CN102526990B

CN102526990B - Comprise the double-core golf of zero gradient center and positive gradient outer nuclear layer

Info

Publication number: CN102526990B
Application number: CN201110452553.7A
Authority: CN
Inventors: M·J·沙利文; B·科莫; D·A·拉德; S·库珀
Original assignee: Acushnet Co
Current assignee: Acushnet Co
Priority date: 2010-12-22
Filing date: 2011-12-20
Publication date: 2016-08-03
Anticipated expiration: 2031-12-20
Also published as: JP5715038B2; CN102526990A; JP2012130694A

Abstract

The present invention relates to comprise the double-core golf of zero gradient center and positive gradient outer nuclear layer.A kind of golf, comprises: kernel, and it has geometric center and the first outer surface, and described kernel is formed by substantially uniform first rubber composition；Outer nuclear layer, it forms by substantially uniform second rubber composition, and described outer nuclear layer has the second outer surface；Inner covering layer, it becomes around described karyomorphism and comprises ionomeric materials；And outer cover, it is formed around described inner covering layer and comprises casting type polyureas or casting type polyurethane.The hardness that described first outer surface has is less than the hardness gradient kernel that the hardness at most about 20 Shore C at described geometric center bears with restriction, and the hardness that described second outer surface has is more than the hardness at most 18 Shore C of described geometric center to limit positive gradient outer nuclear layer and shallow positive hardness gradient core.

Description

Comprise the double-core golf of zero gradient center and positive gradient outer nuclear layer

Cross reference

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

Technical field

Usually, the present invention relates to the golf with the core containing one or more layers, any layer is respectively provided with ' bearing ' or the hardness gradient of ' just ', trans component gradient (transgradient), or both.More particularly, golf has the core of two-layer or more layers, and at least one of which layer, preferred inner nuclear layer have " zero hardness gradient " or " negative hardness gradient ".

Background technology

Entity golf is generally made up of coating cap rock (cover) cladding entity core, and cover layer and core both of which can have multiple layer, such as double-core and have solid centre and outside stratum nucleare, or multilayer coatingn has inside.In general, golf ball core and/or center are formed by thermoset rubber, it is common that compositions based on polybutadiene.Generally heating core and make it cross-link to produce specific character, the most higher or lower compression, it can affect the rotary speed of ball and/or provide preferably " sensation ".Such and other character can adapt in the needs of the golf player with different ability.From the perspective of golf maker, the core of desired display width range of properties, these character such as resilience, durability, rotation and " sensation ", because so can making manufacturer manufacture and selling the golf of the number of different types being suitable for different level of ability.

Up to the present, most of single core golf ball cores have traditional from the center on the surface of core to core by hard to soft hardness gradient, this be also considered as " positive hardness gradient ".But, these gradients are the biggest, up to 15 Shore C hardness, 20 Shore C hardness, even as high as 25 Shore C hardness or higher.Patent documentation includes substantial amounts of list of references, it addition, it discusses the hardness gradient from hard-surface to soft-center across golf ball core.

United States Patent (USP) No.4 of Molitor et al., 650, hardness gradient in 193 surface layers generically disclosing core, it forms as follows: utilizes solidification to change agent (cure-alteringagent) and processes the material block of curable elastomer and be core by material formation of lots subsequently.As mentioned above, such process creates the core with different two regions of composition, Part I be core hard, have elastic mid portion, this part is that residue is not processed, and Part II is the outer layer soft, variable of core, this part is that cured change agent processes.Two " layers " of this core or region are the most integral, it is hereby achieved that from pressure release surface to the such gradient in hard center.

United States Patent (USP) No.3,784,209 of Berman et al. generically discloses soft to hard hardness gradient.Which disclose and there is the heterogeneous of " mixing " elastomer core, the golf of molding.The center spheroid of uncured elastomeric material is surrounded by compatible but different uncured elastomer.When the two-layer of elastomer is exposed simultaneously to firming agent, they can form entirety each other, thus defines the core of mixing.The center of this core has the first elastomeric material of higher concentration, and it is harder than outer layer.One shortcoming of this manufacture method is to manufacture the first elastomer, then manufactures the second elastomer and then they to be molded as one be a time-consuming process.

Other patent discusses and core is carried out surface process so that it has soft " skin (skin) ".But, owing to the interior section of these cores is unprocessed, therefore they have the similar crust gradient to soft center, as traditional core.Such as, United States Patent (USP) No.6 of Nesbitt et al., 113,831 generically disclose traditional core and surround the single moccasin skin of this core.This moccasin skin is prepared: in forming process by following process, the material block being preformed by is exposed under steam (steam), so that maximum forming temperature exceedes steam cure point (steamsetpoint), and in forming process, control the temperature of thermoforming.This skin includes into radial outermost 1/32 inch～1/4 inch of spherical nuclei.United States Patent (USP) No.5 of Nesbitt et al., 976,443 and No.5,733,206 all disclose before shaping to the outer surface interpolation water smoke of material block, and are consequently formed moccasin skin.As it has been described above, by hindering the crosslinking on core surface, water has softened the compression of core, thus has manufactured the softer moccasin skin of the hard mid portion of encirclement.

It addition, multiple patents disclose multi-layer golf ball core, the most each stratum nucleare has different hardness, thereby produces the hardness gradient from stratum nucleare to stratum nucleare.

But, yet suffer from following demand: need to have the multi-layer golf ball (it has shallower hard to soft (" just ") hardness gradient from surface to center) of monolayer core, and need to obtain manufacturing the cheap and effective method of such core.

Summary of the invention

The present invention relates to golf, it comprises inner nuclear layer and outer nuclear layer to form " double base core ".Described golf includes inner covering layer and outer cover.Described inner nuclear layer has geometric center and the first outer surface, and is formed by substantially uniform rubber composition.Described outer nuclear layer is formed by substantially uniform second rubber composition, and it can be identical or different with the first rubber composition, the most different.The hardness of the second outer surface that described outer nuclear layer has is preferably different from the first outer surface.

Inner covering layer, it is put around described caryogamy, preferably includes ionomeric materials.Described layer preferably has the material hardness of about 60 Shore D or bigger.Outer cover, it configures around described inner covering layer, is generally formed by casting type polyureas or casting type polyurethane, and has the material hardness of about 60 Shore D or less.

The hardness gradient inner nuclear layer that the hardness that described first outer surface (kernel) has is born with restriction less than the hardness at most about 20 Shore C at the geometric center of described kernel.The hardness that described second outer surface (outer nuclear layer) has is more than the hardness at most 18 Shore C of described geometric center to limit positive gradient outer nuclear layer and shallow positive hardness gradient double base core.

The hardness of described first outer surface is generally less than the hardness about 1 of described geometric center and is about-1 to about-15 Shore C to about 15 Shore C to limit negative hardness gradient, and the hardness of the most described first outer surface is about-2 to about-12 Shore Cs to about 12 Shore C to limit negative hardness gradient less than the hardness about 2 of described geometric center.

In one embodiment, the external diameter that described kernel has is about 0.5 to about 1.40 inch, even more preferably about 0.8 to about 1.30 inch.The hardness at described Nuclear goemetry center is about 55 to about 82 Shore C, even more preferably about 60 to about 80 Shore C, and most preferably about 65 to 78 Shore C.The hardness of described core surface is about 50 to 82 Shore C, even more preferably about 55 to 78 Shore C, and most preferably about 60 to about 75 Shore C.Described core case hardness is about 82 to about 98 Shore C.

In another embodiment, the antioxidant that described substantially uniform first rubber composition comprises is about 0.4 or bigger to the ratio of initiator.The ionomeric materials of described inner covering layer preferably comprises Na-, Li-or Zn-ionomer, and its acid content is about 11 weight % to about 20 weight %.Or, described ionomeric materials can comprise acid content and be about ionomer and the maleic anhydride grafting, the polyolefin of metallocene catalysis of 16 weight % or bigger.

The invention still further relates to golf, it kernel including there is geometric center and position the first outer surface away from geometric center about 0.8 to about 1.3 inch, described kernel is formed by substantially uniform first rubber composition, and the antioxidant that described substantially uniform first rubber composition comprises is about 0.5 or bigger to the ratio of initiator；And outer nuclear layer, it forms by the second rubber compositions different from the first rubber composition, substantially uniform, and described outer nuclear layer has the position the second outer surface away from geometric center about 1.53 to about 1.58 inch.

Inner covering layer becomes around described karyomorphism, and comprises acid content and be about the ionomer of 16 weight % or bigger and maleic anhydride grafting, the polyolefin of metallocene catalysis.Outer cover configures around described inner covering layer, and comprises casting type polyureas or casting type polyurethane.

The hardness that described first outer surface has is about-1 to about-15 less than the hardness at described geometric center to limit negative hardness gradient, and the hardness that described second outer surface has is more than the hardness at most 12 Shore C at the inner surface of described outer nuclear layer to limit positive hardness gradient outer nuclear layer.

Accompanying drawing explanation

Fig. 1 is the hardness profile figure measured by double base core running through golf of the present invention, and it compares with the hardness distribution of conventional golf ball core.

Detailed description of the invention

The golf of the present invention can include simple layer (one piece) golf, and multi-layer golf ball, such as there is the golf of the covering of core and encirclement core, but preferably by solid centre (also referred to as kernel) and the core of outer nuclear layer, inner covering layer and outer cover are formed.Certainly, any core and/or cover layer can comprise more than one layer.In a preferred embodiment, core is formed by kernel and outer nuclear layer, wherein kernel and outer nuclear layer are respectively provided with from the appearance of a composition towards its penetrale (i.e., the center of kernel or the inner surface of outer nuclear layer) hardness gradient (" bearing " hardness gradient) of radial inside " soft to hard ", but it is also contemplated by other embodiment, the direction of the change of the hardness gradient being directed between nuclear composition and combination are (such as, " bearing " gradient at center and " just " the gradient coupling at outer nuclear layer, vice versa).

The center of core can also is that or by one or more intermediate layers and/or the hollow ball of cover layer encirclement or the ball of liquid-filling, or core can also include the solid by the elastomeric material winding stretched or liquid center.Any around the core hardness gradient (that is, " bearing " gradient) being arranged in these selectable supercentral layers and can showing the present invention.Cover layer can be simple layer or such as, multiple layers such as inner covering layer and outer cover are formed.

As being briefly described above, the core of the present invention can have the hardness gradient being defined below: this hardness gradient is the hardness measured by the center (usually 2-mm increment) at core surface (or outer nuclear layer) radial inwardly kernel and defines.The term used in this article " is born " and " just " refers to from outer surface (such as, the outer surface of entity core at measured composition；The outer surface of the kernel in double-core；The outer surface of the outer nuclear layer in double-core, etc.) hardness number in deduct innermost part (such as, the kernel in the center of entity core or dual-core architecture at measured composition；The inner surface of stratum nucleare；Etc.) hardness number after result.Such as, as the outer surface of sporocarp core has hardness relatively low compared with center (that is, in surface ratio soft-hearted), hardness gradient will be considered to be " bearing " gradient (numerical value of little numerical value-big=negative numerical value).The preferably core 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 prepared by compositions, said composition includes at least one heat-curable matrix rubber (baserubber), such as polybutadiene rubber, it is solidified by least one peroxide and at least one reactive assistant (co-agent), and reactive assistant can be slaine, non-metal auxiliary agent or their mixture of unsaturated carboxylic acid (such as acrylic or methacrylic acid).Preferably, compositions also includes suitable antioxidant.Core preparation can also include optional softening accelerator (softandfastagent) (being the most also cis-anticatalyst), such as organic sulfur or the organosulfur compound containing metal.

Can also use other composition well known by persons skilled in the art, these other compositions are to be understood that and include but not limited to Auto-regulating System of Density of Heavy Medium filler, processing aid, plasticizer, foaming or foaming agent, sulfur accelerator and/or non-peroxide radical source.Matrix thermosetting rubber 130 can be blended with other rubber and polymer, generally includes naturally occurring or synthetic rubber.Preferably base rubber is 1，4-polybutadiene, and its cis-structure is at least 40%, preferably above 80%, and more preferably higher than 90%.Desired polybutadiene rubber example includesCB22 andCB23, CB1221, CB1220, CB24 and CB21, it can be purchased from LANXESSCorporation；360L and150L and UBEPOL-BR rubber, it can be from UBEIndustries, Ltd, and Tokyo, Japan is purchased；7245、7265 and BUDENE1207 and 1208, it can be from GoodyearofAkron, and OH is purchased；SEBR-1220； BR40 and BR60, it can be purchased from PolimeriEuropa；And BR01, BR730, BR735, BR11 and BR51, it can be purchased from JapanSyntheticRubberCo.Ltd；BRNd-40；AndND40, ND50 and ND60, it can be purchased from Karbochem.

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

Base rubber can also include height or middle Mooney viscosity rubber, or its blend." Mooney " unit is the unit of the plasticity for measuring crude rubber or half finished rubber.The plasticity represented by " Mooney " unit is equal to moment of torsion, with random scale, containing on the disk of the container of 100 DEG C of rubber and with the speed wheel measuring of 2 turns per minute.Measured value according to ASTMD-1646 definition Mooney viscosity.Mooney viscosity scope is preferably greater than about 40, more preferably in the scope of about 40 to about 80, and the further preferred scope in about 40 to about 60.The polybutadiene rubber with relatively high Mooney viscosity can also be used, as long as the viscosity of polybutadiene is not up to the blocking of high viscosity polybutadiene or the level of other negative effect manufacture machine.Expect to use viscosity to be less than the polybutadiene of 65 Mooneys in the present invention.In an embodiment of the invention, golf ball core by having-or the polybudiene materials of height-Mooney viscosity make, the resilience (and, therefore distance) that its display improves is without improving the hardness of ball.Such core is soft, i.e. compression is less than about 60 and more specifically in the scope of about 50-55.There is the core of Ratage Coutpressioit in about 30 to about 50 also in the scope of the preferred embodiment of the present invention.

In He Shi-commercial source of paramount-Mooney viscosity polybutadiene includes BayerAGCB23 (Nd-catalysis), it has the Mooney viscosity of about 50 and is the polybutadiene of highly linear, and CB1221 (Co-catalysis).If it is required, polybutadiene can also mix with other elastomer known in the art, such as other polybutadiene rubber, natural rubber, styrene butadiene ribber and/or isoprene rubber, to be modified the character of core further.When using the mixture of elastomer, the content of other composition in core composition is typically based on the main elastomer mixture of 100 weight portions.Preferably buying in the mode of executing at one, base rubber includes the polybutadiene that Nd-is catalyzed, the polybutadiene rubber of rare earth element-catalysis, or their blend.If it is required, polybutadiene can mix with other elastomer as known in the art, such as natural rubber, polyisoprene rubber and/or SBR styrene butadiene rubbers, it is modified with the character to core.Other suitable base rubber includes thermosets, such as ethylene propylene diene monomer rubber, EP rubbers, butyl rubber, halogenated butyl rubber, hydrogenated nitrile-butadiene rubber, nitrile rubber and silicone rubber.

Thermoplastic elastomer (TPE) (TPE) can be used for being modified the character of stratum nucleare, or by uncured stratum nucleare raw material being modified with Matrix thermosetting blend rubber.These TPE include naturally occurring or synthetic natural gum (balata) or high trans-polyisoprene, high trans-polybutadiene or any SBC, such as Styrene Ethylene styrene, styrene-isoprene-phenylethene etc., metallocene or other is through the polyolefin such as ethylene-octene copolymer of single site catalysis, or ethylene-butene copolymer, or thermoplastic polyurethane (TPU), including such as with the copolymer of silicones.Other suitably includes for the TPE blended with the thermoset rubber of the present invention(thinking that it includes polyether amide copolymer),(thinking that it includes polyetherester copolymer), thermoplastic polyurethane, and(thinking that it includes SBC elastomer).Any of above TPE or TPU can also be containing the functional group for grafting, including maleic acid or maleic anhydride.

Extra polymer can also be optionally incorporated in base rubber.nullExample includes but not limited to: thermo-setting elastomer，Such as core abrasive material again (coreregrind)，Thermoplastic elastomer sulfide (vulcanizate)，The ionomer of copolymerization，The ionomer of trimerization，Merlon，Polyamide，The polyamide of copolymerization，Polyester，Polyvinyl alcohol、Acrylonitrile-butadiene-stupid ethylene copolymer、Polyarylate，Polyacrylate，Polyphenylene oxide (polyphenyleneether)，Impact-resistant modified polyphenylene oxide，High impact polystyrene，Diallyl phthalate polyester，SAN (SAN) (includes olefin-modified SAN and acrylonitrile-styrene-acrylonitrile polymer)，Stupid ethylene maleic acid anhydride copolymer，Stupid ethene copolymer，The styrol copolymer of functionalization，The phenylethylene trimer of functionalization，Phenylethylene trimer，Cellulosic polymer，Liquid crystal polymer，Ethylene vinyl acetate，Polyureas，And polysiloxanes，Or the polymer of any metallocene catalysis of these materials.

In compositions within the scope of the present invention, the resin obtained in the following manner is included: (1) (a) dicarboxylic acids such as oxalic acid, adipic acid, decanedioic acid, p-phthalic acid, a stupid dioctyl phthalate or 1 as the suitable polyamides class of extra polymer, 4-cyclohexane dicarboxylic acid and (b) diamine such as ethylenediamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine or decamethylene diamine, Isosorbide-5-Nitrae-cyclohexane diamine or the polycondensation of MXDP；(2) cyclic lactames such as ∈-caprolactam or the ring-opening polymerisation of Ω-lauric lactam；(3) amino carboxylic acid, such as 6-aminocaprolc acid, 9 aminononanoic acid, 11-amino undecanoic acid or the polycondensation of 12 amino dodecanoic acid；Or (4) cyclic lactames and dicarboxylic acids and the copolymerization of diamine.The suitably instantiation of polyamide includes NYLON, NYLONMXD6 and NYLON46 of NYLON6, NYLON66, NYLON610, NYLON11, NYLON12, copolymerization.

Suitably peroxide initiator includes cumyl peroxide；2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane；2,5-dimethyl-2,5-bis-(t-butylperoxy) hexin；2,5-dimethyl-2,5-bis-(benzoylperoxy) hexane；2,2 '-two (t-butylperoxy)-two-cumene；1,1-bis-(t-butylperoxy)-3,3,5-trimethyl-cyclohexanes；4,4-bis-(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-bis--(t-butylperoxy)-2,5-dimethylhexane, lauryl peroxide, tert-butyl hydroperoxide, α, α-two (t-butylperoxy) diisopropyl benzene, two (2-tert butylperoxyisopropyl) benzene, two-t-amyl peroxy compound, di-tert-butyl peroxide.Preferably, this rubber composition includes every 100 parts by weight of rubber of the peroxide (phr) of about 0.25 to about 5.0 weight portion, more preferably 0.5phr to 3phr, most preferably 0.5phr to 1.5phr.In the most preferred embodiment, this peroxide exists with the amount of about 0.8phr.These scopes of given peroxide assume that described peroxide is 100% activity, do not consider any carrier that may be present.Owing to many commercially available peroxide are sold together with carrier compound, therefore the physical presence amount of peroxide actives should be calculated.The peroxide initiator of commercially available acquisition includes the DICUP of the cumyl peroxide that can obtain from Crompton (GeoSpecialtyChemicals)^TMClass (includes DICUP^TMR, DICUP^TM40C and DICUP^TM40KE).Similar initiator can obtain from AkroChem, Lanxess, Flexsys/Harwick and R.T.Vanderbilt.Other commercially available obtainable and preferred initiators have TRIGONOX^TM265-50B (from AkzoNobel), it is 1,1-bis-(t-butylperoxy)-3,3,5-trimethyl-cyclohexanes and the mixture of two (2-tert butylperoxyisopropyl) benzene.TRIGONOX^TMPeroxide is generally sold on carrier compound.

The most reactive auxiliary reagent includes but not limited to be applicable to the diacrylate of the present invention, dimethacrylate and the slaine of monomethacrylate hydrochlorate, including those that wherein metal is zinc, manganese, calcium, barium, stannum, aluminum, lithium, sodium, potassium, ferrum, zirconium and bismuth.Dizinc acrylate resin (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 purpose of the present invention, the amount of zinc stearate is the lowest present in the ZDA, and the purity of ZDA is the highest.ZDA containing less than about 10% zinc stearate is preferred.The more preferably ZDA containing about 4-8% zinc stearate.Suitably, the dizinc acrylate resin of commercially available acquisition includes from those of SartomerCo..The preferred concentration of the ZDA that can use is about 10phr to about 40phr, more preferably 20phr to about 35phr, most preferably 25phr to about 35phr.In particularly preferred embodiments, the amount of reactive auxiliary reagent is about 29phr to about 31phr.

The preferred coagent added can be used alone, it is also possible to be applied in combination with above-mentioned substance, but described coagent includes being not limited to trimethylol-propane trimethacrylate, trimethylolpropane trimethacrylate, etc..As well known to those skilled in the art, when coagent is at room temperature liquid, it is advantageous to these compounds are scattered on suitable carrier, it is easy to it is blended in rubber composition.

Antioxidant refers to those suppression or prevents elastomer generation Oxidative demage and/or suppression or prevent the compound of the reaction caused by oxygen-derived free radicals.The example of the antioxidant that can use in the present invention includes but not limited to quinolines antioxidant, amine antioxidants and phenolic antioxidant.Preferably antioxidant is 2, and 2 '-methylene-bis-(4-methyl-6-tert-butylphenol) can be by being purchased the trade name of RT.Vanderbilt companyThe product of MBPC and obtain.Other Polyphenols antioxidant includes:T、L、SKT、SWP、13、1290。

Preferably antioxidant includes alkylidene-substituted cresol of bis-alkyl, such as: 4,4 '-methylene-bis-(2,5-xylenol)；4,4 '-ethidine-bis-(6-ethyl-m-methyl phenol)；4,4 '-butane-bis-(the 6-tert-butyl group-m-methyl phenol)；4, pitch base-bis-(6-methyl-m-methyl phenols) 4 '-last of the ten Heavenly stems；4,4 '-methylene-bis-(2-amyl group-m-methyl phenol)；4,4 '-propylidene base-bis-(5-hexyl-m-methyl phenol)；3, pitch base-bis-(5-ethyl-p-menthan phenol) 3 '-last of the ten Heavenly stems；2,2 '-butane-bis-(3-n-hexyl-p-methyl phenol)；4,4 '-(2-butane)-bis-(the 6-tert-butyl group-m-methyl phenol)；3,3 '-(4-pitches base the last of the ten Heavenly stems)-bis-(5-ethyl-p-menthan phenol)；(2,5-dimethyl-4-hydroxy phenyl) (2-hydroxyl-3,5-3,5-dimethylphenyl) methane；(2-methyl-4-hydroxyl-5-ethylphenyl) (2-ethyl-3-hydroxy-5-methyl base phenyl) methane；(3-methyl-5-hydroxyl-6-tert-butyl-phenyl) (2-hydroxy-4-methyl-5-decyl phenyl)-normal-butyl methane；(2-hydroxyl-4-ethyl-5-aminomethyl phenyl) (2-decyl-3-hydroxy-4-methyl phenyl) butyl amyl group methane；(3-ethyl-4-methyl-5-hydroxy phenyl) (2,3-dimethyl-3-hydroxy-pheny) nonyl methane；(3-methyl-2-hydroxyl-6-ethylphenyl) (2-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 it is not limited to described example.

Other suitable antioxidant includes substituted phenols, such as: the 2-tert-butyl group-4-methoxyphenol；The 3-tert-butyl group-4-methoxyphenol；3-t-octyl-4-methoxyphenol；2-methyl-4-methoxyphenol；2-octadecyl-4-n-butyloxyphenol；The 3-tert-butyl group-4-octade-cyloxyphenol；3-dodecyl-4-thanatol；2,5-di-t-butyl-4-methoxyphenols；2-methyl-4-methoxyphenol；2-(1-methylcyclohexyl)-4-methoxyphenol；The 2-tert-butyl group-4-dodecyloxy phenol；2-(1-methyl-benzyl)-4-methoxyphenol；2-t-octyl-4-methoxyphenol；Gallicin；N-Propyl gallate；N butyl gallate；Lauryl gallate；Gallic acid myristin；Gallic acid stearyl；2,4,5-trihydroxy-acetophenones；2,4,5-trihydroxies third are n-butyl phenyl ketone；2,4,5-trihydroxy stearophenones；BHT；2,6-bis--t-octyl-4-methylphenols；2,6-di-t-butyl-4-octadecylphenol；2-methyl-4-methyl-6-tert-butylphenol；2,6-bis--octadecyl-4-methylphenols；2,6-bis--dodecyl-4-methylphenols；2,6-bis--n-octyl-4-methylphenols；2,6-bis--n-hexadecyl-4-methylphenols；2,6-bis--(1-methylundecyl)-4-methylphenols；2,6-bis--(1-methyl heptadecyl)-4-methylphenols；2,6-bis--(trimethyl)-4-methylphenols；2,6-bis--(1,1,3,3-tetramethyl octyl group)-4-methylphenols；2-dodecyl-6-tert-butyl-4-methyl-Phenol；2-dodecyl-6-(1-methylundecyl)-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-bis-(1-methyl-benzyl)-4-methylphenol；2,6-bis-(1-methylcyclohexyl)-4-methylphenol；2,6-(1-methylcyclohexyl)-4-methylphenol；2-(1-methyl-benzyl)-4-methylphenol；With relevant substituted phenol, but it is not limited to described example.

More preferably suitably antioxidant packages diphenol Han alkylidene, such as: 4,4 '-butane-bis-(3 methy 6 tert butyl phenol)；2,2 '-butane-bis-(4,6-xylenol)；2,2 '-butane-bis-(4-methyl-6-tert-butylphenol)；2,2 '-butane-bis-(the 4-tert-butyl group-6-methylphenol)；2,2 '-ethidine-bis-(4-methyl-6-tert-butylphenol)；2,2 '-methylene-bis-(4,6 xylenol)；2,2 '-methylene-bis-(4-methyl-6-tert-butylphenol)；2,2 '-methylene-bis-(4-ethyl-6-tert-butyl phenol)；4,4 '-methylene-bis-(2,6-DI-tert-butylphenol compounds)；4,4 '-methylene-bis-(2-methyl-6-tert-butylphenol)；4,4 '-methylene-bis-(2,6-xylenol)；2,2 '-methylene-bis-(the 4-tert-butyl group-6-phenylphenol)；2,2 '-dihydroxy-3,3 ', 5,5 '-tetramethyl；2,2 '-isopropylidene-bis-(4-methyl-6-tert-butylphenol)；Ethylenebis (betanaphthol)；1,5-dihydroxy naphthlene；2,2 '-ethylidene-bis-(4-methyl-6-propylphenol)；4,4 '-methylene-bis-(2-propyl group-6-butylphenol)；4,4 '-ethylidene-bis-(2-methyl-6-propylphenol)；2,2 '-methylene-bis-(5-methyl-6-butylphenol)；With 4,4 '-butane-bis-(the 6-tert-butyl group-3-methylphenol), but it is not limited to described example.

Preferably suitably antioxidant also comprises alkylidene trisphenol, such as: 2,6-pairs (2 '-hydroxyl-3 '-the tert-butyl group-5 '-methyl-benzyl)-4-methylphenol；2,6-pairs (2 '-hydroxyl-3 '-ethyl-5 '-t-butylbenzyl)-4-methylphenol；With 2,6-pair (2 '-hydroxyl-3 '-the tert-butyl group-5 '-benzyl) 4-methylphenol, but it is not limited to described example.

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

The thermoset rubber compositions of the present invention can also comprise optional containing and soften accelerator (softandfastagent)." softening accelerator " as used herein means any compound making the core of manufacture have following character or its blend or its combination in any: with the nuclear phase ratio not used manufactured by softening accelerator, 1) more soft under the conditions of constant COR (low compression), or 2) there is under identical compression higher COR.The softening accelerator preferably contained in the compositions of the present invention is about 0.05phr～about 10.0phr.In one embodiment, the amount of described softening accelerator is about 0.05phr～about 3.0phr, preferably from about 0.05phr～about 2.0phr, even more preferably about 0.05phr～about 1.0phr.In another embodiment, the amount of described softening accelerator is about 2.0phr～about 5.0phr, preferably from about 2.35phr～about 4.0phr, even more preferably about 2.35phr～about 3.0phr.In the embodiment of higher concentration, the amount of described softening accelerator is about 5.0phr～about 10.0phr, even more preferably about 6.0phr～about 9.0phr, most preferably about 7.0phr～about 8.0phr.In highly preferred embodiment, the amount of described softening accelerator is about 2.6phr.

The most suitably softening accelerator and include but not limited to organosulfur compound or the organosulfur compound containing metal, organosulfur compound (includes mono-, di-and polysulfide, mercaptan, or sulfhydryl compound), inorganic sulfide compound, race's VIA compound, or its mixture.Soften the admixture that accelerator component can also be organosulfur compound and inorganic sulfide compound.

The present invention the most suitably softens accelerator and comprises the compound with following formula, but does not limit and do this:

In formula, R₁～R_sCan any be sequentially: C₁～C₈nullAlkyl，Halogen group，Mercapto (-SH)、Carboxylate (salt) group，Sulphonic acid ester (salt) group，And hydrogen，The present invention the most suitably softens accelerator: 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，The stupid thiophenol of 5-fluorine，2，3，4-fluoro thiophenol，3，4，The stupid thiophenol of 5-fluorine，2，3，4，The stupid thiophenol of 5-tetrafluoro，2，3，5，The stupid thiophenol of 6-tetrafluoro，4-chlorine phenyl tetrafluoride thiophenol，The stupid thiophenol of pentachloro-，2-chlorothio-phenol，3-chlorothio-phenol，The stupid thiophenol of 4-chlorine，2，3-chlorothio-phenol，2，4-chlorothio-phenol，3，The stupid thiophenol of 4-chlorine，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，2，3-bromo thiophenol，2，4-bromo thiophenol，3，4-bromo thiophenol，3，5-bromo thiophenol，2，3，4-bromo thiophenol，3，4，5-bromo thiophenol，2，3，4，5-tetrabromo-benzene thiophenol，2，3，5，6-tetrabromo-benzene thiophenol，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.Preferably halogeno-benzene thiol compounds is reptazin, and it can be the most commercially available, it is also possible to commercially available trade nameFinished product, these commodity be on clay medium carrier containing volume containing the sample be 45% reptazin (being equivalent to the PCTP of 2.4 parts).Can be from StruktolCompanyofAmericaofStow, OH company is commercially available.PCTP can be from eChinachemofSanFrancisco, and CA company obtains the form that it is pure, can be from eChinachemofSanFrancisco, and CA company obtains its salt form.Most preferably, halogeno-benzene thiol compounds is the zinc salt of the stupid thiophenol of pentachloro-, can be from eChinachemofSanFrancisco, and CA company is commercially available.

As it is used herein, when relating to the present invention, term " organosulfur compound " refers to the compound of any carbon containing, hydrogen and sulfur, and wherein sulfur is directly connected with at least one carbon atom.As it is used herein, term " sulphur compound " is expressed as elemental sulfur, polymerised sulphur or a combination thereof.It is to be further understood that term " elemental sulfur " refers to S₈Ring structure, " polymerised sulphur " is the structure also including at least another sulfur in addition to elemental sulfur.

Other suitable example softening accelerator (being also considered as cis-to-anticatalyst) include but not limited to 4,4 '-diphenyl disulfide；4,4 '-xylyl disulphide；2,2 '-benzamido diphenyl disulfide；Two (2-aminophenyl) disulphide；Two (4-aminophenyl) disulphide；Two (3-aminophenyl) disulphide；2,2 '-two (4-amino naphthyl) disulphide；2,2 '-two (3-amino naphthyl) disulphide；2,2 '-two (4-amino naphthyl) disulphide；2,2 '-two (5-amino naphthyl) disulphide；2,2 '-two (6-amino naphthyl) disulphide；2,2 '-two (7-amino naphthyl) disulphide；2,2 '-two (8-amino naphthyl) disulphide；1,1 '-two (2-amino naphthyl) disulphide；1,1 '-two (3-amino naphthyl) disulphide；1,1 '-two (3-amino naphthyl) disulphide；1,1 '-two (4-amino naphthyl) disulphide；1,1 '-two (5-amino naphthyl) disulphide；1,1 '-two (6-amino naphthyl) disulphide；1,1 '-two (7-amino naphthyl) disulphide；1,1 '-two (8-amino naphthyl) disulphide；1,2 '-diaminostilbene, 2 '-disulfide group 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 (2,5-Dichlorobenzene base) disulphide；Two (3,5-Dichlorobenzene base) disulphide；Two (2,5-Dichlorobenzene base) disulphide；Two (2,4-Dichlorobenzene base) disulphide；Two (2,6-Dichlorobenzene base) disulphide；Two (2,5-dibromo chlorphenyl) disulphide；Two (3,5-dibromo chlorphenyl) disulphide；Two (2-chloro-5-bromophenyl) disulphide；Two (2,4,6-trichlorophenyl) disulphide；Two (2,3,4,5,6-five chlorophenyl) disulphide；Two (4-cyano-phenyl) disulphide；Two (2-cyano-phenyl) disulphide；Two (4-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-Fonnylphenyl) disulphide；Two (4-Carbamoylphenyl) disulphide；1,1 '-dinaphthyl disulphide；2,2 '-dinaphthyl disulphide；1,2 '-dinaphthyl disulphide；2,2 '-two (1-chlorine dinaphthyl) disulphide；2,2 '-two (1-bromonaphthalene base) disulphide；1,1 '-two (2-chloronaphthyl, methylnaphthyl) disulphide；2,2 '-two (1-cyanonaphthyl) disulphide；2,2 '-two (1-acetyl group naphthyl) disulphide；Deng；Or its mixture.Preferably organic sulphur components includes 4,4 '-diphenyl disulfide；4,4 '-ditolyl disulphide, or 2, the stupid based bisulfide of 2 '-benzamido two, or its mixture.Preferred organic sulphur components includes 4,4 '-xylyl disulphide.In another buys the scheme of executing, the organic sulphur components containing metal can be used according to the present invention.The suitably organic sulphur components on metal includes but not limited to diethyldithiocarbamate (salt), diamyl dithiocarbamate ester (salt) and the cadmium of dimethyldithiocarbamate (salt), copper, lead and tellurium analog, and mixture.

Suitably do not include that the substituted or unsubstituted aromatic series organic principle of sulfur or metal includes but not limited to 4,4 '-dibenzenyl, diphenyl diimide or its mixture.The preferred size of aromatic organic radicals is at C₆To C₂₀Scope, more preferably at C₆To C₁₀Scope.Suitably inorganic sulphide composition includes but not limited to titanium sulfide, Manganese monosulfide., and the sulfide analog of ferrum, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, stannum and bismuth.

Substituted or unsubstituted aromatic organic compounds also is suitable as softening accelerator.Suitable substituted or unsubstituted aromatic series organic principle includes but not limited to have formula (R₁)_x-R₃-M-R₄-(R₂)_yComponent, wherein R₁And R₂It is respectively hydrogen, or substituted or unsubstituted C_1-20Straight chain, side chain or ring-type alkyl, alkoxyl or alkyl sulfenyl, or monocycle or multi-ring or condensed ring C₆-C₂₄Aromatic group；X and y is respectively the integer of 0 to 5；R₃And R₄It each is selected from monocycle or multi-ring or condensed ring C₆-C₂₄Aromatic group；And M includes azo group or metal ingredient.R₃And R₄Each it is preferably selected from C₆To C₁₀Aromatic group, is more preferably selected from phenyl, benzyl, naphthyl, stupid formamido group and benzothiazolyl.R₁And R₂Each it is preferably selected from substituted or unsubstituted C_1-10Straight chain, side chain or ring-type alkyl, alkoxyl or alkyl sulfenyl, or C₆To C₁₀Aromatic group.Work as R₁、R₂、R₃Or R₄During for being substituted, replacement can include one or more substituents: hydroxyl and slaine thereof；Sulfydryl and slaine thereof；Halogen；Amino, nitro, cyano group and amide groups；Carboxyl, including ester, acid and slaine thereof；Silylation；Acrylate group and slaine thereof；Sulfonyl or sulfamoyl；Bound phosphate groups and phosphite group.When M is metal ingredient, it can be any suitable metallic element that those of ordinary skill in the art can obtain.It is said that in general, metal can be transition metal, although being preferably tellurium or selenium.In one embodiment, aromatic organic compounds is substantially free of metal, although in another embodiment, aromatic organic compounds is entirely free of metal.

This softening accelerator can also include group via composition.Elemental sulfur and polymerised sulphur can be from Elastochem, and Inc. (Chardon, OH) buys acquisition.Exemplary sulfur catalyst compound includes PB (RM-S)-80 elemental sulfur and PB (CRST)-65 polymerised sulphur, respectively can be from Elastochem, and Inc. buys acquisition.Exemplary trade nameTellurium catalyst and exemplary trade nameSelenium catalyst respectively from RTVanderbilt buy obtain.

Other suitably soften accelerator and include but not limited to hydroquinones, benzoquinone class, green hydroquinone. class, catechol and resorcinol class.

Suitably hydroquinone compound includes compound and the hydrate thereof being expressed from the next:

The most each R₁、R₂、R₃And R₄For hydrogen；Halogen；Alkyl；Carboxyl；Its slaine, and its ester；Acetate groups (acetate) and ester thereof；Formoxyl；Acyl group；Acetyl group；Halo carbonyl；Sulfo group and ester thereof；Halosulfonyl groups；Sulfino (sulfino)；Alkylsulfinyl；Carbamoyl；Haloalkyl；Cyano group；Alkoxyl；Hydroxyl and slaine thereof；Amino；Nitro；Aryl；Aryloxy；Aryl alkyl；Nitroso-group；Acetylamino；Or vinyl.

Other suitable hydroquinone compounds include but not limited to: hydroquinone；Four chlorohydroquinones；2-chlorohydroquinone；2-bromohydroquinone；2,5-dichloro hydroquinones；2,5-bis-bromohydroquinones；Four bromohydroquinones；2-methylnaphthohydroquinone；TBHQ；2,5-bis-amyl hydroquinone；With 2-(2-chlorphenyl) hydroquinone hydrate.

More suitably hydroquinone compound includes compound and the hydrate thereof being expressed from the next:

The most each R₁、R₂、R₃And R₄Slaine for carboxyl；Acetate groups and ester thereof；Hydroxyl；The slaine of hydroxyl；Amino；Nitro；Aryl；Aryloxy；Aryl alkyl；Nitroso-group；Acetylamino；Or vinyl.

Suitably benzoquinone compound includes compound and the hydrate thereof being expressed from the next:

Other suitable benzoquinone compounds include one or more compounds and the hydrate thereof being expressed from the next:

Suitably green hydroquinone. class includes one or more compounds and the hydrate thereof being expressed from the next:

The most each R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈For hydrogen；Halogen；Alkyl；Carboxyl；Its slaine, and its ester；Acetate groups (acetate) and ester thereof；Formoxyl；Acyl group；Acetyl group；Halo carbonyl；Sulfo group and ester thereof；Halosulfonyl groups；Sulfino (sulfino)；Alkylsulfinyl；Carbamoyl；Haloalkyl；Cyano group；Alkoxyl；Hydroxyl and slaine thereof；Amino；Nitro；Aryl；Aryloxy；Aryl alkyl；Nitroso-group；Acetylamino；Or vinyl.

Other suitable green hydroquinone. classes include that those have the compound of above formula, wherein R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈It is respectively the slaine of carboxyl；Acetate groups (acetate) and ester thereof；Hydroxyl；The slaine of hydroxyl；Amino；Nitro；Aryl；Aryloxy；Aryl alkyl；Nitroso-group；Acetylamino；Or vinyl.

Suitably catechol includes one or more compounds and the hydrate thereof being expressed from the next:

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

Suitable resorcinol includes one or more compounds and the hydrate thereof that following formula represents:

Implant also can be added the thermoset rubber compositions of core, to regulate the density of said composition up or down.Generally, implant includes such as following material: tungsten, zinc oxide, barium sulfate, silicon dioxide, calcium carbonate, zinc carbonate, metal, metal-oxide and salt, then the abrasive material (nuclear material of recovery, generally it is ground to the granule of about 30 mesh), high Mooney (Mooney) bala gutta abrasive material again, trans grinds (trans-regrind) nuclear material (nuclear material of recovery, it comprises the transisomer of polybutadiene of a large amount) etc. again.When there is trans abrasive material again, the amount of transisomer is preferably about 10% to about 60%.In a preferred embodiment of the invention, this core comprises syn-isomerism body burden and is greater than about the polybutadiene of 95% and grinds nuclear material (cured (vulcanized)) again as the trans of implant.The trans nuclear material that grinds again of any particle diameter is all sufficient, but its preferably less than about 125 μm.

Add the implant of the one or more part of this golf to generally include and affect the processing aid of rheology and mixed nature (processingaids) or compound, the implant of change density, tearing strength or strengthening implant etc..Described implant is usually inorganic matter, and suitable implant includes various metals or metal-oxide, such as zinc oxide and stannum oxide and barium sulfate, zinc sulfate, calcium carbonate, brium carbonate, clay, tungsten, tungsten carbide, silicate series, and mixture.Implant may also include multiple foaming agent or foaming agent (blowingagent), and it can easily be selected by those skilled in the art.Implant can include entity or hollow, fill or unfilled polymer, pottery, metal and glass microsphere.Generally implant is added one or more parts of the big ball of this Gao Er, to change its density to meet the unified standard of golf.Implant can be additionally used in change center weight or the weight of such as at least one extra play of Special ball (specialtyballs), and the ball for athlete's low weight of low slew rate is preferred.

Following material such as tungsten, zinc oxide, barium sulfate, silicon oxide, calcium carbonate, zinc carbonate, metal, metal-oxide and salt and again abrasive material (nuclear material of recovery, generally be ground to about 30 mesh granules), also it is suitable implant.

Polybutadiene and/or any other base rubber (baserubber) or elastomer system (elastomersystem), can also carry out foaming or filling with tiny balloon or expandable microsphere, described expandable microsphere is in the curing process in the low-gravity level that the temperature expansion set is the most any.Other compositions such as sulfur accelerator (such as two, three or tetramethylthiuram tetrasulfide (tetramethylthiuramdi, tri, tetrasulfide)) and/or the organic sulphur components containing metal use also dependent on the present invention.The suitable organic sulfur accelerator containing metal includes but not limited to: cadmium, copper, lead and the diethyldithio carbamate of tellurium analog, diamyl dithiocarbamate salt and dimethyl dithio carbamate, or its mixture.Other compositions, such as processing aid (such as fatty acid and/or its slaine, process oil, dyestuff and pigment and other additives well known by persons skilled in the art, it is also possible to be enough to realize the amount of its reached purpose of usual use in the present invention.

It is not limited to theory, it is believed that the percentage ratio of the double bond of anti-configuration can manipulate in the whole core containing at least one main chain unsaturated rubber (i.e. polybutadiene), plastics or elastomer and cause trans component gradient.Trans gradient can be upwardly or downwardly affected by changing the type of co-reagent (coagent) in the type of cis to trans catalyst (or softening accelerator (soft-and-fastagent)) and amount, the type of peroxide and amount and formulation and amount.Such as, the formulation containing about 0.25phrZnPCTP can have the about 5% trans gradient through core, and the preparation containing about 2phrZnPCTP can have about 10% or higher trans gradient.Trans gradient manipulated also by hardening time and temperature.Think that relatively low temperature and shorter hardening time can produce relatively low trans gradient, although the combination of these factors multiple can produce and the different and/or rightabout gradient used obtained by single factors.

In core, the percentage ratio of transisomer manipulates also by there was added organic sulfur compound (the most listed above) in core formulation, and described organosulfur compound includes but not limited to pentachloro-thiophenol, pentachloro-thiophenol zinc, xylyl disulphide (ditolyldisulfide) and diphenyl disulfide.The amount of the transisomer that the amount of this organosulfur compound and the overall status of solidification produce during affecting curing reaction.The another kind of method increasing trans content in core is introducing unsaturated rubber in core formulation, the transisomer (the such as polybutadiene containing high trans or the polyoctenamer (polyoctenamer) containing high trans) of described unsaturated rubber contained high levels.High trans rubber can use when being with or without organic sulfur compound.

Generally, higher and/or faster curing degree is prone to higher levels of trans component content, as higher concentration peroxide, soften effect produced by accelerator and ZDA concentration in a way.The even type of rubber can have impact to trans levels, those being catalyzed by rare earth metal (such as Nd) are compared with those rubber formed by group VIII metal (such as Co, Ni and Li), it is possible to form higher levels of trans polybutadiene.

The measurement of the polybutadiene trans-isomer content of the application indication is, and can complete as follows.Calibration standard is prepared with at least two polybutadiene rubber sample known to trans content (the highest and low-antiform percentage ratio polybutadiene).These samples are used alone or mix to produce the trans polybutadiene content ladder of at least about 1.5% to 50% with such form, or folder includes the amount that (bracket) is unknown, thus the calibration curve of gained is containing at least about 13 equally spaced points.

Use is equipped with the FTIR spectrum instrument being commercially available of Photoacoustic (" PAS ") cell (cell), the PAS using following instrument parameter to obtain each standard composes: sweep speed 2.5KHZ (0.16cm/s optics speed), use 1.2KHz electronic filter, arranging undersampling ratio is 2 (before collecting sample, the number that laser signal 0 passes through), co-interpolation (co-add) minima is 128 scannings, at 375 to 4000cm^-1Scope intermediate-resolution be 4cm^-1, sensitivity is set to 1.

In PAS spectrum, cis, trans and vinyl-polybutadiene peak sees 600-1100cm^-1Between.Area under integrable each trans polybutadiene peak.Determine each peak area mark relative to three isomer peak gross areas, it is allowed to build the calibration curve of trans polybutadiene peak area mark actual trans polybutadiene content.Correlation coefficient (the R of gained calibration curve²) must be minimum 0.95.

Unknown nuclear material for point (surface of such as core or center) place interested, by filling PAS cell with the sample containing the untainted surface without allogenic material (the such as demoulding (moldrelease) etc.) just cut, above-mentioned parameter is used to obtain PAS spectrum.Analyze unknown trans polybutadiene area fraction to determine the trans-isomer content of reality from described calibration curve.

Under a kind of known situation including barium sulfate, the said method detecting trans component content may relatively inaccuracy.Therefore, the other or optional test of the trans component content of polybutadiene is as follows.Calibration standard is prepared with polybutadiene known to the trans component content of at least two (the highest and low-antiform polybutadiene percentage ratio).These samples are used alone or mix by this way with the ladder of the trans polybutadiene content producing at least about 1.5% to 50%, or folder includes the amount of the unknown, thus the calibration curve of gained is containing at least 13 equally spaced points.

Use the FT-Raman spectrogrph being equipped with near-infrared laser, use following instrument parameter to obtain StokesRaman spectrum from each reference material: sufficient laser power (laserpower) (usual 400-800mW) does not cause excessive heating or fluorescence to obtain good signal to noise ratio；Resolution 2cm^-1；At 400-4000cm^-1Raman transfer spectral limit (shiftspectralrange) in；Scan with common interpolation at least 300.

Stoechiometric process and software (such as from the PLSplus/IQ of GalacticIndustriesCorp) can be used to build calibration curve by the data produced above.Utilize this software to use the PLS-1 curve of SNV (detrend) optical path length correction generation, mean center data to prepare (meancenterdatapreparation) and spectral limit is 1600-1700cm^-1Bis-grades of derivants (secondderivative) of 5-point SG, obtain acceptable calibration.Correlation coefficient (the R of gained calibration curve²) must be minimum 0.95.

The core of the golf being most suitable for the present invention has the outer nuclear layer formed on kernel, and is formed by substantially uniform rubber composition.This " double-core " has outer surface (outer surface of outer nuclear layer) and geometric center (central point of inner nuclear layer).Intermediate layer (such as cap layer (interior covering)) is put around caryogamy, and cover layer is formed around intermediate layer, covering (cover) is generally formed by casting type polyureas or casting type polyurethane and (i.e. refers to comprise casting type polyureas (100% urea linker/without carbamate linker), casting type polyurethane (100% carbamate linker/without urea linker), casting type heterozygosis poly-(urethane/urea) (prepolymer is entirely carbamate linker and solidifies with amine)；Poly-with casting type heterozygosis (urea ammonia ester) (prepolymer is entirely urea linker and with polyol curing) is formed.In a preferred embodiment, the outer surface of this core has the trans polybutadiene content of about 6% to 10%, the center of this core has the trans polybutadiene content of about 1% to 3%, and the trans component content more than the trans component content at center about 6% or more of the outer surface of this core, to determine that (i.e. the core of the contrary configuration that the trans component content in surface has trans component content higher than the trans component content in center is considered to have negative trans component gradient (negativetransgradient) to pros-and-cons type component gradient (positivetransgradient) along nuclear radius, and it is also covered by this application).

As it has been described above, the golf of the present invention preferably comprises the core with inner nuclear layer and outer nuclear layer, to form " double-core ".Kernel preferably has " zero " or " bearing " hardness gradient.In one embodiment, the hardness gradient of kernel is about 0 to about-20 (in terms of Shore C point), even more preferably about-1 to about-15 Shore C point, and most preferably about-2 to about-12 Shore C points.

The overall diameter of described kernel is about 0.5 inch to about 1.40 inches, even more preferably about 0.8 inch to about 1.30 inch, and most preferably about 1.00 inches to about 1.20 inches.Hardness at kernel geometric center is about 55 Shore C to about 82 Shore C, even more preferably about 60 Shore C to about 80 Shore C, most preferably 65 Shore C to about 78 Shore C.Inner nuclear layer case hardness is preferably from about 50 Shore C to about 82 Shore C, even more preferably about 55 Shore C to about 78 Shore C, and most preferably about 60 Shore C to about 75 Shore C.

For realizing preferred embodiment above, the antioxidant of the rubber composition (in this application it having been carried out more detail discussion) for forming inner nuclear layer is greater than about 0.4 to the ratio of initiator, and more preferably greater than about 0.5.

The case hardness of outer nuclear layer is preferably from about 82 Shore C to about 98 Shore C, even more preferably about 84 Shore C to about 95 Shore C, even more preferably about 85 Shore C to about 92 Shore C.In a selectable embodiment, outer nuclear layer case hardness is about 55 Shore D to about 75 Shore C, and most preferably about 58 Shore D are to about 72 Shore D.

Described outer nuclear layer is generally of " positive hardness gradient ".Preferably, the hardness gradient across outer nuclear layer is about 16 Shore C or less, even more preferably about 10 Shore C or less, and most preferably about 8 Shore C and less.

Optionally, described double-core can be containing the middle stratum nucleare formed by thermoset rubber compositions.Application discusses applicable rubber and the compositions formed by the rubber being suitable for.Middle stratum nucleare can have any hardness gradient, including " zero hardness gradient " and " negative hardness gradient " or " positive hardness gradient ".

The overall diameter of the core (either double-core still contains the core of optional middle stratum nucleare) of the present invention is about 1.40 inches to about 1.64 inches, even more preferably about 1.50 inches to about 1.60 inches, and most preferably about 1.53 inches to about 1.58 inches.

About hardness gradient, core itself can have integral hardness gradient equally.In a preferred embodiment, the geometric center of the surface ratio kernel of core is harder so that core hardness gradient most about 18 Shore C point, more preferably up to about 15 Shore C points, the most about 12 Shore C points.

Described inner nuclear layer is about 10% or less, preferably from about 1% to about 10%, more preferably from about 2% to about 9% by trans-polybutadiene content, and the rubber composition of most preferably from about 4% to about 8% is formed.Described outer nuclear layer is about 10% or more, more preferably from about 20% or more by trans-polybutadiene content, and most preferably from about 30% or more rubber composition is formed.For realizing various different nulcear properties, the trans component content of inner nuclear layer can change with the ratio of the trans component content of outer nuclear layer.Described ratio is preferably greater than 1.5, and more preferably greater than 2.0, most preferably greater than 3.0.

Form multiple core according to the preparation described in table 1 below and cure cycle, and described core hardness number is as shown in table 2 below

Table 1

Preparation (phr)	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2	Comparative example 3
							SR-526+	34.0	34.0	31.2	29.0	29.0	29.0
ZnO	5	5	5	5	5	5
							BaSO₄	11.2	11.2	16.1	13.8	13.8	13.8
VANOX MBPC^*	0.40	0.40	0.40		0.50
							TRIGONOX-265-50B^**	14	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 antioxidant/initiator	0.57	0.57	0.50		0.31
							Solidification temperature (°F)	305	315	320	350	335	335
Hardening time (nin)	14	11	16	11	11	11

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

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

Table 2

It addition, more produced according to the present invention double-cores, and, carry out the hardness measurement-value across core and reported in following table 3.The curve of result can be found in Fig. 1.Described core is respectively provided with the overall diameter of 1.55 inches.Shore C hardness is measured in the multiple positions across core cross section according to ASTMD-2240.Hereafter geometric center, outer surface and the hardness result from the geometric center of core radially outward 2mm, 4mm, 6mm, 8mm, 10mm, 12mm, 14mm, 16mm and 18mm position are tabulated.Additionally, at the interface (on core surface) of inner nuclear layer and outer nuclear layer or near interface (in about 1mm) (in this embodiment, at the point of geometric distance center 12.7mm) and take hardness strong point in the outer surface (in this embodiment, geometric distance center 19.6mm) of core.Center of the present invention all covers with identical outer nuclear layer with comparison center.

General core preparation is as follows: inner nuclear layer comprises the dizinc acrylate resin (to produce different compressions, see Fig. 1) in the range of about 80phrBSTE1220 polybutadiene rubber, about 20phrCB23 polybutadiene rubber, 30-36phr, about 0.4phrVANOXMBPC antioxidant, about 0.7phrZnPCTP, about 1phrPerkadoxBC peroxide and be enough to the ZnO making density reach about 1.125g/cc.Comparison kernel comprises about 85phrBSTBR1220 polybutadiene, about 15phrCB23 polybutadiene, about 15phrPOLYWATE325 (barium sulfate), about 5phrZnO, about 0.5 part of ZnPCTP, about 0.75phr peroxide, about 25phrZDA, about 1phrAFLUX16 processing aid, coloring agent and abrasive material (regrind) again.Kernel has the overall diameter of about 1.00 inches.Outer nuclear layer comprises about 78phrBSTBR1220 polybutadiene, about 13phrCB23 polybutadiene, about 15phrZnO, about 0.4phrPERKADOXBC peroxide, about 38phrZDA, again abrasive material, coloring agent and balata natural gum (balata) sclerosing agent.

Adjust cure cycle when necessary to change the hardness gradient across core.Temperature/time standard is in about 330 °F/20min, 335 °F/18min, change between 340 ° of P/16min and 345 °F/14min.Kernel of the present invention is moulded about 18 minutes at 305 °F.

Table 3

See table 3 and Fig. 1, it is therefore clear that it is 10 or bigger (hardness at the hardness number of Correlation Centre surface and geometric center) that embodiment 1-3 is respectively provided with the grade of " negative hardness gradient " inner nuclear layer-gradient.On the contrary, comparison golf demonstrates the inner nuclear layer with " positive hardness gradient ".

The case hardness of core is that the meansigma methods from the repetitive measurement of the opposite hemispheres to core obtains, and carefully avoids measuring on the die parting line of core or in surface defect (such as hole or projection).Hardness measurement is to carry out according to ASTMD-2240 " by rubber and the identation hardness (IndentationHardnessofRubberandPlasticbyMeansofaDurometer) of plastics of Durometer measurements ".Curved surface due to core, it is necessary to carefully guarantee obtain the pronucleus of case hardness reading at penetrator under placed in the middle.Use through calibration, the digital durometer that can read 0.1 stiffness units carries out all hardness measurements, and is arranged to use hardness reading when obtaining after full-scale reading 1 second.Digital durometer has to connect to the base portion of automatic station and makes its base parallel with the base portion of automatic station so that weight and impact speed on durometer meet ASTMD-2240.

In order to prepare the core measured for hardness gradient, lightly core is pressed into the hemisphere clamper that internal diameter is substantially smaller than the diameter of core so that core is fixed in the hemispherical portion of clamper, makes the geometric center plane of core expose simultaneously.Core is by being frictionally held in clamper so that it will not move during cutting and grinding steps, but frictional force is not excessive, is not result in the natural shape deformation of core.Core is fixing, so that the die parting line of core is substantially parallel with the top of clamper.Before fixing, to be orientated to 90 degree of diameters measuring core with this.Measure and also carry out to core top the reference point to provide calculate future from clamp base.The geometric center using band saw or other suitable cutting tools to expose at core carries out rough cutting slightly above, it is ensured that core does not move in clamper in this step.The still remainder of the core in clamper, is fixed on the substrate of surface grinding machine." coarse " core surface exposed is ground as smooth flat surface, expose the geometric center of core, it can be verified by measuring the height on the surface that clamp base exposes to core, it is ensured that has removed the just half of as above measured core original height to ± 0.004 inch.

Core is stayed in clamper, find the center of core, and carefully labelling with centre square, and at this centre mark, measure hardness.The hardness measurement of any distance in distance core center can be passed through from centre mark radially outward setting-out, and measures and the excentric distance of labelling, is typically separated about 2mm, measures.All hardness measurements carrying out the plane through geometric center are carried out when described core is thrown away in clamper, do not upset its orientation, so that test surfaces is always parallel with clamp base.Difference of hardness from any precalculated position of core is calculated as average surface hardness and deducts the hardness of suitable reference point (such as, single, the center of entity core), so that the core surface softer than its center can have negative hardness gradient.

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

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

Antioxidant is a factor controlling core case hardness to the ratio of initiator.The data display hardness gradient being shown in table 2 at least but is not limited to the amount of antioxidant and peroxide, their ratio and the function of cure cycle.It should be noted that higher antioxidant also needs to the compression needed for maintaining of the higher peroxide initiator.

The core of comparative example 1, its composition is shown in table 1, is to use conventional curing cycle solidification, and solidification temperature is 350 °F and hardening time is 11 minutes.The core of the present invention is to use 305 °F to carry out 14 minutes, and 315 °F are carried out 11 minutes, and 320 °F carry out the cure cycle of 16 minutes and produce.Measure the hardness gradient of these cores and carried out following observation.For the core in comparative example, as expected, hence it is evident that the crust of visible routine is to the gradient at soft center.The gradient of the core of the present invention follows same shape the most each other.

In all preferred embodiments of the present invention, the core hardness on surface most about equal to or significantly less than the hardness at He center.Additionally, the core rigidities of core is not likely to be point the hardest in core, but in all cases, it is preferably at least hard as surface or specific surface is harder.In some embodiments, during lowest hardness value betides about core surface 6mm in the outer part.But, the lowest hardness value in core can betide any point on distance surface, until but not including center, as long as case hardness is still equal to or is less than core rigidities.It should be noted that in the present invention, in whole core or stratum nucleare, formula is identical, and core does not imposes surface process to obtain preferred case hardness.

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

(1) polyurethane, such as those are prepared from polyhydric alcohol or polyamines and diisocyanate or polyisocyanates and/or its prepolymer, and those are disclosed in United States Patent (USP) No.5,334,673 and 6,506,851；

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

(3) the hybrid thing of polyurethane-urea, blend or the copolymer of carbamate or urea segment are comprised.

Suitably urethane composition comprises the product of at least one polyisocyanates and at least one firming agent.Firming agent can include such as one or more polyamines, one or more polyhydric alcohol or combinations thereof.Can be by polyisocyanates and one or more polyhydric alcohol conjugate to form prepolymer, then by this prepolymer and the combination of at least one firming agent.So, polyhydric alcohol described herein is suitable in one or both of two kinds of compositions of polyurethane material using (i.e. using) as a part for prepolymer or in firming agent.Suitably polyurethane is recorded in U.S. Patent Application Publication text No.2005/0176523, it is completely included by addressing.

The available any polyisocyanates of those of ordinary skill in the art is suitable for using according to the present invention.Exemplary polyisocyanates includes but not limited to 4,4 '-methyl diphenylene diisocyanate (MDI)；Polymeric MDI；The liquid MDI of carbodiimide modified；HMDI (H₁₂MDI)；P-phenylene diisocyanate (PPDI)；-phenylene diisocyanate (MPDI)；Toluene di-isocyanate(TDI) (TDI)；3,3 '-dimethyl-4,4 '-diphenylene diisocyanate；Isophorone diisocyanate；1,6-hexamethylene diisocyanate (HDI)；Naphthalene diisocyanate；XDI；P-tetramethylxylene diisocyanate；M-tetramethylxylene diisocyanate；Ethylidene diisocyanate；Propylidene-1,2-diisocyanate；Tetramethylene-Isosorbide-5-Nitrae-diisocyanate；Cyclohexyl diisocyanate；Dodecane-1,12-diisocyanate；Tetramethylene .-1,3-diisocyanate；Hexamethylene-1,3-diisocyanate；Hexamethylene-Isosorbide-5-Nitrae-diisocyanate；1-NCO-3,3,5-trimethyl-5-isocyanatomethyl hexamethylene；Methylcyclohexylidene diisocyanate；The triisocyanate of HDI；2,4,4-trimethyl-1, the triisocyanate of 6-hexane diisocyanate；Aphthacene diisocyanate (tetracenediisocyanate)；Naphthalene two Carbimide.；Anthracene two Carbimide.；The isocyanide urea of toluene diisocynate；The uretdione of hexa-methylene two Carbimide.；And mixture.Skilled addressee will appreciate that polyisocyanates has more than an isocyanate groups, such as di-isocyanate, tri-isocyanate and four-isocyanates.Preferably, polyisocyanates includes MDI, PPDI, TDI or its mixture, and it is highly preferred that polyisocyanates includes MDI.It is to be understood that, as used in this article, term MDI includes 4,4 '-methyl diphenylene diisocyanate, polymeric MDI, the liquid MDI of carbodiimide modified and their mixture, and, it addition, the diisocyanate used can be " low free monomer ", those of ordinary skill in the art are interpreted as " dissociating " the monomeric diisocyanate group with reduced levels, generally less than about 0.1% free monomeric isocyanates group.The example of " low free monomer " diisocyanate includes but not limited to low free monomer MDI, low free monomer TDI and low free monomer PPDI.At least one polyisocyanates described should have less than about 14% unreacted NCO group.Preferably, at least one polyisocyanates described has no more than about 8.0%NCO, and more preferably no more than about 7.8%, and the most no more than about 7.5%NCO, normally used NCO level is about 7.2% or the NCO of 7.0% or 6.5%.

The available any polyhydric alcohol of those of ordinary skill in the art is suitable for using according to the present invention.Exemplary polyhydric alcohol includes but not limited to polyether polyol, hydroxy-end capped polybutadiene (including the derivant partially completely hydrogenated), PEPA, polycaprolactone polyol and polycarbonate polyol.In a preferred embodiment, polyhydric alcohol includes polyether polyol.Example includes but not limited to polytetramethylene ether diol (PTMEG), Polyethylene Glycol propylene glycol, polyoxypropylene glycol and mixture thereof.Hydrocarbon chain can have saturated or unsaturated key and substituted or unsubstituted aromatic series and cyclic group.Preferably, the polyhydric alcohol of the present invention includes PTMEG.

In another embodiment, polyurethane material includes PEPA.Suitably PEPA includes but not limited to 10PE27 glycol；Polybutylene glyool adipate；10PE27 propylene glycol ester glycol；O-phthalate ester-1,6-hexanediol；Poly-(adipic acid hexanediol ester) glycol；And mixture.Hydrocarbon chain can have saturated or unsaturated key or substituted or unsubstituted aromatic series and cyclic group.

In another embodiment, the material of the present invention includes polycaprolactone polyol.Suitably polycaprolactone polyol includes but not limited to 1, polycaprolactone, the polycaprolactone of diethylene glycol initiation, the polycaprolactone of trimethylolpropane initiation, the polycaprolactone of dimethyltrimethylene glycol initiation, the polycaprolactone of BDO initiation and the mixture thereof that 6-hexanediol causes.Hydrocarbon chain can have saturated or unsaturated key or substituted or unsubstituted aromatic series and cyclic group.

In also embodiment, the polyurethane material of the present invention includes polycarbonate polyol.Suitably Merlon includes but not limited to poly-carbonic acid O-phthalic ester and poly-(carbonic acid hexanediol ester) glycol.Hydrocarbon chain can have saturated or unsaturated key or substituted or unsubstituted aromatic series and cyclic group.In one embodiment, the molecular weight of polyhydric alcohol is about 200 to about 4000.

Polyamine curing agent also is adapted in the urethane composition of the present invention using, and has been found that cutting resistance, shear resistant and the impact resistance improving gained ball.Preferably polyamine curing agent includes but not limited to 3,5-dimethyl sulfenyl-2,4-toluenediamine and isomer thereof；3,5-diethyltoluene-2,4-diamidogen and isomer thereof, such as 3,5-diethyltoluene-2,6-diamidogen；4,4 '-two-(sec-butyl amino)-diphenyl methanes；Isosorbide-5-Nitrae-two-(sec-butyl amino)-benzene, 4,4 '-methylene-two-(2-chloroaniline)；4,4 '-methylene-two-(3-chloro-2,6-diethyl aniline)；Polytetramethylene oxygen-two-p-amino benzoic Acid；N, N '-dialkyl diamidogen diphenyl methane；P, p '-methylene dianiline (MDA)；M-diaminobenzene.；4,4 '-methylene-two-(2-chloroaniline)；4,4 '-methylene-two-(2,6-diethylaniline)；4,4 '-methylene-two-(2,3-dichloroaniline)；4,4 '-diaminourea-3,3 '-diethyl-5,5 '-dimethyl diphenylmethane；2,2 ', 3,3 '-tetrachloro diaminodiphenyl-methane；Trimethylene two-p-Aminobenzoate；And mixture.Preferably, the firming agent of the present invention includes 3,5-dimethyl sulfenyl-2,4-toluenediamine and isomer thereof, such as300, it is purchased from AlbermarleCorporation (BatonRouge, LA).Suitably polyamines (including primary amine and secondary amine) firming agent preferably has the molecular weight of scope about 64 to about 2000.

Can be by glycol, triol, tetrol or hydroxy-end capped firming agent, at least one adds to urethane composition mentioned above.Suitably glycol, triol and four alcohol groups include ethylene glycol；Diethylene glycol；Polyethylene Glycol；Propylene glycol；Polypropylene glycol；Lower molecular weight polytetramethylene ether diol；1,3-bis-(2-hydroxyl-oxethyl] benzene；1,3-bis--[2-(2-hydroxyl-oxethyl) ethyoxyl] benzene；1,3-bis--{ 2-[2-(2-hydroxyl-oxethyl) ethyoxyl] ethyoxyl } benzene；BDO；1,5-PD；1,6-hexanediol；Resorcinol-two-(beta-hydroxy ethyl) ether；Hydroquinone-two-(beta-hydroxy ethyl) ether；And mixture.The most hydroxy-end capped firming agent includes 1,3-bis-(2-hydroxyl-oxethyl) benzene；1,3-bis--[2-(2-hydroxyl-oxethyl) ethyoxyl] benzene；1,3-bis--{ 2-[2-(2-hydroxyl-oxethyl) ethyoxyl] ethyoxyl } benzene；BDO, and mixture.Preferably, hydroxy-end capped firming agent has scope and is about the molecular weight of 48 to 2000.Should be appreciated that molecular weight is absolute weight mean molecule quantity, as those of ordinary skill in the art will understand that as used in this article.

Hydroxy-end capped firming agent and amine hardener may each comprise one or more saturated, undersaturated, aromatic and ring-type group.It addition, hydroxy-end capped firming agent and amine hardener can include one or more halogen group.Urethane composition can be formed with the mixture of several firming agent or admixture.But, when needed, urethane composition can be formed with single curing agent.

In a preferred embodiment of the invention, use saturated polyurethane to form one or more cover layer, preferably outer cover, and pourable thermosetting and thermoplastic polyurethane can be selected from.In this embodiment, the saturated polyurethane of the present invention there is no aromatic group or part.The saturated polyurethane being suitable for using in the present invention is the product of the reaction between at least one polyurethane prepolymer and the firming agent that at least one is saturated.Polyurethane prepolymer is the product that the reaction between the polyhydric alcohol saturated by least one and the diisocyanate that at least one is saturated is formed.As is well known the art, catalyst can be used to promote the reaction between firming agent Yu isocyanates and polyhydric alcohol, or firming agent and prepolymer.

The saturated diisocyanate that can use includes but not limited to ethylidene diisocyanate；Propylidene-1,2-diisocyanate；Tetramethylene-Isosorbide-5-Nitrae-diisocyanate；1,6-hexamethylene diisocyanate (HDI)；2,2,4-trimethyl hexamethylene diisocyanates；2,4,4-trimethyl hexamethylene diisocyanates；Dodecane-1,12-diisocyanate；Dicyclohexyl methyl hydride diisocyanate；Tetramethylene .-1,3-diisocyanate；Hexamethylene-1,3-diisocyanate；Hexamethylene-Isosorbide-5-Nitrae-diisocyanate；1-NCO-3,3,5-trimethyl-5-isocyanatomethyl hexamethylene；Isophorone diisocyanate；Methylcyclohexylidene diisocyanate；The triisocyanate of HDI；2,2,4-trimethyl-1, the triisocyanate of 6-hexane diisocyanate.The most saturated diisocyanate is HMDI and isophorone diisocyanate.

The saturated polyhydric alcohol being suitable for using in the present invention includes but not limited to polyether polyol such as polytetramethylene ether diol and poly-(oxygen propylidene) glycol.The most saturated PEPA includes 10PE27 glycol, 10PE27 propylene glycol ester glycol, polybutylene glyool adipate, polycarbonate polyol and the polyoxypropylene glycol of oxirane capping.The most useful saturated polycaprolactone polyol include polycaprolactone that polycaprolactone that diethylene glycol causes, BDO cause, 1, the polycaprolactone that 6-hexanediol causes；The polycaprolactone that polycaprolactone, the polycaprolactone of dimethyltrimethylene glycol initiation and the polytetramethylene ether diol that trimethylolpropane causes causes.The most saturated polyhydric alcohol is polytetramethylene ether diol and the polycaprolactone of PTMEG initiation.

The most saturated firming agent includes BDO, ethylene glycol, diethylene glycol, polytetramethylene ether diol, propylene glycol；Trihydroxymethyl propane；Four-(2-hydroxypropyl) ethylenediamines；The isomer of cyclohexane dimethanol and isomer mixture, the isomer of hexamethylene two (methyl amine) and isomer mixture；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 two-(aminopropyl) ether；4,4 '-two-(sec-butyl amino)-dicyclohexyl methyl hydrides；1,2-bis--(sec-butyl amino) hexamethylene；Isosorbide-5-Nitrae-two-(sec-butyl amino) hexamethylene；Isophorone diamine；Hexamethylene diamine；Propane diamine；1-methyl-2,4-cyclohexyl diamine；1-methyl-2,6-cyclohexyl diamine；1,3-diaminopropanes；Dimethylamino propylamine；Diethyl amino propylamine；Imino group-two-propylamine；The isomer of diamino-cyclohexane and isomer mixture；Monoethanolamine；Diethanolamine；Triethanolamine；Monoisopropanolamine；And diisopropanolamine (DIPA).The most saturated firming agent is BDO, Isosorbide-5-Nitrae-cyclohexane dimethanol and 4,4 '-two-(sec-butyl amino)-dicyclohexyl methyl hydrides.

Or, the polymer of ionomer, metallocene or other single site catalysed that other suitable polymer includes partially or completely neutralizing, polyester, polyamide, non-ionomeric 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, etc. and their mixture.Heat-curable urethane or polyureas are suitable for the outer cover of the golf of the present invention.

It addition, polyurethane can be replaced by polyurea materials or be blended with polyurea materials.Polyureas is completely different with urethane composition, but also causes desired aerodynamic and aesthetic features when using in golf composition.Compositions based on polyureas is saturated the most in nature.

Without being bound by any particular theory, it is presently believed that substitute the long-chain polyhydric alcohol segment in polyurethane prepolymer with long-chain polyamines oligomer soft chain segment and improve the property sheared, cutting and resilience, and the adhesiveness to other composition.So, can be by forming the polyurea composition of the present invention by the product of firming agent crosslinking isocyanates and polyamines prepolymer.For example, it is possible to prepare present invention compositions based on polyureas from least one isocyanates, at least one polyetheramine and at least one two polyol curing agent or at least one diamine curing agent.

The available any polyamines of those of ordinary skill in the art is suitable in polyurea prepolymer using.Polyetheramine is particularly suitable in prepolymer using.As used in this article, " polyetheramine " refers at least to the polyoxy alkylene amine containing the primary amino radical being attached to polyether backbone end.But, due to isocyanates and the fast reaction of amine and the indissolubility of many urea products, the selection of diamidogen and polyetheramine is limited to allow those being successfully formed polyurea prepolymer.In one embodiment, polyether backbone is based on tetramethylene, propylene, ethylene, trihydroxymethyl propane, glycerol and mixture thereof.

Suitably polyetheramine includes but not limited to methyl diethanolamine；Polychlorostyrene Alkylenediamine such as polytetramethylene ether diamine, polyoxypropylene triamine and polyoxypropylene diamine；Poly-(ethylene oxide-capped oxygen propylidene) ether diamine；Triamine based on expoxy propane；Triethylene glycol diamidogen；Triamine based on trihydroxymethyl propane；Triamine based on glycerol；And their mixture.In one embodiment, the polyetheramine being used for being formed prepolymer isD2000 (HuntsmanChemicalCo., Austin, TX).

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

Such as short discussion above, some amine may be unsuitable for reacting with isocyanates, because both becomes branch that fast reaction occurs.Specifically, the amine of relatively short chain can occur fast reaction.But, in one embodiment, the secondary diamine being obstructed is applicable to prepolymer.It is reluctant to arrest in any particular theory, it is believed that there is the amine of high-level steric hindrance (stearichindrance) (tertiary butyl groups on such as nitrogen-atoms) slower than the reaction rate of the amine without steric hindrance or the amine with low-level steric hindrance.For example, 4,4 '-two-(s-butylamino)-dicyclohexyl methyl hydride (1000) may be adapted to combine with isocyanates to form polyurea prepolymer.

The spendable isocyanates of any those of ordinary skill in the art is suitable for polyurea prepolymer.Isocyanates for the present invention includes that per molecule has the aliphatic of two or more NCOs (NCO) group, alicyclic, the compound of araliphatic, aromatics, and any derivant, and the combination of these compounds.Described isocyanates can be end be the prepolymer of organic multiple isocyanate.Described can may also include any isocyanate functional monomer, dimer, trimer or its many polyadducts, prepolymer, quasi-prepolymer (quasi-prepolymer), or its mixture by reacted constituent containing isocyanates.Isocyanate functional compound can include monoisocyanates or polyisocyanates, and the latter includes two or more any isocyanate functional groups.

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

The example of the diisocyanate that can be used for the present invention includes but not limited to: the mixture of substituted and isomery, including 2,2 '-, 2,4 '-and 4,4 '-methyl diphenylene diisocyanate；3,3 '-dimethyl-4,4 '-biphenylene diisocyanate；Toluene di-isocyanate(TDI)；Polymeric MDI；The liquid 4 of carbodiimide modified, 4 '-methyl diphenylene diisocyanate；PPDI；M-benzene diisocyanate；Triphenyl methane-4,4 '-and triphenyl methane-4,4 ' triisocyanates；Naphthalene-1,5-diisocyanate；2,4 '-, 4,4 '-and 2,2 '-diphenyl diisocyanate；Polyphenyl polymethylene polyisocyanates；The mixture of MDI and PMDI；The mixture of PMDI and TDI；Ethylidene diisocyanate；Propylidene-1,2-diisocyanate；Tetramethylene-1,2-diisocyanate；Tetramethylene-1,3-diisocyanate；Tetramethylene-Isosorbide-5-Nitrae-diisocyanate；1,6-hexamethylene diisocyanate；Eight methylene diisocyanates；Decamethylene diisocyanate；2,2,4-trimethyl hexamethylene diisocyanates；2,4,4-trimethyl hexamethylene diisocyanates；Dodecyl-1,12-diisocyanate；Tetramethylene .-1,3-diisocyanate；Hexamethylene-1,2-diisocyanate；Hexamethylene-1,3-diisocyanate；Hexamethylene-Isosorbide-5-Nitrae diisocyanate；Methyl-cyclohexylene diisocyanate；2,4-methylcyclohexane diisocyanates；2,6-methylcyclohexane diisocyanates；4,4 '-dicyclohexyl diisocyanate；2,4 '-dicyclohexyl diisocyanate；1,3,5-hexamethylene triisocyanate；Isocyanatomethyl cyclohexyl isocyanate；1-NCO-3,3,5-trimethyl-5-isocyanatomethyl hexamethylene；Isocyanatoethyl cyclohexyl isocyanate；Two (isocyanatomethyl)-cyclohexane diisocyanates；4,4 '-two (isocyanatomethyl) bicyclohexane；2,4 '-two (isocyanatomethyl) bicyclohexane；Isophorone diisocyanate；The triisocyanate of HDI；2,2,4-trimethyl-1, the triisocyanate of 6-hexane diisocyanate；HMDI；2,4-hexahydrotoluene diisocyanate；2,6-hexahydrotoluene diisocyanate；1,2-, 1,3-and Isosorbide-5-Nitrae-phenylene vulcabond；Aromatic aliphatic isocyanates, such as 1,2-, 1,3-and the stupid diisocyanate of Isosorbide-5-Nitrae-diformazan；M-tetramethylxylene diisocyanate；P-tetramethylxylene diisocyanate；The isocyanuric acid ester of the trimerizing of any polyisocyanates, isocyanuric acid ester such as 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 isophorone diisocyanate, and mixture.The dimerization uretdione of any polyisocyanates, such as the uretdione of toluene di-isocyanate(TDI), the uretdione of hexamethylene diisocyanate, and mixture；Derive from the modified polyisocyanate of above-mentioned isocyanates and polyisocyanates；And mixture.

The example of the saturated diisocyanate that can be used for the present invention includes but not limited to: ethylidene diisocyanate；Propylidene-1,2 diisocyanate；Tetramethylene diisocyanate；Tetramethylene-Isosorbide-5-Nitrae-diisocyanate；1,6-hexamethylene diisocyanate；Eight methylene diisocyanates；Decamethylene diisocyanate 2,2,4-trimethyl hexamethylene diisocyanate；2,4,4-trimethyl hexamethylene diisocyanates；Dodecane-1,12 diisocyanate；Tetramethylene .-1,3-diisocyanate；Hexamethylene-1,2-diisocyanate；Hexamethylene-1,3-diisocyanate；Hexamethylene-Isosorbide-5-Nitrae-diisocyanate；Methyl-cyclohexylene diisocyanate；2,4-methylcyclohexane diisocyanates；2,6-methylcyclohexane diisocyanates；4,4 '-dicyclohexyl diisocyanate；2,4 '-dicyclohexyl diisocyanate；1,3,5-hexamethylene triisocyanate；Isocyanatomethyl cyclohexyl isocyanate；1-NCO-3,3,5-trimethyl-5-isocyanatomethyl hexamethylene；Isocyanatoethyl cyclohexyl isocyanate；Two (isocyanatomethyl)-cyclohexane diisocyanates；4,4 '-two (isocyanatomethyl) bicyclohexane；2,4 '-two (isocyanatomethyl) bicyclohexane；Isophorone diisocyanate；The triisocyanate of HDI；2,2,4-trimethyl-1, the triisocyanate of 6-hexane diisocyanate；HMDI；2,4-hexahydrotoluene diisocyanate；2,6-hexahydrotoluene diisocyanate；And mixture.Aromatic aliphatic isocyanates also can be used for forming light stabilizing material.The example of this type of diisocyanate includes 1,2-, 1,3-and Isosorbide-5-Nitrae-XDI；The stupid diisocyanate of m-tetramethyl xylene；P-tetramethylxylene diisocyanate；Three poly-isocyanurates of any polyisocyanates, isocyanuric acid ester such as 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 isophorone diisocyanate, and mixture；The dimerization uretdione of any polyisocyanates, such as the uretdione of toluene di-isocyanate(TDI), the uretdione of hexamethylene diisocyanate, and mixture；Derive from the modified polyisocyanate of above-mentioned isocyanates and polyisocyanates；And mixture.Additionally, for the purposes of the present invention, described aromatic aliphatic isocyanates can mix with any saturated isocyanates listed above.

Unreacted NCO group number can be changed in the polyurea prepolymer of isocyanates and polyetheramine to control such as factors such as reaction rate, resulting composition hardness.Such as, in the polyurea prepolymer of isocyanates and polyetheramine, unreacted NCO group number can less than about 14%.In one embodiment, described polyurea prepolymer has the unreacted NCO group of about 5% to about 11%, and even more preferably with the unreacted NCO group of about 6% to about 9.5%.In one embodiment, the percentage ratio of unreacted NCO group is about 3% to about 9%.Selectively, unreacted NCO group percentage ratio in polyurea prepolymer can be about 7.5% or less, and more preferably about 7% or less.In another embodiment, unreacted NCO content is about 2.5% to about 7.5%, and more preferably about 4% to about 6.5%.

When formed, polyurea prepolymer can comprise the free isocyanate-monomer accounting for described prepolymer about 10% to about 20% by weight.Therefore, in one embodiment, described polyurea prepolymer can eliminate free isocyanate-monomer.Such as, after eliminating, described prepolymer can include about the free isocyanate-monomer of 1% or less.In another embodiment, described prepolymer comprises the free isocyanate-monomer of by weight about 0.5% or less.

Described polyetheramine can mix with other polyhydric alcohol to prepare copolymer, makes described copolymer be reacted to form polyurea prepolymer with the isocyanates of excess.In one embodiment, the polyhydric alcohol of based on copolymer weight less than about 30% is mixed with saturated polyetheramine.In another embodiment, the polyhydric alcohol of based on copolymer weight less than about 20% preferably based on copolymer weight less than about 15% is mixed with described polyetheramine.Polyhydric alcohol listed above, relative to polyurethane prepolymer, such as polyether polyol, polycaprolactone polyol, PEPA, polycarbonate polyol, hydrocarbon polyhydric alcohol, other polyhydric alcohol, and mixture, it is also adapted to mix with described polyetheramine.The molecular weight of these polymer can be about 200 to about 4000, but also can be about 1000 to about 3000, and even more preferably about 1500 to about 2500.

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

Suitably amine end-blocking firming agent includes but not limited to: ethylenediamine；Hexamethylene diamine；1-methyl-2,6-cyclohexyl diamine；Tetrahydroxy propylidene ethylenediamine；2,2,4-and 2,4,4-trimethyl-1,6-hexane diamine；4,4 '-two-(s-butylamino)-dicyclohexyl methyl hydride；Isosorbide-5-Nitrae-two-(s-butylamino)-hexamethylene；1,2-bis--(s-butylamino)-hexamethylene；The derivant of 4,4-bis--(s-butylamino)-dicyclohexyl methyl hydride；4,4 '-dicyclohexyl methyl hydride diamidogen；Isosorbide-5-Nitrae-hexamethylene-two-(methylamine)；1,3-hexamethylene-two-(methylamine)；Diethylene glycol two-(aminopropyl) ether；2-methyl pentamethylene-diamidogen；Diamino-cyclohexane；Diethylenetriamines；Trien；Tetren；Trimethylene diamine；1,3-diaminopropanes；Dimethylamino propylamine；Diethyl amino propylamine；Dipropylenetriamine；Imido grpup-two-propylamine；Monoethanolamine, diethanolamine；Triethanolamine；Single 2-aminopropane., diisopropylamine；Isophorone diamine；4,4 '-methylene, two-(2-chloroaniline)；3,5-dimethyl sulphur-based-2,4-toluenediamine；3,5-dimethyl sulphur-based-2,6-toluenediamine；3,5-diethyl sulfenyl-2, the stupid diamidogen of 4-first；3,5-diethyl sulfenyl-2,6-toluenediamine；The stupid methane of 4,4 '-two-(s-butylamino)-two and derivant thereof；Isosorbide-5-Nitrae-two-(s-butylamino)-benzene；1,2-bis--(s-butylamino)-benzene；N, N '-dialkyl amido-diphenyl-methane；N, N, N ', N '-four (2-hydroxypropyl) ethylene diamine；Trimethylene-two-p-aminobenzoate；Oxolane-two-p-aminobenzoate；4,4 '-methylene, two-(3-chloro-2,6-diethylidene aniline)；4,4 '-methylene, two-(2,6-diethylaniline)；-phenylene diamidogen；P-pHENYLENE dI AMINE；And mixture.In one embodiment, the firming agent of described amine end-blocking is 4,4 '-two-(s-butylamino)-dicyclohexyl methyl hydride.

Suitable saturated amine end firming agent includes but not limited to: ethylenediamine；Hexamethylene diamine；1-methyl-2,6-cyclohexyl diamine；Tetrahydroxy propylidene ethylenediamine；2,2,4-and 2,4,4-trimethyl-1,6-hexamethylene diamine；4,4 '-two-(s-butylamino)-dicyclohexyl methyl hydride；Isosorbide-5-Nitrae-two (s-butylamino)-hexamethylene；1,2-bis--(s-butylamino)-hexamethylene；The derivant of 4,4 '-two-(s-butylamino)-dicyclohexyl methyl hydride；4,4 '-dicyclohexyl methyl hydride diamidogen；4,4 '-methylene, two-(2,6-diethyl amino butylcyclohexane)；Isosorbide-5-Nitrae-hexamethylene-two-(methylamine)；1,3-hexamethylene-two-(methylamine)；Diethylene glycol two-(aminopropyl) ether；2-methyl pentamethylene diamine；Diamino-cyclohexane；Diethylenetriamines；Trien；Tetren；Trimethylene diamine；1,3-diaminopropanes；Dimethylamino propylamine；Diethyl amino propylamine；Imido grpup-two-propylamine；Monoethanolamine, diethanolamine；Triethanolamine；Monoisopropanolamine, diisopropanolamine (DIPA)；Isophorone diamine；Triisopropanolamine；And mixture.Additionally, any polyetheramine listed above can be used as firming agent to react with polyurea prepolymer.

The cover layer of golf of the present invention also can be made from the ionomer (HNP) of ionomer preferably height neutralization.In a preferred embodiment, at least one intermediate layer of described golf is made up of the mixture of HNP material or HNP material.The acidic moiety of HNP, is typically based on the ionomer of ethylidene, is preferably neutralized greater than about 70%, more preferably greater than about 90%, and most preferably at least about 100%.HNP also can mix with the second polymers compositions, if described component is containing acid groups, then can use usual manner to neutralize, and is neutralized by the organic aliphatic acid of the present invention, or both are all.Described second polymers compositions, can partially or completely neutralize, and preferably comprises ionomeric copolymer and trimer, ionomer precursor, thermoplastic, polyamide, Merlon, polyester, polyurethane, polyureas, thermoplastic elastomer (TPE), polybutadiene rubber, balata (balata), the polymer of metallocene catalysis (grafting and non-grafted), point of the polymer units, highly crystalline acid polymer, cationic ionomer etc..HNP polymer is generally of the material hardness of about 20 to about 80 Shore D, and about 3000psi is to the bending modulus of about 200000psi.

In one embodiment of the invention, HNP is ionomer, and/or its acid precursors, preferably neutralizes wholly or in part through organic acid copolymer or its salt.Described acid copolymer is preferably the copolymer of following material: alpha-olefin, such as ethylene, C_3-8α, β-ethylenic unsaturated carboxylic acid, such as acrylic acid and methacrylic acid.It optionally comprises softening comonomer, and such as alkyl acrylate and alkyl methacrylate, wherein said alkyl group has 1 to 8 carbon atom.

Described acid copolymer can be described as e/x/y copolymer, and wherein E is ethylene, and X is α, β-ethylenic unsaturated carboxylic acid, and Y is for softening comonomer.In preferred embodiments, X is acrylic or methacrylic acid, and Y is acrylic acid C_1-8Arrcostab or methacrylic acid C_1-8Arrcostab.X preferably with the percentage by weight of about 1 to about 35 of polymer, the more preferably percentage by weight of about 5 to about 30 of polymer, and the amount of the most preferably percentage by weight of about 10 to about 20 of polymer exists.Y preferably with the percentage by weight of about 0 to about 50 of polymer, the more preferably percentage by weight of about 5 to about 25 of polymer, and the amount of the most preferably percentage by weight of about 10 to about 20 of polymer exists.

The concrete ethylene copolymer containing acid includes but not limited to ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/n-butyl acrylate, ethylene/methacrylic acid/Isobutyl 2-propenoate, ethylene/acrylic acid/Isobutyl 2-propenoate, ethylene/methacrylic acid/n-BMA, ethylene/acrylic acid/methyl methacrylate, ethylene/acrylic acid/acrylic acid methyl ester., ethylene/methacrylic acid/acrylic acid methyl ester., ethylene/methacrylic acid/methyl methacrylate and ethylene/acrylic acid/n-BMA.The preferably ethylene copolymer containing acid includes ethylene/methacrylic acid/n-butyl acrylate, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/acrylic acid methyl ester., ethylene/acrylic acid/ethyl acrylate, ethylene/methacrylic acid/ethyl acrylate and ethylene/acrylic acid/methyl acrylate copolymer.Most preferably the ethylene copolymer containing acid is ethylene/(methyl) acrylic acid/n-butyl acrylate, ethylene/(methyl) acrylic acid/ethyl acrylate and ethylene/(methyl) acrylic acid/methyl acrylate copolymer.

Generally with metal cation such as Li, Na, Mg, K, Ca or Zn, ionomer is neutralized.However, it has been found that by being added to together with suitable alkali in described acid copolymer or ionomer by the salt of enough organic acid or organic acid, this ionomer can be neutralized to level much higher for metal cation, and does not lose processability.Preferably, this acid moieties is neutralized greater than about 80%, preferably 90-100%, most preferably 100%, and does not lose processability.This is along with to ethylene-alpha, β-ethylenic copolymers of unsaturated carboxylic acids carries out melt blending with the salt of such as organic acid or organic acid, and the cationic source adding q.s rises above 90% (preferably greater than 100%) with the neutralization levels by all acid moieties (being included in those acid moieties in acid copolymer and in organic acid).

The organic acid of the present invention is the single or multiple sense of aliphatic (saturated, unsaturated or the most unsaturated) organic acid.It is used as the salt of these organic acid.The salt of the organic acid of the present invention includes the salt of barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, caesium, ferrum, nickel, silver, aluminum, stannum or calcium, fatty acid particularly stearic acid, behenic acid, sinapic acid, oleic acid, linoleic acid or the salt of its dimerization derivant.Preferably, the organic acid of the present invention and salt are relative non-migratory (they do not move on the surface of polymer at ambient temperature) and nonvolatile (they needed for melt blending at a temperature of non-volatile).

The ionomer of the present invention is alternatively more conventional ionomer, i.e. neutralizes by metal cation part.By cation such as lithium, sodium, potassium, magnesium, calcium, barium, lead, stannum, zinc, aluminum or its mixture by the acid moieties in this acid copolymer and about 1 to about 90%, preferably at least about 20 to about 75%, and more preferably at least about 40 to about 70%, thus form ionomer.

In a preferred embodiment, the monolayer core of the present invention is encapsulated with two cover layers, wherein the thickness of inner cover is about 0.01 inch to about 0.06 inch, even more preferably about 0.015 inch to about 0.040 inch, and most preferably about 0.02 inch to about 0.035 inch, and described inner cover formed by the ionomer partially or completely neutralized, the Shore D hardness of the described ionomer partially or completely neutralized is greater than about 55, more preferably greater than about 60, and 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, even more preferably about 0.02 inch to about 0.04 inch, and most preferably about 0.025 inch to about 0.035 inch, and hardness is about Shore D 60 or less, more preferably 55 or less, and most preferably about 52 or less.Described inner cover should be harder than described outer cover.In this embodiment, outer cover includes ionomer, polyurethane, polyureas or its blend partially or completely neutralized.Most preferably outer cover be pourable or can the polyurethane of reaction injection molding, polyureas or its copolymer or mixture, its Shore D hardness is about 40 to about 50.Most preferably inner cover material is the ionomer that part neutralizes, and it contains the ionomer of zinc, sodium or lithium neutralization such as8940,8945,9910,7930,7940 or its Shore D hardness be about the blend of 63 to about 68.

In another kind of multilamellar cover layer-monokaryon embodiment, outer cover and inner cover material and thickness are identical, but the i.e. outer cover that hardness range is contrary is harder than inner cover.

In selectable preferred implementation, golf is the golf of monoblock, it has the surface (dimpledsurface) of depression, and has the case hardness equal with core rigidities or the case hardness less than core rigidities (i.e. bearing hardness gradient).The diameter of the spheroid of this monoblock is preferably from about 1.680 inches to about 1.690 inches, and weight is about 1.620oz, Atti compression and is about 40 to 120, and COR is about 0.750 to 0.825.

In preferred two pieces of spheroid embodiments, the monolayer core monolayer with negative hardness gradient covers material cladding, the Shore D hardness of this covering material is about 20 to about 80, even more preferably about 40 to about 75, and most preferably about 45 to about 70, and include thermoplasticity or heat-curable urethane, polyureas, polyamide, polyester, polyester elastomer, polyether-amide or polyester-amides, the ionomer partially or completely neutralized, polyolefin such as polyethylene, polypropylene, polyethylene and ethylene copolymers such as Ethylene-butyl acrylate or ethylene-methyl acrylate, poly-(ethylene methacrylic acid) copolymer and terpolymer, the polyolefin of metallocene catalysis and the polyolefin of polar group functionalization and blend thereof.In two pieces of embodiments, preferably covering material is ionomer (conventional or HNP), and its hardness is about 50 to about 70 Shore D.In two pieces of embodiments, the another kind of material that preferably covers is thermoplasticity or heat-curable urethane or polyureas.Preferably ionomer is peracidity ionomer, and it comprises ethylene and methacrylic acid or acrylic acid copolymer, and acid content is at least 16 to about 25wt%.In this case, the rotation (reducedspin) of the reduction contributed by the peracidity ionomer of relative stiffness can be offset to a certain extent by the negative gradient core (spin-increasingnegativegradientcore) that increase rotates.The diameter of this core can be about 1.0 inches to about 1.64 inches, preferably from about 1.30 inches to about 1.620, and even more preferably about 1.40 inches to about 1.60 inches.

The another kind of material that preferably covers includes pourable or can the polyurethane of reaction injection molding, polyureas or the copolymer of polyurethane/polyurea or mixture.Preferably, this cover layer is heat cured, but can be thermoplastic, and Shore D hardness is about 20 to about 70, even more preferably about 30 to about 65, and most preferably about 35 to about 60.Between this cover layer and core, optionally use moist steam barrier layer (for example, see United States Patent (USP) 6,632,147,6,932,720,7,004,854 and 7,182,702, the full content of all these documents is incorporated by reference into the application).

Although any embodiment of the application all can have any of depression number and pattern, but preferably depression number is 252 to 456, and more preferably 330 to 392.Depression can include any width, the degree of depth and edge angles (edgeangle) disclosed in prior art, and pattern can include multiple depression with different in width, the degree of depth and edge angles.The separator bar configuration of described pattern can be straight line or staggered wave separator bar (SWPL).Most preferably, depression number is 330,332 or 392, and includes 5 to 7 kinds of depression sizes, and separator bar is SWPL.

In these embodiments any, monolayer core can replace with two-layer core or more layers core, and at least one of which stratum nucleare has negative hardness gradient.Different from operation embodiment, or unless otherwise specifically noting, all numerical rangies, measure, be worth and percentage such as those numerical rangies for the amount of other things in the amount of material and description, measure, be worth and percentage ratio read like similarly is above to have term " about " to modify like that, even if term " about " possibility will not occur clearly together with value, amount or scope.Therefore, unless the contrary indicated otherwise, numerical parameter listed in description and appended claims is approximation, and it can change according to the desired character obtained desired by the present invention.At least, and being not intended to, should be used for limiting the scope of claim with identical teaching, each numerical parameter should be explained according at least to given significant digits with by applying the common technology of rounding up.

Although the wide in range numerical range enclosed and the parameter that provide the present invention are approximations, but the numerical value be given in specific embodiment is given as accurately as possible.But any numerical value itself necessarily contains some error caused due to standard deviation present in their each measurement means.Additionally, when the application provides various numerical range, any combination (comprising described value) of these values any can be used.While it is apparent that be that the illustrated embodiment of the herein disclosed present invention meets above-described purpose, it is to be understood that it may occur to persons skilled in the art that many improvement and other embodiment.It will therefore be appreciated that all these improvement that are intended to cover in the spirit and scope of the present invention of appended claim and embodiment.

Claims

1. a golf, comprises:

The core formed by kernel and outer nuclear layer；

This kernel has geometric center and the first outer surface, and described kernel is formed by substantially uniform first rubber composition；

This outer nuclear layer is formed by substantially uniform second rubber composition, and described outer nuclear layer has the second outer surface；

Inner covering layer, it puts around described caryogamy, and described inner covering layer comprises ionomeric materials and has the material hardness of 60 Shore D or bigger；With

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

The hardness that wherein said first outer surface has is less than the hardness gradient kernel that the hardness at most 20 Shore C at described geometric center bears with restriction, and the hardness that described second outer surface has is more than the hardness at most 18 Shore C of described geometric center to limit positive gradient outer nuclear layer and positive hardness gradient core.

2. the golf of claim 1, the hardness of wherein said first outer surface is less than hardness 1 to the 15 Shore C of described geometric center to limit negative hardness gradient as-1 to-15 Shore C.

3. the golf of claim 2, the hardness of wherein said first outer surface is less than hardness 2 to the 12 Shore C of described geometric center to limit negative hardness gradient as-2 to-12 Shore C.

4. the golf of claim 1, wherein said kernel has the external diameter of 0.5 to 1.40 inch.

5. the golf of claim 4, wherein said kernel has the external diameter of 0.8 to 1.30 inch.

6. the golf of claim 1, the hardness of wherein said geometric center is 55 to 82 Shore C.

7. the golf of claim 6, the hardness of wherein said geometric center is 60 to 80 Shore C.

8. the golf of claim 7, the hardness of wherein said geometric center is 65 to 78 Shore C.

9. the golf of claim 1, the hardness of wherein said first outer surface is 50 to 82 Shore C.

10. the golf of claim 9, the hardness of wherein said first outer surface is 55 to 78 Shore C.

The golf of 11. claim 10, the hardness of wherein said first outer surface is 60 to 75 Shore C.

The golf of 12. claim 1, the hardness of wherein said second outer surface is 82 to 98 Shore C.

The golf of 13. claim 1, the antioxidant that wherein said substantially uniform first rubber composition comprises is 0.4 or bigger to the ratio of initiator.

The golf of 14. claim 1, wherein said ionomeric materials comprises Na-, Li-or Zn-ionomer, and its acid content is that 11 weight % are to 20 weight %.

The golf of 15. claim 1, wherein said ionomeric materials comprises the ionomer and maleic anhydride grafting, the polyolefin of metallocene catalysis that acid content is 16 weight % or bigger.

16. 1 kinds of golf, comprise:

The core formed by kernel and outer nuclear layer；

This kernel has geometric center and position the first outer surface away from geometric center 0.8 to 1.3 inch, described kernel is formed by substantially uniform first rubber composition, and the antioxidant that described substantially uniform first rubber composition comprises is 0.5 or bigger to the ratio of initiator；

This outer nuclear layer is formed by the second rubber compositions different from the first rubber composition, substantially uniform, and described outer nuclear layer has the position the second outer surface away from geometric center 1.53 to 1.58 inches；

Inner covering layer, it puts around described caryogamy, and described inner covering layer comprises the ionomer and maleic anhydride grafting, the polyolefin of metallocene catalysis that acid content is 16 weight % or bigger；With

Outer cover, it configures around described inner covering layer, and described outer cover comprises casting type polyureas or casting type polyurethane；

The hardness that wherein said first outer surface has is less than the hardness at described geometric center to limit negative hardness gradient as-1 to-15 Shore C, and the hardness that has of described second outer surface is more than hardness at most 12 Shore C at the inner surface of described outer nuclear layer with the positive hardness gradient outer nuclear layer of restriction.