succinic acid ester glycol; Polyethylene glycol adipate propylene glycol ester glycol; O-phthalate ester-1, the 6-hexylene glycol; Gather (adipic acid hexylene glycol ester) glycol; And composition thereof.Hydrocarbon chain can have substituted or unsubstituted aromatic series of saturated or unsaturated key and cyclic group.

In another embodiment, comprise polycaprolactone polyol in the material of the present invention.Suitable polycaprolactone polyol includes but not limited to 1; The polycaprolactone, 1 that the polycaprolactone that the polycaprolactone that the polycaprolactone that the 6-hexylene glycol causes, diethylene glycol (DEG) cause, trimethylolpropane cause, dimethyltrimethylene glycol cause, the polycaprolactone that the 4-butanediol causes, and composition thereof.Hydrocarbon chain can have substituted or unsubstituted aromatic series of saturated or unsaturated key and cyclic group.

In also having an embodiment, comprise polycarbonate polyol in the polyurethane material of the present invention.Suitable Merlon includes but not limited to gather carbonic acid O-phthalic ester and gathers (carbonic acid hexylene glycol ester) glycol.Hydrocarbon chain can have substituted or unsubstituted aromatic series of saturated or unsaturated key and cyclic group.In one embodiment, the molecular weight of polyalcohol is about 200 to about 4000.

Polyamine curing agent also is adapted at using in the urethane composition of the present invention, and has been found that anti-cutting, shear resistant and the impact resistance of improving the gained ball.Preferred polyamine curing agent includes but not limited to 3,5-dimethyl sulfenyl-2,4-toluenediamine and isomers thereof; 3,5-diethyl Toluene-2,4-diisocyanate, 4-diamines and isomers thereof, such as 3,5-diethyl Toluene-2,4-diisocyanate, 6-diamines; 4,4 '-two-(second month in a season-butyl is amino)-diphenyl methane; 1,4-two-(second month in a season-butyl is amino)-benzene, 4,4 '-methylene-two-(2-chloroaniline); 4,4 '-methylene-two-(3-chloro-2,6-diethylaniline); Polytetramethylene oxygen-two-p-amino benzoic Acid; N, N '-dialkyl diamines diphenyl methane; P, p '-methylene dianiline (MDA); The m-phenylenediamine; 4,4 '-methylene-two-(2-chloroaniline); 4,4 '-methylene-two-(2, the 6-diethylaniline); 4,4 '-methylene-two-(2, the 3-dichloroaniline); 4,4 '-diaminourea-3,3 '-diethyl-5,5 '-dimethyl diphenylmethane; 2,2 ', 3,3 '-tetrachloro diaminodiphenyl-methane; Trimethylene two-p-Aminobenzoate; And composition thereof.Preferably; Curing agent of the present invention comprises 3; 5-dimethyl sulfenyl-2,4-toluenediamine and isomers thereof are such as

300; Can available from Albermarle Corporation (Baton Rouge, LA).The molecular weight that suitable polyamines (comprising primary amine and secondary amine) curing agent preferably has scope about 64 to about 2000.

Can be added into urethane composition mentioned above with at least a in glycol, triol, tetrol or the hydroxy-end capped curing agent.Suitable glycol, triol and tetrol group comprise ethylene glycol; Diethylene glycol; Polyethylene glycol; Propane diols; Polypropylene glycol; The lower molecular weight polytetramethylene ether diol; 1, and 3-two (the 2-hydroxyl-oxethyl] benzene; 1,3-two-[2-(2-hydroxyl-oxethyl) ethyoxyl] benzene; 1,3-two-{ 2-[2-(2-hydroxyl-oxethyl) ethyoxyl] ethyoxyl } benzene; 1, the 4-butanediol; 1, the 5-pentanediol; 1, the 6-hexylene glycol; Resorcinol-two-(beta-hydroxy ethyl) ether; Quinhydrones-two-(beta-hydroxy ethyl) ether; And composition thereof.Preferred hydroxy-end capped curing agent comprises 1,3-two (2-hydroxyl-oxethyl) benzene; 1,3-two-[2-(2-hydroxyl-oxethyl) ethyoxyl] benzene; 1,3-two-{ 2-[2-(2-hydroxyl-oxethyl) ethyoxyl] ethyoxyl } benzene; 1, the 4-butanediol, and composition thereof.Preferably, to have scope be about molecular weight of 48 to 2000 for hydroxy-end capped curing agent.Should be appreciated that molecular weight is the absolute weight mean molecule quantity, will appreciate that as those of ordinary skills like what use among this paper.

Hydroxy-end capped curing agent and amine hardener all can comprise the group of one or more saturated, undersaturated, aromatic and ring-types.In addition, hydroxy-end capped curing agent and amine hardener can comprise one or more halogen groups.Can form urethane composition with the mixture or the admixture of several kinds of curing agent.Yet, when needed, can form urethane composition with single curing agent.

In a preferred embodiment of the invention, use saturated polyurethane to form one or more cover layers, preferred outer cover, and can be selected from pourable thermosetting and thermoplastic polyurethane.In this embodiment, saturated polyurethane of the present invention does not have aromatic group or part on basically.The saturated polyurethane that is fit to use in the present invention is the product of the reaction between at least a polyurethane prepolymer and at least a saturated curing agent.Polyurethane prepolymer is the product that forms through the reaction between at least a saturated polyalcohol and at least a saturated vulcabond.As well known in the art, can adopt catalyst to promote curing agent and isocyanates and polyalcohol, the perhaps reaction between curing agent and the prepolymer.

Operable saturated vulcabond includes but not limited to ethylidene diisocyanate; Propylidene-1, the 2-vulcabond; Tetramethylene-1, the 4-vulcabond; 1,6-hexamethylene diisocyanate (HDI); 2,2, the 4-trimethyl hexamethylene diisocyanate; 2,4, the 4-trimethyl hexamethylene diisocyanate; Dodecane-1, the 12-vulcabond; Dicyclohexyl methyl hydride diisocyanate; Cyclobutane-1, the 3-vulcabond; Cyclohexane-1, the 3-vulcabond; Cyclohexane-1, the 4-vulcabond; 1-NCO-3,3,5-trimethyl-5-NCO hexahydrotoluene; Different phorone vulcabond; Methyl cyclohexylidene vulcabond; The triisocyanate of HDI; 2,2,4-trimethyl-1, the triisocyanate of 6-hexane diisocyanate.Most preferred saturated vulcabond is 4,4 '-dicyclohexyl methyl hydride diisocyanate and different phorone vulcabond.

The saturated polyalcohol that is fit to use in the present invention includes but not limited to PPG such as polytetramethylene ether diol and gathers (oxygen propylidene) glycol.Suitable saturated PEPA comprises the polyoxy trimethylene glycol of polyethylene glycol adipate glycol, polyethylene glycol adipate propylene glycol ester glycol, poly adipate succinic acid ester glycol, polycarbonate polyol and oxirane capping.Useful in the present invention saturated polycaprolactone polyol comprises the polycaprolactone, 1 that diethylene glycol (DEG) causes, the polycaprolactone, 1 that the 4-butanediol causes, the polycaprolactone that the 6-hexylene glycol causes; The polycaprolactone that polycaprolactone that the polycaprolactone that trimethylolpropane causes, dimethyltrimethylene glycol cause and polytetramethylene ether diol cause.Most preferred saturated polyalcohol is the polycaprolactone that polytetramethylene ether diol and PTMEG cause.

Suitable saturated curing agent comprises 1,4-butanediol, ethylene glycol, diethylene glycol (DEG), polytetramethylene ether diol, propane diols; Trihydroxymethyl propane; Four-(2-hydroxypropyl) ethylenediamines; The isomers of cyclohexyl dimethanol and isomer mixture, the isomers and the isomer mixture of cyclohexane two (methyl amine); Triisopropanolamine; Ethylenediamine; Diethylenetriamines; Trien; Tetren; 4,4 '-dicyclohexyl methanediamine; 2,2,4-trimethyl-1,6-hexamethylene diamine; 2,4,4-trimethyl-1,6-hexamethylene diamine; Diethylene glycol (DEG) two-(aminopropyl) ether; 4,4 '-two-(second month in a season-butyl is amino)-dicyclohexyl methyl hydride; 1,2-two-(second month in a season-butyl is amino) cyclohexane; 1,4-two-(second month in a season-butyl is amino) cyclohexane; Different phorone diamines; Hexamethylene diamine; Propane diamine; 1-methyl-2,4-cyclohexyl diamines; 1-methyl-2,6-cyclohexyl diamines; 1, the 3-diaminopropanes; Dimethylamino propylamine; Diethyl amino propylamine; Imino group-two-propylamine; The isomers of DACH and isomer mixture; MEA; Diethanol amine; Triethanolamine; Monoisopropanolamine; And diisopropanolamine (DIPA).Most preferred saturated curing agent is 1,4-butanediol, 1, and 4-cyclohexyl dimethanol and 4,4 '-two-(second month in a season-butyl is amino)-dicyclohexyl methyl hydride.

Perhaps, other suitable polymers comprise partially or completely ionomer, metallocene or other single site catalysed of neutralization polymer, polyester, polyamide, nonionic cross-linked polymer thermoplastic elastomer (TPE), copolymerization ether-ester, copolymerization ether-amide, Merlon, polybutadiene, polyisoprene, polystyrene block copolymer (such as s-B-S), styrene-ethylene-propylene-styrene, styrene-ethylene-butylene-styrene, or the like, and their mixture.Heat-curable urethane or polyureas are suitable for the outer cover of golf of the present invention.

In addition, polyurethane can with polyurea materials replacement or with the polyurea materials blend.Polyureas and urethane composition are completely different, also cause aerodynamics and the aesthetic features expected when still in the golf composition, using.Composition based on polyureas is saturated in nature preferably.

Not fettered by any particular theory, now phase credit long-chain polyamines oligomer soft chain segment substitutes long-chain polyhydric alcohol segment in the polyurethane prepolymer and improves and shear property, cutting and resilience, and to the adhesiveness of other composition.So, can form polyurea composition of the present invention through product with crosslinked isocyanates of curing agent and polyamines prepolymer.For example, can prepare the composition that the present invention is based on polyureas from least a isocyanates, at least a polyetheramine and at least a two polyol curing agents or at least a diamine curing agent.

Any polyamines that those of ordinary skills can get is adapted at using in the polyureas prepolymer.Polyetheramine is particularly suitable in prepolymer, using.Like what use among this paper, " polyetheramine " to oligodactyly contains the polyoxy alkylene amine that is attached to the terminal primary amino radical of polyether backbone.Yet because isocyanates and the fast reaction of amine and the indissolubility of many urea products, the selection of diamines and polyetheramine is limited to those and allows and successfully form the polyureas prepolymer.In one embodiment, polyether backbone based on tetramethylene, propylene, ethene, trihydroxymethyl propane, glycerine, and composition thereof.

Suitable polyetheramine includes but not limited to methyl diethanolamine; Polyoxy alkylidene diamines such as polytetramethylene ether diamine, polyoxy propylidene triamine and polyoxy trimethylene diamine; Gather (the oxygen propylidene that oxirane adds cap) ether diamine; Triamine based on expoxy propane; The triethylene glycol diamines; Triamine based on trihydroxymethyl propane; Triamine based on glycerine; And their mixture.In one embodiment; The polyetheramine that is used to form prepolymer is

D2000 (Huntsman Chemical Co.; Austin, TX).

The molecular weight ranges of the polyetheramine that in the polyureas prepolymer, uses can be about 100 to about 5000.In one embodiment, the polyetheramine molecular weight is about 200 or bigger, preferred about 230 or bigger.In another embodiment, the molecular weight of polyetheramine is about 4000 or littler.In another embodiment, the molecular weight of polyetheramine is about 600 or bigger.In also having an embodiment, the molecular weight of polyetheramine is about 3000 or littler.In also having an embodiment, the molecular weight of polyetheramine is 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 the solid polyureas; So the oligomer of preferred higher molecular weight is such as D2000.

Like the short discussion of preceding text, some amine possibly be inappropriate for and isocyanate reaction, because these two kinds become branch that fast reaction takes place.Particularly, fast reaction can take place in the amine than short chain.Yet in one embodiment, the secondary diamine that is obstructed is applicable to prepolymer.Be reluctant to arrest in any concrete theory, think that the amine of (stearic hindrance) (the for example tertiary butyl groups on the nitrogen-atoms) that have high-level steric hindrance is than the amine that does not have steric hindrance or to have the reaction rate of amine of low-level steric hindrance slow.For example; 4,4 '-two-(sec-butyl is amino)-dicyclohexyl methyl hydride (

1000) can be suitable for making up to form the polyureas prepolymer with isocyanates.

The spendable isocyanates of any those of ordinary skills is applicable to the polyureas prepolymer.Be used for isocyanates of the present invention and comprise that per molecule has the compound of the aliphatic of two or more NCOs (NCO) group, alicyclic, araliphatic, aromatics, and any derivative and these combination of compounds.Said isocyanates can be the prepolymer of organic multiple isocyanate for end.But the said reacted constituent that contains isocyanates also can comprise any isocyanate functional monomer, dimer, trimer or its poly adduct, prepolymer, quasi-prepolymer (quasi-prepolymer), or its mixture.The isocyanate functional compound can comprise monoisocyanates or polyisocyanates, and the latter comprises two or more any isocyanate functional groups.

The suitable isocyanate prepolymer composition that contains comprises the vulcabond with formula structure: 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 atoms.Said vulcabond also can comprise one or more cyclic groups or one or more phenyl group.When having a plurality of ring-types or aromatic group, comprise about 1 alkyl and can be used as spacer groups (spacer) and be present between said ring-type or the aromatic group to the straight chain of about 10 carbon atoms and/or branching.In some cases, said ring-type or aromatic group can distinguished 2-, 3-and/or 4-position, or ortho position, a position and/or contraposition are substituted.Substituted radical can include but not limited to halogen, primary, uncle or sechy-drocarbyl group, or its combination.

The instance that can be used for vulcabond of the present invention includes but not limited to: the mixture of substituted and isomery, comprise 2,2 '-, 2,4 '-with 4,4 '-methyl diphenylene diisocyanate; 3,3 '-dimethyl-4,4 '-xenyl vulcabond; Toluene di-isocyanate(TDI); Polymeric MDI; The liquid state 4 of carbodiimide modified, 4 '-methyl diphenylene diisocyanate; PPDI; M-benzene diisocyanate; Triphenyl methane-4,4 '-and triphenyl methane-4,4 ' triisocyanate; Naphthalene-1, the 5-vulcabond; 2,4 '-, 4,4 '-with 2,2 '-diphenyl diisocyanate; Polyphenyl polymethylene polyisocyanates; The mixture of MID and PMDI; The mixture of PMDI and TDI; Ethylidene diisocyanate; Propylidene-1, the 2-vulcabond; Tetramethylene-1, the 2-vulcabond; Tetramethylene-1, the 3-vulcabond; Tetramethylene-1, the 4-vulcabond; 1, the 6-hexamethylene diisocyanate; Eight methylene diisocyanates; The decamethylene vulcabond; 2,2, the 4-trimethyl hexamethylene diisocyanate; 2,4, the 4-trimethyl hexamethylene diisocyanate; Dodecyl-1, the 12-vulcabond; Cyclobutane-1, the 3-vulcabond; Cyclohexane-1, the 2-vulcabond; Cyclohexane 1, the 3-vulcabond; Cyclohexane-1, the 4-vulcabond; Methyl-cyclohexylidene vulcabond; 2, the 4-methylcyclohexane diisocyanate; 2, the 6-methylcyclohexane diisocyanate; 4,4 '-dicyclohexyl vulcabond; 2,4 '-dicyclohexyl vulcabond; 1,3,5-cyclohexane triisocyanate; NCO hexahydrotoluene isocyanates; 1-NCO-3,3,5-trimethyl-5-NCO hexahydrotoluene; NCO ethyl cyclohexane isocyanates; Two (isocyanates ylmethyl)-cyclohexane diisocyanates; 4,4 '-two (isocyanates ylmethyl) bicyclohexane; 2,4 '-two (isocyanates ylmethyl) bicyclohexane; IPDI; The triisocyanate of HDI; 2,2,4-trimethyl-1, the triisocyanate of 6-hexane diisocyanate; 4,4 '-dicyclohexyl methyl hydride diisocyanate; 2,4-hexahydrotoluene vulcabond; 2,6-hexahydrotoluene vulcabond; 1,2-, 1,3-and 1,4-phenylene vulcabond; The aromatics aliphatic isocyanate, as 1,2-, 1,3-and 1,4-XDI; Between-tetramethylxylene diisocyanate; Right-tetramethylxylene diisocyanate; The isocyanuric acid ester of the trimerizing of any polyisocyanates such as the isocyanuric acid ester of toluene di-isocyanate(TDI); The trimer of methyl diphenylene diisocyanate; The trimer of tetramethylxylene diisocyanate; The isocyanuric acid ester of hexamethylene diisocyanate, the isocyanuric acid ester of IPDI, and composition thereof.The dimerization uretdione of any polyisocyanates, like toluene di-isocyanate(TDI), the uretdione of hexamethylene diisocyanate, and composition thereof; Derive from the polyisocyanates of the modification of above-mentioned isocyanates and polyisocyanates; And composition thereof.

The instance that can be used for saturated vulcabond of the present invention includes but not limited to: ethylidene diisocyanate; Propylidene-1, the 2-vulcabond; Tetramethylene diisocyanate; Tetramethylene-1, the 4-vulcabond; 1, the 6-hexamethylene diisocyanate; Eight methylene diisocyanates; Decamethylene vulcabond 2,2, the 4-trimethyl hexamethylene diisocyanate; 2,4, the 4-trimethyl hexamethylene diisocyanate; Dodecane-1, the 12-vulcabond; Cyclobutane-1, the 3-vulcabond; Cyclohexane-1, the 2-vulcabond; Cyclohexane-1, the 3-vulcabond; Cyclohexane-1, the 4-vulcabond; Methyl-cyclohexylidene vulcabond; 2, the 4-methylcyclohexane diisocyanate; 2, the 6-methylcyclohexane diisocyanate; 4,4 '-dicyclohexyl vulcabond; 2,4 '-dicyclohexyl vulcabond; 1,3,5-cyclohexane triisocyanate; NCO hexahydrotoluene isocyanates; 1-NCO-3,3,5-trimethyl-5-NCO hexahydrotoluene; NCO ethyl cyclohexane isocyanates; Two (isocyanates ylmethyl)-cyclohexane diisocyanates; 4,4 '-two (isocyanates ylmethyl) bicyclohexane; 2,4 '-two (isocyanates ylmethyl) bicyclohexane; IPDI; The triisocyanate of HDI; 2,2,4-trimethyl-1, the triisocyanate of 6-hexane diisocyanate; 4,4 '-dicyclohexyl methyl hydride diisocyanate; 2,4-hexahydrotoluene vulcabond; 2,6-hexahydrotoluene vulcabond; And composition thereof.The aromatics aliphatic isocyanate also can be used for forming the light stabilizing material.The instance of this type of vulcabond comprises 1,2-, 1,3-and 1,4-XDI; Between-tetramethylxylene diisocyanate; Right-tetramethylxylene diisocyanate; Three poly-isocyanurates of any polyisocyanates such as the isocyanuric acid ester of toluene di-isocyanate(TDI); The trimer of methyl diphenylene diisocyanate; The trimer of tetramethylxylene diisocyanate; The isocyanuric acid ester of hexamethylene diisocyanate, the isocyanuric acid ester of IPDI, and composition thereof; The dimerization uretdione of any polyisocyanates, like the uretdione of toluene di-isocyanate(TDI), the uretdione of hexamethylene diisocyanate, and composition thereof; Derive from the modified polyisocyanate of above-mentioned isocyanates and polyisocyanates; And composition thereof.In addition, for the purposes of the present invention, said aromatics aliphatic isocyanate can mix with the listed saturated isocyanates of any preceding text.

Can change in polyureas prepolymer and the polyetheramine of isocyanates unreacted NCO group number with control like reaction speed, factors such as the composition hardness of gained.For example, can be at the polyureas prepolymer of isocyanates and the unreacted NCO group number in the polyetheramine and be less than about 14%.In one embodiment, said polyureas prepolymer has about 5% to about 11% unreacted NCO group, and even more preferably has a unreacted NCO group of about 6% to about 9.5%.In one embodiment, the percentage of unreacted NCO group is about 3% to about 9%.Perhaps, the percentage of the unreacted NCO group in the polyureas prepolymer can be about 7.5% or still less, and more preferably, and about 7% or still less.In another embodiment, unreacted NCO content is about 2.5% to about 7.5%, and more preferably is about 4% to about 6.5%.

When forming, the polyureas prepolymer can comprise about 10% to about 20% the free isocyanate monomer that accounts for said prepolymer by weight.Therefore, in one embodiment, said polyureas prepolymer can have been got rid of free isocyanate-monomer.For example, after getting rid of, prepolymer can comprise about 1% or free isocyanate-monomer still less.In another embodiment, said prepolymer comprises about by weight 0.5% or free isocyanate monomer still less.

Said polyetheramine can mix with other polyalcohols with the preparation copolymer, and copolymer and excess isocyanate are reacted to form the polyureas prepolymer.In one embodiment, will be less than about 30% polyalcohol by copolymer weight mixes with saturated polyetheramine.In another embodiment, will be less than about 20% polyalcohol, preferably be less than approximately 15%, mix with said polyetheramine by copolymer weight by copolymer weight.The listed polyalcohol of preceding text is with respect to polyurethane prepolymer, PPG for example, and polycaprolactone polyol, PEPA, polycarbonate polyol, the hydrocarbon polyalcohol, other polyalcohols, and composition thereof, also be suitable for mixing with said polyetheramine.The molecular weight of these polymer can be about 200 to about 4000, but also can be about 1000 to about 3000, and more preferably about 1500 to about 2500.

Said polyurea composition can be through with polyureas prepolymer and single curing agent or curing agent mixture is crosslinked processes.Curing agent of the present invention is preferably the curing agent (amine-terminated curing agent) of amine end-blocking, and more preferably the secondary diamine curing agent makes composition only comprise urea and connects base.In one embodiment, the curing agent of said amine end-blocking can have about 64 or bigger molecular weight.In another embodiment, the molecular weight of said amine hardener is about 2000 or still less.As discussed above, the curing agent of some amine end-blocking can use the mixture of compatible amine end-blocking freezing point inhibitor (amine-terminated freezing point depressing agent) or compatible freezing point inhibitor to come modification.

Suitable amine end-blocking curing agent includes but not limited to ethylenediamine; Hexamethylene diamine; 1-methyl-2,6-cyclohexyl diamines; Tetrahydroxy propylidene ethylenediamine; 2,2,4-and 2,4,4-trimethyl-1,6-hexane diamines; 4,4 '-two-(sec-butyl is amino)-dicyclohexyl methyl hydride; 1,4-two-(sec-butyl is amino)-cyclohexane; 1,2-two-(sec-butyl is amino)-cyclohexane; 4, the derivative of 4-two-(sec-butyl is amino)-dicyclohexyl methyl hydride; 4,4 '-dicyclohexyl methyl hydride diamines; 1,4-cyclohexane-two-(methylamine); 1,3-cyclohexane-two-(methylamine); Diethylene glycol two-(aminopropyl) ether; 2-methyl pentamethylene-diamines; DACH; Diethylenetriamines; Trien; Tetren; Trimethylene diamine; 1, the 3-diaminopropanes; Dimethylamino propylamine; Diethyl amino propylamine; Dipropylenetriamine; Imido grpup-two-propylamine; MEA, diethanol amine; Triethanolamine; Single isopropylamine, diisopropylamine; IPD; 4,4 '-methylene two-(2-chloroaniline); 3,5-diformazan sulfenyl-2,4-toluenediamine; 3,5-diformazan sulfenyl-2,6-toluenediamine; 3,5-diethyl sulfenyl-2,4-toluenediamine; 3,5-diethyl sulfenyl-2,6-toluenediamine; 4,4 '-two-(sec-butyl is amino)-diphenyl-methane and derivative thereof; 1,4-two-(sec-butyl is amino)-benzene; 1,2-two-(sec-butyl is amino)-benzene; N, N '-dialkyl amido-diphenyl-methane; N, N, N ', N '-four (2-hydroxypropyl) ethylene diamine; Trimethylene-two-p-aminobenzoic acid ester; Oxolane-two-p-aminobenzoic acid ester; 4,4 '-methylene two-(3-chloro-2,6-diethylidene aniline); 4,4 '-methylene two-(2, the 6-diethylaniline); Between-phenylenediamine; P-pHENYLENE dI AMINE; And composition thereof.In one embodiment, the curing agent of said amine end-blocking is 4,4 '-two-(sec-butyl is amino)-dicyclohexyl methyl hydride.

The terminal curing agent of suitable saturated amine includes but not limited to: ethylenediamine; Hexamethylene diamine; 1-methyl-2,6-cyclohexyl diamines; Tetrahydroxy propylidene ethylenediamine; 2,2,4-and 2,4,4-trimethyl-1,6-hexamethylene diamine; 4,4 '-two-(sec-butyl is amino)-dicyclohexyl methyl hydride; 1,4-two-(sec-butyl is amino)-cyclohexane; 1,2-two-(sec-butyl is amino)-cyclohexane; The derivative of 4,4 '-two-(sec-butyl is amino)-dicyclohexyl methyl hydride; 4,4 '-dicyclohexyl methyl hydride diamines; 4,4 '-methylene two-(2,6-diethylamino cyclohexane); 1,4-cyclohexane-two-(methylamine); 1,3-cyclohexane-two-(methylamine); Diethylene glycol two-(aminopropyl) ether; The 2-methyl pentamethylene diamine; DACH; Diethylenetriamines; Trien; Tetren; Trimethylene diamine; 1, the 3-diaminopropanes; Dimethylamino propylamine; Diethyl amino propylamine; Imido grpup-two-propylamine; MEA, diethanol amine; Triethanolamine; Monoisopropanolamine, diisopropanolamine (DIPA); IPD; Triisopropanolamine; And composition thereof.In addition, the listed polyetheramine of any preceding text can be used as curing agent and the reaction of polyureas prepolymer.

The cover layer of golf of the present invention also can be processed from the ionomer (HNP) of ionomer preferred heights neutralization.In a preferred embodiment, process from HNP material or HNP mixtures of material at least one intermediate layer of said golf.The acidic moiety of HNP is generally the ionomer based on ethylidene, preferably is neutralized greater than about 70%, and more preferably greater than about 90%, and most preferably at least about 100%.HNP also can mix with second polymers compositions, and said component is if contain acid groups, and available usual manner neutralization neutralize through organic aliphatic acid of the present invention, or both all is.Said second polymers compositions can partially or completely neutralize, and preferably comprises the copolymer and the trimer of ionomer polymerization, ionomer precursor, thermoplastic; Polyamide, Merlon, polyester, polyurethane; Polyureas, thermoplastic elastomer (TPE), polybutadiene rubber, balata (balata); The polymer of metallocene catalysis (grafting with non-grafting), unit point polymer, the acid polymer of high crystallization, cationic ionomer etc.The HNP polymer has about 20 bending moduluses to the material hardness of about 80 Shore D and about 3000psi to about 200000psi usually.

In one embodiment of the invention, HNP is an ionomer, and/or its acid precursors, preferably neutralizes wholly or in part through organic acid copolymer or its salt.Said acid copolymer is preferably alpha-olefin, like ethene, and C _3-8α, β-ethylenic unsaturated carboxylic acid is like acrylic acid and methacrylic acid copolymer.It can preferably comprise softening comonomer, and like alkyl acrylate and alkyl methacrylate, wherein said alkyl group has 1 to 8 carbon atom.

Said acid copolymer can be described as e/x/y copolymer, and wherein E is an ethene, and X is α, β-ethylenic unsaturated carboxylic acid, and Y is softening comonomer.In a preferred embodiment, X is acrylic or methacrylic acid, and Y is acrylic acid C _1-8Arrcostab or methacrylic acid C _1-8Arrcostab.X preferably exists with the amount of the percentage by weight of polymer about 1 to about 35, about 5 of polymer to about 30 percentage by weight more preferably, and most preferably be about 10 to about 20 percentage by weight of polymer.Y preferably exists with the amount of the percentage by weight of polymer about 0 to about 50, about 5 of polymer to about 25 percentage by weight more preferably, and most preferably be about 10 to about 20 percentage by weight of polymer.

The concrete ethylene copolymer that contains 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 ethylene copolymer that preferably contains acid comprises ethylene/methacrylic acid/n-butyl acrylate, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/acrylic acid/ethyl acrylate, ethylene/methacrylic acid/ethyl acrylate and ethylene/acrylic acid/methyl acrylate copolymer.The most preferred ethylene copolymer that contains acid is ethene/(methyl) acrylic acid/n-butyl acrylate, ethene/(methyl) acrylic acid/ethyl acrylate and ethene/(methyl) acrylic acid/methyl acrylate copolymer.

Usually with metal cation Li for example, Na, Mg, K, Ca, or Zn neutralizes ionomer.But, have been found that through with enough organic acids or organic acid salt; With suitable alkali together; Add said acid copolymer or ionomer to, this ionomer can be neutralized to level much bigger for metal cation, and does not lose processability.Preferably, with the neutralization of this acid moieties greater than about 80%, preferred 90-100%, most preferably 100%, and do not lose processability.This is accompanied by the melt blending ethylene-alpha; β-the ethylenic copolymers of unsaturated carboxylic acids (for example; With organic acid or the copolymerization of organic acid salt); And add the cationic source of q.s the neutralization levels of all acid moieties (be included in the acid copolymer and in organic acid those) is increased to greater than 90% (being preferably greater than 100%).

Organic acid of the present invention is an aliphatic, single-or many-sense (saturated, undersaturated, or polyunsaturated) organic acid.Also can use these organic acid salt.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, aluminium, tin, or the salt of calcium, the salt of the derivative of the salt of aliphatic acid, particularly stearic acid, mountain Yu acid, sinapic acid, oleic acid, linoleic acid or its dimerization.Preferred this organic acid and salt of the present invention are relative non-migrating property (they do not move on the surface of polymer at ambient temperature) and nonvolatile (they are non-volatile under the required temperature of melt blending).

Ionomer of the present invention also can be conventional more ionomer, that is, partly neutralize with metal cation.For example lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminium or its mixture will be in the acid moieties in this acid copolymer and about 1 to about 90% through cation; Preferably at least about 20 to about 75%; More preferably at least about 40 to about 70%, thereby form ionomer.

In preferred embodiment; Individual layer nuclear of the present invention is with two cover encloses; 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, and most preferably from about 0.02 inch to about 0.035 inch; With said inner cover by part-or the ionomer of all neutralizations form; Said part-or all the Shore D hardness of the ionomers of neutralization be greater than about 55, more preferably greater than about 60 with most preferably 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 and most preferably from about 0.025 inch to about 0.035 inch and hardness be about Shore D 60 or littler; More preferably 55 or littler, and most preferably from about 52 or littler.Said inner cover should be harder than said outer cover.In this embodiment, outer cover comprises the ionomer of part-or fully-neutralization, polyurethane, polyureas, or its blend.But most preferred outer cover is pourable or the polyurethane of reaction injection molding, polyureas or its copolymer or mixture, and its Shore D hardness is about 40 to about 50.Most preferred inner cover material is the ionomer of part neutralization; It contains zinc, and the ionomer of sodium or lithium neutralization is 8940,8945 for example; 9910; 7930,7940, or its Shore D hardness is about 63 to about 68 mixture.

Another multilayer cover layer, single examining in the mode of executing, outer cover is identical with inner cover material and thickness, but hardness range is opposite, that is, outer cover is harder than inner cover.

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

In preferred two-ball embodiment; Individual layer nuclear with negative hardness gradient is with the coating of individual layer cladding material, and the Shore D hardness of this cladding material is about 20 to about 80, and more preferably from about 40 to about 75; Most preferably from about 45 to about 70; And comprise thermoplasticity or heat-curable urethane, polyureas, polyamide, polyester, polyester elastomer, polyether-amide or polyester-amides, the ionomer that partly or completely neutralizes, polyolefin is polyethylene for example; Polypropylene; Polyethylene and ethylene copolymers is ethylene-propylene acid butyl ester or ethylene-methyl acrylate for example, gathers (ethylene-methyl methacrylate) copolymer-and terpolymer, the polyolefin of metallocene-catalysis and polar group functionalized polyolefin and blend thereof.Preferred cladding material is ionomer (is conventional or HNP) in two embodiments, and its hardness is about 50 to about 70 Shore D.Another preferred cladding material is thermoplasticity or heat-curable urethane or polyureas in two embodiments.Preferred ionomer is the peracidity ionomer, and it comprises ethene and methacrylic acid or acrylic acid copolymer, and acid content is at least 16 to about 25wt%.In this case, the rotation (reduced spin) of the reduction of the contribution of the peracidity ionomer through relative stiffness can be offset through the negative gradient nuclear (spin-increasing negative gradient core) that increases rotation to a certain extent.The diameter of this nuclear can be about 1.0 inches to about 1.64 inches, preferred about 1.30 inches to about 1.620 and more preferably from about 1.40 inches to about 1.60 inches.

Another preferred cladding material comprises the polyurethane of pourable or reaction injection molding, the copolymer of polyureas or polyurethane/polyurea or mixture.Effectively, this cover layer is heat cured, but can be thermoplastic, and Shore D hardness is about 20 to about 70, and more preferably from about 30 to about 65, most preferably from about 35 to about 60.Randomly between this cover layer and nuclear, use the moist steam barrier layer (for example to be disclosed in United States Patent (USP) 6,632,147; 6,932,720; 7,004,854; With 7,182, in 702, with the full content of all these documents through with reference to incorporating the application into).

Though any embodiment of the application all can have any known depression number and pattern, preferred depression number is 252 to 456, more preferably 330 to 392.This depression number can comprise any width, the degree of depth and the seamed edge angle (edge angle) that discloses in the prior art, and this pattern can comprise a plurality of depressions with different in width, the degree of depth and seamed edge angle.The separator bar configuration of said pattern can be straight line or staggered wave separator bar (SWPL).Most preferably this depression number is 330,332, or 392, and comprise 5 to 7 depression sizes, and separator bar is SWPL.

In any of these embodiment, this individual layer endorse with 2 or more the nuclear of multilayer replace, wherein at least one stratum nucleare has negative hardness gradient.With different among the operation embodiment; Only if perhaps specifically note in addition; Otherwise, all number ranges, amount; Value and percentage similarly are that the front has term " pact " to modify like those read likes of the amount of other things of being used for material and specification, and " pact " possibly occur with this value, amount or scope ambiguously even this term.Therefore, only if point out on the contrary, listed numerical parameter is similar in specification and the appended claim, the character that it can the expectation of desired acquisition according to the present invention and changing.At least, and do not attempt, with the scope that should be used for limiting claim of identical instruction, each numerical parameter should be explained according to given significant digits with through applying the common technology of rounding up at least.Be similar to although provide wide in range number range of enclosing of the present invention and parameter, the numerical value that provides in the specific embodiment as far as possible accurately provides.Some error that the standard deviation that in their each measurement means, exists but any numerical value itself must contain causes.In addition, when the application provides various number range, can use any combination (comprising the value of being put down in writing) of any of these value.Though obvious is that the illustrated embodiment of the present invention that the application discloses satisfies above-described purpose, should be appreciated that, it may occur to persons skilled in the art that many improvement and other embodiment.Therefore, should be appreciated that appended claim intention covers within the spirit and scope of the present invention all these improvement and embodiment.

Claims

1. golf comprises:

Single nuclear, it has outer surface and geometric center, and by basically uniformly rubber compsn form;

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

Outer cover, it is around said inner covering layer configuration, and said outer the covering comprises casting type polyureas or casting type polyurethane and has about 60 Shore D or littler material hardness;

Wherein said outer surface has about 12% or the hardness of trans component content still less and about 71 to 88 Shore C; Said geometric center has about 10% or the hardness of trans component content still less and about 70 to 80 Shore C, and the nuclear case hardness greater than about 1 to the 10 Shore C of geometric center case hardness to limit shallow positive hardness gradient.

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

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

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

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

6. the golf of claim 1, the hardness of wherein said nuclear geometric center is about 72 to 78 Shore C.

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

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

9. the golf of claim 1, wherein said outer surface have about 10% or trans component content still less, and geometric center has about 8% or trans component content still less.

10. golf comprises:

Single nuclear has about 1.5 to 1.55 inches external diameter, outer surface and geometric center, and by basically uniformly rubber compsn form.

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

Outer cover, it is around said inner covering layer configuration, and said outer the covering has about 0.04 inch thickness, and comprises the ionomer that material hardness is about 64 to 68 Shore D, or has the thermosetting casting type polyurethane of about 51 to 55 Shore D;

Wherein said outer surface has about 12% or the hardness of trans component content still less and about 74 to 78 Shore C; Said geometric center has about 10% or the hardness of trans component content still less and about 72 to 78 Shore C; And to limit shallow positive hardness gradient, said nuclear has about 50 to 70 Atti compression to said nuclear case hardness greater than about 1 to the 5 Shore C of geometric center hardness.

11. the golf of claim 10, wherein said golf also comprise the intermediate layer that is disposed between inner covering layer and the nuclear, said intermediate layer has the hardness of about 0.06 inch thickness and about 43 to 47 Shore D.

12. the golf of claim 0, wherein said interior covering hardness is about 66 Shore D, and said intermediate layer hardness is about 45 Shore D, and outer cover hardness is about 53 Shore D.

13. a golf comprises:

Single nuclear has about 1.45 inches external diameter, outer surface, and geometric center, and by basically uniformly rubber compsn form;

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

Outer cover, it is around said inner covering layer configuration, and said outer the covering has about 0.05 inch thickness and comprises the ionomer with about 66 to 70 Shore D material hardnesses;

Wherein said outer surface has about 12% or the hardness of trans component content still less and about 74 to 78 Shore C; Said geometric center has about 10% or the hardness of trans component content still less and about 72 to 78 Shore C, and said nuclear case hardness greater than about 1 to the 5 Shore C of geometric center hardness to limit shallow positive hardness gradient.