CN103977541A

CN103977541A - Golf ball having a hollow center

Info

Publication number: CN103977541A
Application number: CN201410008333.9A
Authority: CN
Inventors: 迈克尔·J·沙利文; 马克·L·比内特; 布莱恩·科莫
Original assignee: Acushnet Co
Current assignee: Acushnet Co
Priority date: 2013-01-09
Filing date: 2014-01-08
Publication date: 2014-08-13
Anticipated expiration: 2034-01-08
Also published as: CN103977541B; KR20140090568A; JP2014158683A

Abstract

A golf ball including a spherical inner core shell layer formed from a thermoset rubber composition, the shell layer having an outer surface, an inner surface, and an inner diameter to define a hollow center. A thermoplastic outer core layer is formed about the shell layer. An optional inner cover layer is formed about the outer core layer, the inner cover including an ion cross-linked polymer material. An outer cover layer is formed over the core or option inner cover layer, the outer cover including a polyurea or a polyurethane and having a second hardness less than the optional inner cover layer. The hollow center has a diameter of about 0.15 to 1.1 inches.

Description

The golf with hollow centre

Technical field

The present invention relates generally to the golf of the core with hollow centre, described hollow centre is by one or more stratum nucleares and one or more cover encloses.The structure that depends on expectation, any described stratum nucleare and cover layer all can have the hardness gradient of " bearing " or " just ".More particularly, golf comprises the core with hollow centre, and described hollow centre is surrounded by thermosetting " shell " and thermoplasticity stratum nucleare that at least one is other.

Background technology

In recent years, nearly all golf all has entity structure, generally includes and has the coated entity core of coating cap rock, and cover layer and entity core both can have a plurality of layers, such as thering is the double-core of entity center and outer nuclear layer, or there is the multilayer coatingn of kernel and outer cover.Golf ball and/or center are formed by the thermoset rubber composition having as the polybutadiene of primer.Conventionally core heated and make it crosslinked to produce some expection characteristics, such as compressibility or hardness, it makes golf have the character of applicable specific player's group, no matter this player is the player of professional player, low not good enough (handicap), or in-to-the not good enough golf player of Gao.From the angle of golf ball manufacturers, expectation presents the core of wide region character, and these character are resilience, durability, rotation and " sensation " for example, because can make like this manufacturer manufacture and sale is suitable for the golf of different ability levels.

Yet, still need to allow to obtain Golf ball structure of different nature.There is no in the past commercial successful a kind of new construction is the golf with hollow core---refer to that the penetrale of core is by the hollow centre of " shell " and one or more stratum nucleare and cover encloses.Although in the past, the obtainable golf of much business is by non-entity center such as liquid center builds, very rare hollow centre golf is fabricated.

Although patent documentation is mainly mentioned the hollow core of the general alternative structure that is suitable in rough mode, seldom relate to practically hollow core golf.For example, U.S. Patent number No.6,315,683 are usually directed to the hollow entity golf of oversized dimensions (being greater than 1.70 inches), and wherein said hollow core is included in thermoset rubber layer and by single ionomeric covers and covers.Recently, U.S. Patent number No.8,262,508 have summarized the golf with hollow centre, intermediate layer, inner covering layer and outer cover.Described hollow centre and intermediate layer form by thermoset rubber composition, and have routine " positive hardness gradient " (along the internal direction layer hardness deliquescing of described layer).Described hollow " cavity " has the diameter of 0.08 to 0.5 inch, and described stratum nucleare has the low case hardness of 25 to 55 Shore C.Golf is covered by covering in the outer covering of harder ionomer and softer ionomer.

Yet golf of the present invention has the hollow core of being surrounded by thermosetting " shell " and other thermoplasticity stratum nucleare, optionally one or more thermosetting or thermoplastic interlayer, and one or more cover layer.Associating hollow core structure has solved the many problems relevant with the aforementioned trial of hollow core configuration aspects with the variation of the hardness gradient of adjacent heat plasticity and/or thermosetting stratum nucleare.

Invention summary

The present invention relates to comprise the golf of hollow core.Described golf comprises the spherical inner core shell being formed by the first thermoset rubber composition, and described shell has outer surface, inner surface and internal diameter to limit hollow centre.Thermoplasticity outer nuclear layer is configured in around described shell.Optional inner covering layer is configured in around described outer nuclear layer.In one embodiment, described inner covering layer comprises ionomer polymeric material and has the first hardness.Preferably, outer cover is formed on optional inner covering layer around, and comprises polyureas or optimization polyurethane.The hardness that described outer cover preferably has is less than the hardness of optional inner covering layer.

Hollow centre has the diameter of approximately 0.15 to 1.1 inches.The case hardness that shell has is greater than its inner surface hardness approximately 3 to 25 Shore C, to define hardness gradient.Thermoplasticity outer nuclear layer has the second hardness gradient.Preferably, shell has the case hardness that is greater than approximately 55 Shore C.In one embodiment, when the incidence rate with 125ft/s is measured, spherical inner core shell has the coefficient of resilience that is less than approximately 0.700.Preferably, outer nuclear layer has the coefficient of resilience 10-50% of the kernel shell that the coefficient of resilience measured with the incidence rate of 125ft/s measures higher than the incidence rate with 125ft/s.

In one embodiment, the second hardness gradient is approximately 0 Shore C.In another embodiment, the second hardness gradient is the negative hardness gradient of approximately 1 to 10 Shore C.In another embodiment still, the second hardness gradient is the positive hardness gradient of approximately 1 to 10 Shore C.The hardness that inner covering layer has is greater than approximately 60 Shore D, and the hardness that outer cover has is less than approximately 60 Shore D.Alternatively, described golf has the first volume, and hollow centre has 2% to 30% the second volume that is about the first volume.

The invention still further relates to the golf that comprises hollow core, described golf comprises the spherical inner core shell being formed by the first thermoset rubber composition, and described shell has outer surface, inner surface and internal diameter to limit hollow centre.Thermoplasticity outer nuclear layer is formed on shell.In the middle of thermoplasticity, stratum nucleare is formed between shell and outer nuclear layer.Optional inner covering layer is configured in around outer nuclear layer, and inner covering layer comprises ionomer polymeric material and has the first hardness.Outer cover is preferably configured in around inner covering layer, comprises polyureas or polyurethane and has the second hardness that is less than the first hardness.Hollow centre has the diameter of approximately 0.15 to 1.1 inches, and the case hardness that shell has is greater than inner surface hardness approximately 3 to 25 Shore C to define the first hardness gradient, and in the middle of thermoplasticity outer nuclear layer or thermoplasticity, stratum nucleare has the second hardness gradient.

In one embodiment, the second hardness gradient is approximately 0 Shore C.In another embodiment, the second hardness gradient is the negative hardness gradient of approximately 1 to 10 Shore C.In another embodiment still, the second hardness gradient is the positive hardness gradient of approximately 1 to 10 Shore C.

The invention further relates to the golf that comprises hollow core, described golf comprises the spherical inner core shell being formed by the first thermoset rubber composition, and described shell has outer surface, inner surface and internal diameter to limit hollow centre.Thermoplasticity outer nuclear layer is formed on shell.In the middle of thermosetting, stratum nucleare is configured between shell and outer nuclear layer, and described middle stratum nucleare comprises the second thermoset rubber composition identical or different with the first thermoset rubber composition.Inner covering layer is optionally configured in around outer nuclear layer, and described inner covering layer comprises ionomer polymeric material and has the hardness that is greater than approximately 60 Shore D.Outer cover is configured on described core or optional inner covering layer, and described outer cover comprises polyureas or polyurethane and has the hardness that is less than approximately 60 Shore D.Hollow centre has the diameter of approximately 0.51 to 1.1 inches, the case hardness that shell has is greater than inner surface hardness approximately 3 to 25 Shore C to define the first hardness gradient, thermoplasticity outer nuclear layer has the second hardness gradient, and in the middle of thermosetting, stratum nucleare has the 3rd hardness gradient that is different from the first or second hardness gradient.

In one embodiment, shell has the case hardness that is greater than approximately 55 Shore C.Alternatively, when the incidence rate with 125ft/s is measured, described spherical inner core shell has the coefficient of resilience that is less than approximately 0.700.Outer nuclear layer also can have the coefficient of resilience 10-50% of the kernel shell of measuring higher than the incidence rate with 125ft/s with the coefficient of resilience of the incidence rate measurement of 125ft/s.

In one embodiment, the second hardness gradient is approximately 0 Shore C.In another embodiment, the second hardness gradient is the negative hardness gradient of approximately 3 to 25 Shore C.In another embodiment still, the second hardness gradient is the positive hardness gradient of approximately 3 to 25 Shore C.In a preferred embodiment, golf has the first volume, and hollow centre has 2% to 30% the second volume that is about the first volume.

Accompanying drawing explanation

Fig. 1 a is that Shore C hardness is with respect to the curve map with centre distance for an embodiment of thermosetting (TS)/thermoplasticity (TP) hollow core golf;

Fig. 1 b is that Shore C hardness is with respect to the curve map with centre distance for second embodiment of thermosetting (TS)/thermoplasticity (TP) hollow core golf;

Fig. 2 a is that Shore C hardness is with respect to the curve map with centre distance for an embodiment of thermoplasticity (TP)/thermosetting (TS) hollow core golf;

Fig. 2 b is that Shore C hardness is with respect to the curve map with centre distance for second embodiment of thermoplasticity (TP)/thermosetting (TS) hollow core golf;

Fig. 3 a is that Shore C hardness is with respect to the curve map with centre distance for an embodiment of thermoplasticity (TP)/thermoplastic (TS) hollow core golf;

Fig. 3 b is that Shore C hardness is with respect to the curve map with hollow core centre distance for second embodiment of thermoplasticity (TP)/thermoplastic (TS) hollow core golf.

Detailed Description Of The Invention

Golf of the present invention can comprise multi-layer golf ball, such as having the golf of the covering of core and encloses core, but preferably by hollow core and at least one outer nuclear layer, inner covering layer and outer cover, is formed.Any core or cover layer can comprise more than one deck.The cover layer of golf can be individual layer or be formed by multilayer, such as inner covering layer and outer cover.

Hollow core is formed by thermosetting " shell ", and described shell is included in the spherical hollow space of its inside.In a preferred embodiment, golf comprises thermosetting hollow core and at least two outer nuclear layers and middle stratum nucleare, wherein said shell is formed by thermosets, and outer nuclear layer is formed by thermoplastic, and middle stratum nucleare is configured between shell and outer nuclear layer and by thermoplastic and forms.In an optional preferred embodiment, golf comprises thermosetting hollow core and at least two outer nuclear layers and middle stratum nucleare, wherein said shell is formed by thermosets, outer nuclear layer is formed by thermoplastic, and described middle stratum nucleare is configured between shell and outer nuclear layer and by thermosets and forms.

When the outer surface from each composition or part to its penetrale (, from the outer surface/part of shell and/or stratum nucleare to inner surface/part) while radially inwardly measuring, described shell, outer core or middle stratum nucleare can have the hardness gradient (outmost surface/the part of layer is harder than inner surface/part) of conventional " firmly arriving soft ", be called " positive hardness gradient ", or the hardness gradient (that is, " bearing " hardness gradient) of " soft to hard ".For the term of hardness gradient, " bear " as used herein and " just " refers to for example, to deduct the hardness number of the outer surface (outer surface of outer nuclear layer) from the composition measured for example, result after the hardness number of the penetrale (, the inner surface of stratum nucleare) at measured composition.For example, if the outer surface of stratum nucleare has the hardness lower than inner surface, hardness gradient will be considered to be " bearing " gradient (little numerical value-large numerical value=negative), although this numerical value can be disclosed as and the absolute value of subtraction result of specifying the combination of " bearing " in this application.

That thermoplastic shell of the present invention, middle stratum nucleare and outer nuclear layer can have is as above " positive hardness gradient " or " negative hardness gradient ".Alternatively, thermoplastic layer can have " zero hardness gradient ", is defined as herein and comprises 0 Shore C hardness gradient ± 2 Shore C.Thermoplastic layer's " positive hardness gradient " or " negative hardness gradient " can be for approximately 0 Shore C be to approximately 10 Shore C, and more preferably from about 2 Shore C are to approximately 8 Shore C, and most preferably from about 3 Shore C are to approximately 5 Shore C.

That thermosetting shell of the present invention, middle stratum nucleare and outer nuclear layer can have is as above " positive hardness gradient " or " negative hardness gradient ".Alternatively, thermoset layer can have " zero hardness gradient ", is defined as herein and comprises 0 Shore C hardness gradient ± 2 Shore C." the positive hardness gradient " of thermoset layer or " negative hardness gradient " can be for approximately 1 Shore C be to approximately 30 Shore C, and preferably approximately 2 Shore C are to approximately 27 Shore C, and more preferably from about 5 Shore C are to approximately 25 Shore C, most preferably from about 10 to 20 Shore C.Other suitable heat cured " positive hardness gradient " or " negative hardness gradient " stratum nucleare can be 7,537, and 529 and 7,537, in No. 530 United States Patent (USP)s, find, its full content is incorporated herein by reference.

Various above-mentioned thermosetting and thermoplasticity hardness gradient layer are all expected, and " positive hardness gradient " and/or " negative hardness gradient " can combine formation hollow core of the present invention, and it has the multilayer of this character.

The case hardness of shell or stratum nucleare is to obtain from the mean value of repeatedly measuring to the relative hemisphere of certain layer, carefully avoids measuring on the die parting line of core or in any blemish (such as hole or projection).Hardness measurement is to carry out according to ASTM D-2240 " rubber of measuring by hardometer and the identation hardness of plastics ".Due to the curved surface of hollow core or stratum nucleare, must careful operation to guarantee that core is placed in the middle under penetrator before obtaining case hardness reading.Use is carried out all hardness measurements through digital hardometer calibration, that can read 0.1 stiffness units, and is arranged to adopt the hardness reading of acquisition full-scale reading in the time of 1 second afterwards.Numeral hardometer must be connected to the base portion of automatic station, and makes its base parallel with the base portion of automatic station, makes weight and impact speed on hardometer meet ASTM D-2240.

For the hollow core of preparing to measure for hardness gradient, lightly core (shell or with one or two stratum nucleare) is pressed into the roughly hemisphere clamper more smaller than the diameter of core of internal diameter, core is fixed in the hemispherical portion of clamper, makes the geometric center plane of core expose simultaneously.Core is fixed in clamper by frictional force, it can not moved during cutting and grinding steps, but frictional force is inexcessive, can not cause the natural shape distortion of core.Core is fixed, the die parting line that makes core roughly with the top almost parallel of clamper.Before fixing, to be orientated to this diameter that 90 degree are measured core.Equally also measure from clamp base to core top, so that the reference point of further calculating to be provided.Use band saw or other suitable cutting tool to carry out rough cutting above the geometric center of core exposure is omited, guarantee in clamper, not move at this step center.The remainder of the core in clamper still, is fixed on the substrate of surface grinding machine." coarse " core surface exposing is ground as smooth flat surface, the hollow centre of exposing core, it can verify by measuring clamp base to the surperficial height that core exposes, guarantee to remove as above measured core original height just in time half within ± 0.004 inch.

Core is stayed in clamper, with centre square, found He center, and mark carefully, and measure hardness at this centre mark place.Can by from centre mark through the hardness of any distance in setting-out measuring distance core center radially outward, measure and the excentric distance of mark, be conventionally spaced apart 1 or 2mm, measure.All to the hardness measurements of carrying out through the plane of hollow centre, and described core is still in clamper, and do not upset its orientation, thus make test surfaces always parallel with clamp base.Difference of hardness from any precalculated position of core is calculated as the hardness that average surface hardness deducts suitable reference point.

One or more shells and/or stratum nucleare can be formed by following composition, described composition comprises at least one heat-curable matrix rubber, such as polybutadiene rubber, it solidifies by least one peroxide and at least one reactive auxiliary agent, and described reactive auxiliary agent can be slaine, non-metal assistant or its mixture of unsaturated carboxylic acid (such as acrylic or methacrylic acid).Preferably, composition also comprises suitable antioxidant.In caryogamy side, can also comprise optional softening accelerator (soft and fast agent) (sometimes also referred to as cis-anticatalyst), such as organic sulfur or the organosulfur compound that contains metal.Can also use other composition well known by persons skilled in the art, these other compositions should be understood to include, but are not limited to Auto-regulating System of Density of Heavy Medium filler, processing aid, plasticizer, foaming or blowing agent, sulphur promoter and/or non--peroxide radical source.

Matrix thermoset rubber can with other rubber and polyblend, generally include natural or synthetic rubber.Preferred base rubber is Isosorbide-5-Nitrae-polybutadiene, and its cis-structure having is at least 40%, is preferably greater than 80%, and more preferably greater than 90%.

The example of the polybutadiene rubber of expectation comprises cB22 and cB23, CB1221, CB1220, CB24 and CB21, obtain from LANXESS Corporation is commercially available; 360L and 150L and UBEPOL-BR rubber, from UBE Industries, Ltd.of Tokyo, Japan is commercially available to be obtained; 7245, 7265 and BUDENE1207 and 1208, from Goodyear of Akron, OH is commercially available to be obtained; SE BR-1220; bR40 and BR60, obtain from Polimeri Europa is commercially available; And BR01, BR730,, BR735, BR11 and BR51, from Japan Synthetic Rubber Co., Ltd is commercially available to be obtained; bRNd-40; With nD40, ND45 and ND60, obtain from Karbochem is commercially available.

From Lanxess Corporation, the rank of Nd and Co-catalysis most preferably, but following listedly all can use: Buna CB21; Buna CB22; Buna CB23; Buna CB24; Buna CB25; Buna CB29MES; Buna CB Nd40; Buna CB Nd40H; Buna CB Nd60; Buna CB55NF; Buna CB60; Buna CB45B; Buna CB55B; Buna CB55H; Buna CB55L; Buna CB70B; Buna CB1220; Buna CB1221; Buna CB1203; Buna CB45.In addition, multiple suitable rubber is obtainable from JSR (Japan Synthetic Rubber), Ube Industries Inc, the Ubepol that Japan sells, BST Elastomers, the BST that Thailand sells; Indian Petrochemical Ltd, the IPCL that India sells; The Nitsu that the Karbochem Ltd of Karbochem or South Africa sells; The PETROFLEX of Brazil; The LG of Korea; And the Kuhmo Petrochemcial of Korea.

Base rubber can also comprise high or medium Mooney viscosity rubber, or its admixture." Mooney " unit is that it defines according to ASTM D-1646 for measuring the unit of the plasticity of crude rubber or half finished rubber.The scope of Mooney viscosity is preferably more than approximately 40, is more preferably approximately 40 to 60 scope, is most preferably approximately 40 to 52 scope.

The suitable commercial source of polybutadiene comprises Bayer AG CB23 (Nd-catalysis), and it has approximately 50 Mooney viscosity and is the polybutadiene of highly linear, and CB1221 (Co-catalysis).If needed, polybutadiene can also mix with other elastomer known in the art, such as other polybutadiene rubber, natural rubber, butadiene-styrene rubber and/or isoprene rubber, further the character of core is carried out to modification.When using elastomeric mixture, the content of other composition during core forms is normally in the main elastomer mixture based on 100 weight portions.

In a preferred embodiment, base rubber comprises the polybutadiene of Nd-catalysis, the polybutadiene rubber of rare earth element-catalysis, or its admixture.If needed, polybutadiene also can mix with other elastomer as known in the art, such as natural rubber, polyisoprene rubber and/or SBR styrene butadiene rubbers, to the character of core is carried out to modification.Other suitable base rubber comprises thermosets, such as ethylene propylene diene monomer rubber, EP rubbers, butyl rubber, halogenated butyl rubber, hydrogenated nitrile-butadiene rubber, nitrile rubber and silicone rubber.

Suitable peroxide initiator comprises cumyl peroxide; 2,5-dimethyl-2,5-bis-(t-butylperoxy) hexane; 2,5-dimethyl-2,5-bis-(t-butylperoxy) hexin; 2,5-dimethyl-2,5-bis-(benzoyl peroxy) hexane; 2,2 '-bis(t-butylperoxy)-bis--iso-propylbenzene; 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane; 4,4-bis(t-butylperoxy) valeric acid n-butyl; T-butyl perbenzoate; Benzoyl peroxide; 4,4 '-bis-(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-bis(t-butylperoxy) diisopropyl benzene, two (2-t-butylperoxy isopropyl) benzene, two-t-amyl peroxy thing, di-tert-butyl peroxide.Preferably, rubber composition comprises peroxide/100 parts by weight of rubber (phr) of approximately 0.25 to approximately 5.0 weight portion, more preferably 0.5phr to 3phr, most preferably 0.5phr to 1.5phr.In the most preferred embodiment, the amount of peroxide is about 0.8phr.These scopes of given peroxide are that the described peroxide of hypothesis is 100% activity, do not consider any carrier that may exist.Because many commercially available peroxide are sold together with carrier compound, therefore must calculate the physical presence amount of peroxide actives.Commercially available obtainable peroxide initiator comprises that the DICUPTM family of the cumyl peroxide that can obtain from Crompton (Geo SpecialtyChemicals) (comprises DICUP ^tMr, DICUP ^tM40C and DICUP ^tM40KE).Similarly initator can be from AkroChem, Lanxess, and Flexsys/Harwick and R.T.Vanderbilt obtain.Other commercially available obtainable and preferred initator is the TRIGONOX from Akzo Nobel ^tM265-50B, it is 1,1-bis-(t-butylperoxy)-3,3, the mixture of 5-trimethyl-cyclohexane and two (2-t-butylperoxy isopropyl) benzene.TRIGONOX ^tMperoxide is sold conventionally on carrier compound.

Being applicable to suitable reactive auxiliary agent of the present invention comprises, but be not limited to, the slaine of diacrylate, dimethacrylate and monomethyl acrylates, comprises that metal is wherein those of zinc, manganese, calcium, barium, tin, aluminium, lithium, sodium, potassium, iron, 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 the purity of various grades.For object of the present invention, the amount of the zinc stearate existing in ZDA is lower, and the purity of ZDA is higher.It is preferred comprising the ZDA that is less than approximately 10% zinc stearate.The ZDA that more preferably comprises about 4-8% zinc stearate.Suitable, commercially available obtainable dizinc acrylate resin comprises from those of Sartomer Co..The preferred concentration of operable ZDA is extremely about 40phr of about 10phr, and more preferably 20phr is to about 35phr, and most preferably 25phr is to about 35phr.In an especially preferred embodiment, the amount of reactive auxiliary agent is that about 29phr is to about 31phr.

Preferred auxiliary agent in addition can be used separately or be used in combination with above-mentioned substance, and described auxiliary agent comprises, but is not limited to trimethylol-propane trimethacrylate, trimethylolpropane triacrylate, etc.It will be appreciated by those skilled in the art that these auxiliary agents are at room temperature, in the situation of liquid, advantageously these compounds to be scattered on suitable carrier therein, be easy to it and be blended in rubber composition.

Antioxidant is for suppressing or preventing elastomer generation Oxidative demage and/or inhibition or the compound of the reaction that prevents from being caused by oxygen radical.In the present invention, the example of more operable exemplary antioxidant includes, but are not limited to quinolines antioxidant, amine antioxidants and phenolic antioxidant.Preferred antioxidant is 2,2'-methylene-bis-(4-methyl-6-tert-butylphenols), from RT.Vanderbilt conduct mBPC is obtainable.Other polyphenol antioxidant comprises sKT, sWP, 13 Hes 1290.

Suitable antioxidant comprises, but is not limited to the cresols that alkylidene-bis--alkyl replaces; The phenols replacing; Alkylidene diphenol; Alkylidene triphenol.The amount of antioxidant is generally about 0.1phr to 5phr, and preferred about 0.1phr is to about 2phr, and more preferably from about 0.1phr is to about 1phr.In an optional embodiment, the amount of antioxidant should guarantee that the hardness gradient of stratum nucleare bears.Preferably, in stratum nucleare formula, add about 0.2phr to the antioxidant of about 1phr, more preferably from about 0.3phr to 0.8phr, most preferably 0.4phr to 0.7phr.Preferably, to the peroxide that adds about 0.25phr to 1.5phr in caryogamy side, in 100% activity, more preferably from about 0.5phr to 1.2phr, most preferably is about 0.7phr to 1.0phr.Can adjust the amount of ZDA to realize the needed compression of golf, rotation and the feel obtaining.The temperature range that curing scheme can have is approximately 290 °F to 350 °F, more preferably from about 300 °F to 335 °F, and raw material stores at least about 10 minutes to 30 minutes at temperature described in it.

In thermoset rubber composition, can also comprise optional softening accelerator." softening accelerator " instigates the core of manufacture as used herein, with the nuclear phase ratio that does not use softening accelerator manufacturing, any compound or its admixture or its any combination with following character: 1) more soft under constant COR (low compression), or 2) under identical compression, there is higher COR.Preferably, the softening accelerator that thermosetting stratum nucleare composition comprises about 0.05phr to 10.0phr.In one embodiment, the amount of softening accelerator is that about 0.05phr is to about 3.0phr, preferred about 0.05phr to 2.0phr, more preferably from about 0.05phr to 1.0phr.In another embodiment, the amount of softening accelerator is about 2.0phr to 5.0phr, preferred about 2.35phr to 4.0phr, more preferably from about 2.35phr to 3.0phr.Suitable softening accelerator includes, but not limited to organosulfur compound or metallic organosulfur compound, organosulfur compound (comprising list, two and polysulfide, mercaptan, or sulfhydryl compound), inorganic sulfide compound, VIA compounds of group, or its mixture.Softening accelerator component can be also the admixture of organosulfur compound and inorganic sulfide compound.

Filler can join thermoset rubber composition, generally includes, but is not limited to, and affects filler, tearing strength or the strengthening filler etc. of the processing aid (processing aids) of rheology and mixed nature and/or compound, change density.Filler comprises than material described as follows: tungsten, zinc oxide, barium sulfate, silica, calcium carbonate, zinc carbonate, metal, metal oxide and salt, the abrasive material (nuclear material of recovery again, conventionally be ground to approximately 30 object particle diameters), high Mooney viscosity rubber abrasive material, the trans nuclear material (nuclear material of recovery, the transisomer of the polybutadiene that it comprises a large amount) etc. that grinds again again.When there is trans abrasive material again, the amount of transisomer is preferably about 10% to approximately 60%.Described filler is generally inorganic matter, and suitable filler comprises various metals or metal oxide, such as zinc oxide and tin oxide and barium sulfate, zinc sulfate, calcium carbonate, brium carbonate, clay, tungsten, tungsten carbide, silicate series, and composition thereof.Filler also can comprise multiple blowing agent or foaming agent, and it can easily be selected by those of ordinary skills.Filler can comprise entity or hollow, filling or unfilled polymer, pottery, metal and glass microsphere.Conventionally filler is joined in one or more layers of the large ball of Gao Er, to change its density.

Thermoset rubber shell and/or stratum nucleare optionally comprise at least one additive and/or filler.These materials are also applicable to be included in thermoplastic layer of the present invention.Suitable additive and filler comprise, but be not limited to chemical blowing agent and blowing agent, optical brightener, colouring agent, fluorescer, brightening agent, UV absorbent, light stabilizer, defoamer, processing aid, antioxidant, stabilizing agent, softening agent, fragrance ingredient, plasticizer, impact modifying agent, TiO ₂, acid and wax copolymer, surfactant, performance additive (for example, A-C performance additive, particularly A-C low-molecular-weight ionomer and copolymer, the polyethylene of A-C oxidation, with A-C ethylene vinyl acetate wax, by commercially available acquisition of Honeywell International Inc.), fatty acid amide (for example, ethylenebis-stearmide and ethylenebis-oleamide), aliphatic acid and salt thereof are (for example, stearic acid, oleic acid, zinc stearate, dolomol, zinc oleate and magnesium oleate), and filler, such as zinc oxide, tin oxide, barium sulfate, zinc sulfate, calcium oxide, calcium carbonate, zinc carbonate, brium carbonate, tungsten, tungsten carbide, silicate, lead silicate, abrasive material again, clay, mica, talcum powder, nano-filled thing, carbon black, glass flake, the glass grinding, short fiber, fiber, and composition thereof.Suitable additive is described in greater detail in the No.7 announcing on May 9th, 2006, in 041, No. 721 United States Patent (USP), its content is incorporated herein by reference.In a particular, additive and the filler total amount in particulate composition is gross weight meter 20wt% based on particulate composition or following or 15wt% or following or 12wt% or following or 10wt% or following or 9wt% or following or 6wt% or following or below 5wt% or 4wt% or following or 3wt% or following, have 02 or 3 or the scope of the lower limit of 5wt% within, and on be limited to gross weight meter 9 based on particulate composition or 10 or 12 or 15 or 20wt%.A particular aspects in this embodiment, described particulate composition comprises and is selected from following filler: carbon black, micron order and nanoscale clay and organic clay are (for example, from Southern Clay Products, the commercially available obtainable CLOISITE of Inc. and NANOFIL nanoclay; From Nanocor, Inc. commercially available obtainable NANOMAX and NANOMER nanoclay, with from the commercially available obtainable PERKALITE nanoclay of Akzo Nobel Polymer Chemicals), micron order and nanoscale talcum powder (for example, from Luzenac America, Inc. commercially available obtainable LUZENAC HAR high aspect ratio talcum), glass (for example, glass flake, the glass grinding, micro-glass and glass fibre), micron order and nanoscale mica and mica-based pigment (for example,, from the commercially available obtainable IRIODIN pearlescent pigment of The Merck Group) and combination thereof.The combination of specially suitable filler includes, but are not limited to the combination of micron order filler and nanoscale filler, and the combination of organic filler and inorganic filler.

For thermoset rubber layer of the present invention, the amount of filler and/or additive is the about 50wt% of gross weight meter based on composition or following, preferably 30wt% or following, more preferably 20wt% or following, most preferably 15wt% or following.Alternatively, for thermoplastic layer of the present invention, the amount of filler and/or additive is the about 10wt% of gross weight meter based on composition or following, more preferably 6wt% or following, most preferably 3wt% or following.

Particulate composition optionally comprises one or more melt flows conditioning agents.Suitable melt flows conditioning agent comprises as used ASTM-D-1238, condition E, at 190 ℃, while using 2160-g weight measurement, increase the material of the melt flows of composition.The example of suitable melt flows conditioning agent includes, but not limited to aliphatic acid and soap, includes but not limited to, at No.5, those disclosed in 306, No. 760 United States Patent (USP)s, is incorporated herein by reference its content at this; Fatty acid amide and salt thereof; Polyalcohol, includes but not limited to, at No.7, and 365,128 and 8,163, those disclosed in No. 823 United States Patent (USP)s, is incorporated herein by reference its full content at this; PLA, includes but not limited to, at No.7, those disclosed in 642, No. 319 United States Patent (USP)s, is incorporated herein by reference its content at this; And at No.8, disclosed conditioning agent in 163, No. 823 United States Patent (USP)s and No.2009/0203469 U.S. Patent Application Publication, will play content at this and be incorporated herein by reference.The enhancing additive that flows also comprises, but be not limited to, the ester of montanic acid, montanic acid and salt thereof, two-stearoyl ethylenediamine, unit alcohol and polyol ester are such as the polyethylene of pentaerythritol tetrastearate, zwitterionic compound and metallocene-catalysis and polypropylene wax (comprising the form that its maleic anhydride is modified), amide waxe and alkylenediamides are such as distearyl acid amides.Specially suitable fatty acid amide includes, but are not limited to saturated fatty acid monoamides (for example, lauramide, palmitamide, arachidic acid acid amides, behenic acid acid amides, stearmide and 12-hydroxyl stearmide); Unrighted acid monoamides (for example, oleamide, erucyl amide and castor oil acid amides); Fatty acid amide (for example, N-stearyl stearmide, N-mountain Yu base behenic acid acid amides, N-stearyl behenic acid acid amides, N-mountain Yu base stearmide, N-oil base oleamide, N-oil base stearmide, N-stearyl oleamide, N-stearyl erucyl amide, mustard base erucyl amide and mustard base stearmide, N-oil base palmitamide, methylol amide (more preferably methylol stearmide, methylol mountain Yu acid amides) that N-replaces; Saturated fatty acid bisamide (for example, di-2-ethylhexylphosphine oxide stearmide, vinyl bis-stearamides, the two isostearoyl amine of vinyl, the two hydroxyl stearmides of vinyl, the two behenic acid acid amides of vinyl, hexamethylene bis-stearamides, the two behenic acid acid amides of hexamethylene, the two hydroxyl stearmides of hexamethylene, N, N'-distearyl adipamide and N, N'-distearyl decanediamide); Unrighted acid bisamide (for example, the two oleamide of vinyl, the two oleamide of hexamethylene, N, N'-bis-oil base adipamides, N, N'-bis-oil base decanediamides); And saturated and the two oleamide of undersaturated aliphatic acid four acid amides, stearyl erucyl amide, vinyl bis-stearamides and vinyl.The suitable example of commercially available obtainable fatty acid amide comprises, but be not limited to, KEMAMIDE aliphatic acid, such as KEMAMIDE B (behenic acid acid amides/arachidic acid acid amides), KEMAMIDE W40 (N, N'-ethylene bis stearamide), KEMAMIDE P181 (oil base palmitamide), KEMAMIDE S (stearmide), KEMAMIDE U (oleamide), KEMAMIDE E (erucyl amide), KEMAMIDE O (oleamide), KEMAMIDE W45 (N, N'-ethylene bis stearamide), KENAMIDE W20 (N, N'-ethylene oleamide), KEMAMIDE E180 (stearyl erucyl amide), KEMAMIDE E221 (mustard base erucyl amide), KEMAMIDE S180 (stearyl stearmide), KEMAMIDE S221 (mustard base stearmide), from Chemtura Corporation is commercially available, obtain, with CRODAMIDE fatty acid amide, such as CRODAMIDE OR, ((oleamide), CRODAMIDE ER (erucyl amide), CRODAMIDE SR (stearmide), CRODAMIDE BR (behenic acid acid amides), CRODAMIDE203 (oil base palmitamide) and CRODAMIDE212 (stearyl erucyl amide), from commercially available acquisition of Croda Universal Ltd.

The shell of hollow golf, middle stratum nucleare and outer nuclear layer also can be by thermoplastic the polymer such as ionomer polymerization, preferred heights-and the ionomer (HNP) of completely-neutralization make.The acidic moiety of HNP, is generally the ionomer based on ethylidene, and be preferably neutralized and be greater than approximately 80%, be more preferably greater than approximately 90%, and most preferably at least about 100%.HNP also can mix with the second polymers compositions, if described component contains acid groups, can neutralize with usual manner, neutralize, or both is all by organic aliphatic acid of the present invention.Described the second polymers compositions, can partially or completely neutralize, preferably include polymer (grafting with non-grafting), unit point polymer, the acid polymer of high crystallization, cationic ionomer of ionomer polymerization copolymer and trimer, ionomer precursor, thermoplastic, polyamide, Merlon, polyester, polyurethane, polyureas, thermoplastic elastomer (TPE), polybutadiene rubber, balata, metallocene catalysis etc.HNP polymer has approximately 20 material hardnesses to approximately 80 Shore D conventionally, and about 3000psi is to the bending modulus of about 200000psi.

Preferably, HNP is ionomer and/or its acid precursors, preferably with organic acid copolymer or its salt, neutralizes wholly or in part.Described acid copolymer is preferably the copolymer of following material: alpha-olefin, and as ethene, 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 has 1 to 8 carbon atom.

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

Concrete comprises containing sour ethylene copolymer, but be not limited to ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/n-butyl acrylate, ethylene/methacrylic acid/isobutyl acrylate, ethylene/acrylic acid/isobutyl acrylate, ethylene/methacrylic acid/n-BMA, ethylene/acrylic acid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl methacrylate and ethylene/acrylic acid/n-BMA.Preferably containing sour ethylene copolymer, comprise ethylene/methacrylic acid/n-butyl acrylate, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/acrylic acid/ethyl acrylate, ethylene/methacrylic acid/ethyl acrylate and ethylene/acrylic acid/methyl acrylate copolymer.Most preferred is ethene/(methyl) acrylic acid/n-butyl acrylate, ethene/(methyl) acrylic acid/ethyl acrylate and ethene/(methyl) acrylic acid/methyl acrylate copolymer containing sour ethylene copolymer.

Conventionally with metal cation such as Li, Na, Mg, K, Ca or Zn neutralize ionomer.Yet, have been found that this ionomer can be neutralized to level much higher for metal cation, and does not lose processing characteristics by enough organic acids or organic acid salt are joined in described acid copolymer or ionomer with together with suitable alkali.Preferably, the neutralization of this acid moieties is greater than to approximately 80%, preferred 90-100%, most preferably 100%, and do not lose processing characteristics.This is accompanied by ethylene-alpha, β-ethylenic copolymers of unsaturated carboxylic acids carries out melt blending with for example organic acid or organic acid salt, and adds the cationic source of q.s so that the neutralization levels of all acid moieties (being included in those acid moieties in acid copolymer and in organic acid) is increased to and is greater than 90% (being preferably greater than 100%).

Organic acid of the present invention is aliphatic list or multifunctional (saturated, unsaturated or polyunsaturated) organic acid normally.Also can use these organic acid salt.Organic acid salt of the present invention comprises the salt of barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, caesium, iron, nickel, silver, aluminium, tin or calcium, and aliphatic acid is the salt of stearic acid, behenic acid, sinapic acid, oleic acid, linoleic acid or its dimerization derivative particularly.Preferably, organic acid of the present invention is relative non-migrating (they can not move on the surface of polymer at ambient temperature) and nonvolatile (they are non-volatile at the required temperature of melt blending) with salt.

Ionomer of the present invention can be also more conventional ionomer, with metal cation, partly neutralizes.By cation for example lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminium or its mixture by the acid moieties in this acid copolymer and approximately 1 to approximately 90%, preferably at least about 20 to approximately 75%, and more preferably at least about 40 to approximately 70%, to form ionomer.

Preferred thermoplastic is disclosed in No.7, in 591, No. 742 United States Patent (USP)s, its full content is incorporated to herein as a reference.

Many thermoplastic elastomer (TPE)s (TPE) also can be for thermoplastic shell or stratum nucleare so that the character of this shell and/or stratum nucleare is carried out to modification, or by uncured stratum nucleare raw material being carried out to modification with the blend of matrix thermoset rubber.These TPE comprise natural or synthetic balata or homo-anti-polyisoprene, high trans-polybutadiene or any styrene block copolymer, such as styrene ethylene butadiene styrene, styrene-isoprene-phenylethene etc., the polyolefin of metallocene or other single-point position catalysis is such as ethylene-octene, or ethene-butylene, or thermoplastic polyurethane (TPU), for example comprise the copolymer with silicones.Other is suitable for comprising with the TPE of thermoset rubber blend of the present invention (it is believed to comprise polyether amide copolymer), (it is believed to comprise polyetherester copolymer), thermoplastic polyurethane, and (it is believed to comprise SBC elastomer).Any above-mentioned TPE or TPU can also comprise the functional group for grafting, comprise maleic acid or maleic anhydride.

Other polymer can also optionally be incorporated to the base rubber for shell and stratum nucleare.Example comprises, but be not limited to: thermo-setting elastomer is such as core abrasive material again, TPV, the ionomer of copolymerization, the ionomer of trimerization, Merlon, polyamide, the polyamide of copolymerization, polyester, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polyarylate, polyacrylate, polyphenylene oxide, impact-resistant modified polyphenylene oxide, high impact polystyrene, diallyl phthalate polyester, SAN (SAN) (comprising olefin-modified SAN and acrylonitrile-styrene-acrylonitrile polymer), styrene-maleic anhydride copolymer, styrene copolymer, functionalized styrol copolymer, functionalized phenylethylene trimer, phenylethylene trimer, cellulosic polymer, liquid crystal polymer, vinyl-vinyl-acetic ester copolymer, polyureas, and polysiloxanes, or the polymer of any metallocene catalysis of these materials.

In composition within the scope of the present invention, suitable polyamides class as other polymeric material also comprises the resin obtaining in the following manner: (1) (a) dicarboxylic acids such as oxalic acid, adipic acid, decanedioic acid, terephthalic acid (TPA), M-phthalic acid or 1,4-cyclohexane dicarboxylic acid and (b) diamine, polycondensation such as ethylenediamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine or decamethylene diamine, Isosorbide-5-Nitrae-cyclohexane diamine or meta-xylene base diamines; (2) cyclic lactames such as the ring-opening polymerisation of-caprolactam or Ω-lauric lactam; (3) amino carboxylic acid, such as the polycondensation of 6-aminocaprolc acid, 9 aminononanoic acid, the amino hendecanoic acid of 11-or 12-amino-nonanoic acid; Or the copolymerization of (4) cyclic lactames and dicarboxylic acids and diamine.The instantiation of suitable polyamide comprises NYLON, NYLON MXD6 and the NYLON46 of NYLON6, NYLON66, NYLON610, NYLON11, NYLON12, copolymerization.

The diameter that the hollow inside of shell has is approximately 0.1 inch to approximately 1.1 inches, preferably approximately 0.2 inch to approximately 0.9 inch, and more preferably from about 0.25 inch to approximately 0.75 inch, most preferably from about 0.3 inch to approximately 0.5 inch.In a preferred embodiment, the diameter that the hollow inside of shell has is greater than 0.5 inch.The thickness range that shell has is 0.01 inch to approximately 0.4 inch.When expectation shell is relatively thick, the thickness of this shell is approximately 0.125 inch to approximately 0.375 inch, preferably approximately 0.2 inch to approximately 0.3125 inch, and more preferably from about 0.25 inch to approximately 0.3 inch, most preferably from about 0.26 inch to approximately 0.275 inch.When expectation shell relative thin, the thickness of this shell is approximately 0.01 inch to approximately 0.1 inch, preferably approximately 0.02 inch to approximately 0.075 inch, and more preferably from about 0.025 inch to approximately 0.04 inch, most preferably from about 0.03 inch to approximately 0.035 inch.When shell relative thin and while being formed by thermoplastic, that thermoplastic is preferably chosen as is slightly heat-resisting (or with heat-resisting thermoplastic blend), to avoid causing the melting of described layer due to the other core of mold pressing subsequently and/or cover layer.

Consider the size of hollow inside, the external diameter that hollow core of the present invention (shell, shell and outer nuclear layer) preferably has is approximately 0.75 inch to approximately 1.58 inches, preferably approximately 1.0 inches to approximately 1.57 inches, more preferably from about 1.3 inches to approximately 1.56 inches, most preferably from about 1.4 inches to approximately 1.55 inches.In preferred embodiments, the external diameter that shell has is approximately 0.75 inch, 1.0 inches, 1.20 inches or 1.30 inches, and most preferred external diameter is 0.75 inch or 1.0 inches.In another embodiment, the external diameter that outer nuclear layer should have (integral hollow core, shell adds outer nuclear layer) is approximately 1.30 inches to approximately 1.62 inches, preferably 1.4 inches to approximately 1.6 inches, and more preferably from about 1.5 inches to approximately 1.59 inches.In preferred embodiments, the external diameter that outer nuclear layer has is approximately 1.51 inches, 1.53 inches, or most preferably 1.550 inches.

The thickness that inner covering layer and outer cover preferably have is approximately 0.010 to 0.080 inch, more preferably from about 0.015 to 0.060 inch, and most preferably from about 0.020 to 0.040 inch.Alternatively, the thickness that described inner covering layer and outer cover have is approximately 0.015 inch to approximately 0.055 inch, more preferably from about 0.02 inch to approximately 0.04 inch, and most preferably from about 0.025 inch to approximately 0.035 inch.If present, the thickness that inner covering layer preferably has be approximately 60 Shore D or more than, more preferably from about 65 Shore D or more than, most preferably from about 70 Shore D or more than.Inner covering layer is preferably harder than outer cover, although outer cover is harder than inner covering layer in one embodiment.Outer cover preferably has for approximately 60 Shore D or following hardness, more preferably from about 55 Shore D or following, most preferably from about 50 Shore D or following.

The formation of shell of the present invention and outer nuclear layer can realize in many ways, such as at No.5, and 480,155,6,315,683 and 8,262, those disclosed method in No. 508 United States Patent (USP)s, is all incorporated herein by reference the full content of these patents.

In a preferred embodiment, golf of the present invention comprises hollow core.As discussed above, described hollow core comprises the spherical inner core shell being formed by the first thermoset rubber composition.Described shell has outer surface, inner surface and internal diameter to limit hollow centre or inside.In this embodiment, single thermoplasticity outer nuclear layer is configured in shell around to complete hollow core.Single cover layer or preferably inner covering layer are formed on around outer nuclear layer.When there is inner covering layer, outer cover is formed on inner covering layer.Most preferably, inner covering layer is formed by ionomer polymeric material, and outer cover is formed by polyurethane material, and the hardness that outer cover has is less than the hardness of inner covering layer.Preferably, inner covering layer has the hardness that is greater than approximately 60 Shore D, and outer cover has the hardness that is less than approximately 60 Shore D.

The diameter that hollow centre has is approximately 0.15 to 1.1 inches, preferably approximately 0.25 to 1.0 inches, and more preferably from about 0.25 to 0.75 inch, most preferably from about 0.3 to 0.5 inch.In this embodiment, the case hardness that shell has is greater than its inner surface hardness approximately 3 to 25 Shore C to define the first hardness gradient.

Thermoplasticity outer nuclear layer has the second hardness gradient.Shell has the case hardness that is greater than approximately 55 Shore C.When the incidence rate with 125ft/s is measured, described spherical inner core shell has the coefficient of resilience (COR) that is less than approximately 0.750.Preferably, described COR is less than approximately 0.700, and more preferably from about 0.500 to 0.700, most preferably from about 0.600 to 0.700.While measuring with the incidence rate of 125ft/s, the COR that whole core (combination of hollow core and any outer nuclear layer) has is greater than approximately 5% higher than the COR of kernel shell, and more preferably from about 10 to 50%, most preferably from about 15 to 30%.

In another embodiment, the hardness gradient of thermoplasticity outer nuclear layer has " zero hardness gradient ".Zero hardness gradient is generally approximately 0 Shore C (being defined as ± 2 Shore C) herein.The hardness gradient of thermoplasticity outer nuclear layer also can have " negative hardness gradient ", preferably approximately 1 to 10 Shore C, more preferably from about 2 to 8 Shore C, most preferably from about 2 to 5 Shore C.The hardness gradient of thermoplasticity outer nuclear layer also can have " positive hardness gradient ", preferably approximately 1 to 10 Shore C, more preferably from about 2 to 8 Shore C, most preferably from about 2 to 5 Shore C.

Golf has the first volume, and hollow centre has the second volume.The volume of hollow centre is about 2% to 30% of golf volume, is more preferably about 5% to 25% of golf volume, is most preferably 10% to 20% of golf volume.

With reference to Fig. 1 a and 1b, two different embodiments of TS/TP hollow core golf are disclosed.Fig. 1 a describes the hardness curve of the golf with hollow core, ionomer inner covering layer and polyurethane outer cover.Thermosetting shell has the thickness of approximately 0.375 inch and the external diameter of approximately 1.0 inches, and spherical hollow inside has the diameter of approximately 0.25 inch.Thermosetting shell has approximately 12 " positive hardness gradient " across its thickness.Thermoplasticity HNP outer nuclear layer has the thickness of approximately 0.275 inch and the external diameter of approximately 1.55 inches.Thermoplasticity HNP outer nuclear layer has " zero hardness gradient " across its thickness.Inner covering layer has the thickness of approximately 0.035 inch, and outer cover has the thickness of approximately 0.03 inch.Fig. 1 b describes the hardness curve of another golf with hollow core, ionomer inner covering layer and polyurethane outer cover.Thermosetting shell has the thickness of approximately 0.3125 inch and the external diameter of approximately 0.75 inch, and spherical hollow inside has the diameter of approximately 0.125 inch.Thermosetting shell has approximately 12 " positive hardness gradient " across its thickness.Thermoplasticity HNP outer nuclear layer has the thickness of approximately 0.39 inch and the external diameter of approximately 1.53 inches.Thermoplasticity HNP outer nuclear layer has " zero hardness gradient " across its thickness.Inner covering layer has the thickness of approximately 0.045 inch, and outer cover has the thickness of approximately 0.03 inch.

In another embodiment of the invention, hollow core further comprises the middle stratum nucleare of the thermoplasticity being configured between shell and thermoplasticity outer nuclear layer.In another embodiment still, hollow core further comprises stratum nucleare in the middle of the thermosetting being configured between shell and outer nuclear layer.Middle stratum nucleare is formed by thermoset rubber composition, and described thermoset rubber composition is identical or different with the thermoset rubber composition that is used to form shell.Preferably, hollow centre has the diameter of approximately 0.51 to 1.1 inches, and shell has the case hardness that is greater than approximately 55 Shore C.

Golf of the present invention comprises the hollow core being formed by shell, and described shell is included in the spherical hollow space of its inside.Described spherical inner core shell is by thermoplastic compounds, and the ionomer of preferred conventional ionomer or neutralization completely forms.Described shell has outer surface, inner surface and internal diameter, the size of its definition hollow centre.Single thermosetting outer nuclear layer is formed on shell, and comprises thermoset rubber composition.The combination of thermoplasticity shell and thermosetting outer nuclear layer obtains TP/TS hollow core.Conventionally, inner covering layer and outer cover are formed on thermosetting outer nuclear layer.In a preferred embodiment, inner covering layer comprises ionomer polymeric material, and outer cover comprises polyureas or more preferably polyurethane.Outer cover can be harder than inner covering layer, but preferably softer than inner covering layer.

The diameter that hollow centre has is approximately 0.15 to 1.1 inches, preferably approximately 0.25 to 1.0 inches, and more preferably from about 0.25 to 0.75 inch, most preferably from about 0.3 to 0.5 inch.The case hardness of thermoplasticity shell is preferably more than hardness approximately 1 to the 5 Shore C of this shell inner surface, to define the first hardness gradient.Thermosetting outer nuclear layer has the second hardness gradient, and it is greater than the hardness gradient of thermoplasticity shell.In another embodiment, the hardness gradient of thermosetting outer nuclear layer has " zero hardness gradient ".Zero hardness gradient is generally approximately 0 Shore C (being defined as ± 2 Shore C) herein.The hardness gradient of thermosetting outer nuclear layer also can have " negative hardness gradient ", preferably approximately 3 to 25 Shore C, more preferably from about 5 to 20 Shore C, most preferably from about 8 to 15 Shore C.The hardness gradient of thermosetting outer nuclear layer also can have " positive hardness gradient ", preferably approximately 3 to 25 Shore C, more preferably from about 5 to 20 Shore C, most preferably from about 8 to 15 Shore C.

With reference to Fig. 2 a and 2b, two different embodiments of TS/TP hollow core golf are disclosed.Fig. 2 a describes the hardness curve of the golf with hollow core, ionomer inner covering layer and polyurethane outer cover.Thermoplasticity shell has the thickness of approximately 0.375 inch and the external diameter of approximately 1.0 inches, and spherical hollow inside has the diameter of approximately 0.25 inch.Thermoplasticity shell has " zero hardness gradient " across its thickness.Thermosetting outer nuclear layer has the thickness of approximately 0.275 inch and the external diameter of approximately 1.55 inches.Described thermosetting outer nuclear layer has " zero hardness gradient " across its thickness.Inner covering layer has the thickness of approximately 0.035 inch, and outer cover has the thickness of approximately 0.03 inch.Fig. 2 b described there is hollow core, the hardness curve of the another kind of golf of ionomer inner covering layer and polyurethane outer cover.Thermoplasticity shell has the thickness of approximately 0.3125 inch and the external diameter of approximately 0.75 inch, and spherical hollow inside has the diameter of approximately 0.125 inch.Described thermoplasticity shell has " zero hardness gradient " across its thickness.Thermosetting outer nuclear layer has the thickness of approximately 0.39 inch and the external diameter of approximately 1.53 inches.Described thermosetting outer nuclear layer has " the positive hardness gradient " across approximately 27 Shore C of its thickness.Inner covering layer has the thickness of approximately 0.045 inch, and outer cover has the thickness of approximately 0.03 inch.

In another embodiment of the invention, hollow core further comprises the middle stratum nucleare of the thermoplasticity being configured between shell and thermoplasticity outer nuclear layer.The thermoplastic that in the middle of described thermoplasticity, stratum nucleare can be identical or different by the thermoplastic with shell forms.In another embodiment still, hollow core further comprises stratum nucleare in the middle of the thermosetting being configured between thermoplasticity shell and thermosetting outer nuclear layer.The thermoset rubber composition that in the middle of described, stratum nucleare can be identical or different by the thermoset rubber composition with being used to form thermosetting outer nuclear layer forms.In these embodiments, hollow centre preferably has the diameter of approximately 0.15 to 1.1 inches, the case hardness that thermoplasticity shell has is greater than inner surface hardness approximately 1 to 5 Shore C to define the first hardness gradient, preferably " positive hardness gradient ", in the middle of thermosetting outer nuclear layer or thermosetting, stratum nucleare has the second hardness gradient.

Golf of the present invention comprises the hollow core being formed by shell, and described shell is included in the spherical hollow space of its inside.Described spherical inner core shell is by thermoplastic compounds, and the ionomer of preferred conventional ionomer or neutralization completely forms.Described shell has outer surface, inner surface and internal diameter, the size of its definition hollow centre.Single thermoplasticity outer nuclear layer is formed on shell, and preferably includes ionomer polymeric compositions.The combination of thermoplasticity shell and thermoplasticity outer nuclear layer obtains TP/TP hollow core.Conventionally, inner covering layer and outer cover are formed on thermoplasticity outer nuclear layer.In a preferred embodiment, inner covering layer comprises ionomer polymeric material, and outer cover comprises polyureas or more preferably polyurethane.Described outer cover is preferably softer than inner covering layer.

The diameter that hollow centre has is approximately 0.15 to 1.1 inches, preferably approximately 0.25 to 1.0 inches, and more preferably from about 0.25 to 0.75 inch, most preferably from about 0.3 to 0.5 inch.The case hardness of thermoplasticity shell is preferably more than hardness approximately 0 to the 5 Shore C of this shell inner surface, to define hardness gradient.It is identical or be greater than its hardness gradient that thermoplasticity outer nuclear layer also has hardness gradient with thermoplasticity shell.In another embodiment, the hardness gradient of thermoplasticity outer nuclear layer has " zero hardness gradient ".Zero hardness gradient is generally approximately 0 Shore C (being defined as ± 2 Shore C) herein.The hardness gradient of thermoplasticity outer nuclear layer also can have " negative hardness gradient ", preferably approximately 1 to 10 Shore C, more preferably from about 2 to 8 Shore C, most preferably from about 3 to 5 Shore C.The hardness gradient of thermoplasticity outer nuclear layer also can have " positive hardness gradient ", preferably approximately 1 to 10 Shore C, more preferably from about 2 to 8 Shore C, most preferably from about 3 to 5 Shore C.

When incident speed measurement with 125ft/s, thermoplasticity kernel shell has the COR that is less than approximately 0.750.Preferably, described COR is less than approximately 0.700, and more preferably from about 0.500 to 0.700, most preferably from about 0.600 to 0.700.While measuring with the incidence rate of 125ft/s, the COR that whole hollow core (combination of thermoplasticity shell and thermoplasticity outer nuclear layer) has is greater than approximately 5% higher than the COR of kernel shell, and more preferably from about 10 to 50%, most preferably from about 15 to 30%.

With reference to Fig. 3 a and 3b, two different embodiments of TP/TP hollow core golf are disclosed.Fig. 3 a describes the hardness curve of the golf with hollow core, ionomer inner covering layer and polyurethane outer cover.Thermoplasticity shell has the thickness of approximately 0.375 inch and the external diameter of approximately 1.0 inches, and spherical hollow inside has the diameter of approximately 0.25 inch.Thermoplasticity outer nuclear layer has the thickness of approximately 0.275 inch and the external diameter of approximately 1.55 inches.Inner covering layer has the thickness of approximately 0.035 inch, and outer cover has the diameter of approximately 0.03 inch.Thermoplasticity shell and thermoplasticity outer nuclear layer all have " zero hardness gradient " across its respective thickness.Fig. 3 b described there is hollow core, the hardness curve of the another kind of golf of ionomer inner covering layer and polyurethane outer cover.Thermoplasticity shell has the thickness of approximately 0.3125 inch and the external diameter of approximately 0.75 inch, and spherical hollow inside has the diameter of approximately 0.125 inch.Thermoplasticity outer nuclear layer has the thickness of approximately 0.39 inch and the external diameter of approximately 1.53 inches.Inner covering layer has the thickness of approximately 0.045 inch, and outer cover has the thickness of approximately 0.03 inch.Thermoplasticity shell and thermoplasticity outer nuclear layer all have " zero hardness gradient " across its respective thickness.

In another embodiment of the invention, hollow core further comprises the middle stratum nucleare of the thermoplasticity being configured between thermoplasticity shell and thermoplasticity outer nuclear layer.In another embodiment still, hollow core further comprises stratum nucleare in the middle of the thermosetting being configured between thermoplasticity shell and thermoplasticity outer nuclear layer.In the middle of described, stratum nucleare is preferably formed by thermoset rubber composition.In these embodiments, hollow centre preferably has the diameter of approximately 0.15 to 1.1 inches, and the case hardness that thermoplasticity shell has is greater than inner surface hardness approximately 1 to 10 Shore C, to define hardness gradient, preferably " positive hardness gradient ".The hardness gradient that described thermoplasticity outer nuclear layer preferably has is different from the hardness gradient in thermoplasticity shell or intermediate layer.

In a preferred embodiment, golf of the present invention comprises hollow core.Described hollow core is formed by the spherical inner core shell that is included in the spherical hollow space of its inside.Described shell is formed by thermoset rubber composition, and has outer surface, inner surface and internal diameter to define the size of hollow centre.In this embodiment, single outer nuclear layer is formed on around shell, to produce hollow golf ball.Described outer nuclear layer is also formed by thermosets, and this thermosets can be the rubber composition identical with described shell, but is preferably different thermoset rubber compositions.Single cover layer or many cover layers are formed in TS/TS hollow core.Preferably, inner covering layer and outer cover are formed on outer nuclear layer.In one embodiment, inner covering layer comprises ionomer polymeric material, and outer cover comprises polyureas or optimization polyurethane.Outer cover is conventionally softer than inner covering layer, and such as inner covering layer wherein has the hardness that is greater than approximately 60 Shore D, outer cover has the hardness that is less than approximately 60 Shore D.

In the above-described embodiment, hollow centre preferably has the diameter of approximately 0.51 to 1.1 inches.The case hardness of shell is preferably more than hardness approximately 3 to the 25 Shore C of this shell inner surface, to define the first hardness gradient.In a preferred embodiment, the hardness gradient that thermosetting outer nuclear layer has is different from the hardness gradient of thermosetting shell.Most preferably, described shell has the case hardness that is greater than approximately 55 Shore C.

When incident speed measurement with 125ft/s, thermosetting kernel shell has the coefficient of resilience (COR) that is less than approximately 0.750.Preferably, described COR is less than approximately 0.700, and more preferably from about 0.500 to 0.700, most preferably from about 0.600 to 0.700.While measuring with the incidence rate of 125ft/s, the COR that whole hollow core (combination of thermosetting shell and thermosetting outer nuclear layer) has is greater than approximately 5% higher than the COR of kernel shell, and more preferably from about 10 to 50%, most preferably from about 15 to 30%.

In another embodiment, the hardness gradient of thermosetting outer nuclear layer has " zero hardness gradient ".Zero hardness gradient is generally approximately 0 Shore C (being defined as ± 2 Shore C) herein.The hardness gradient of thermosetting outer nuclear layer also can have " negative hardness gradient ", preferably approximately 3 to 25 Shore C, more preferably from about 5 to 20 Shore C, most preferably from about 8 to 15 Shore C.The hardness gradient of thermosetting outer nuclear layer also can have " positive hardness gradient ", preferably approximately 3 to 25 Shore C, more preferably from about 5 to 20 Shore C, most preferably from about 8 to 15 Shore C.

In another embodiment of the invention, hollow core further comprises the middle stratum nucleare of the thermoplasticity being configured between thermosetting shell and thermosetting outer nuclear layer.In another embodiment still, hollow core further comprises stratum nucleare in the middle of the thermosetting being configured between thermosetting shell and thermosetting outer nuclear layer.In the middle of described, stratum nucleare can be formed by thermoset rubber composition, and this thermoset rubber composition is identical or different with the thermoset rubber composition that is used to form thermosetting shell or thermosetting outer nuclear layer.In these embodiments, hollow centre preferably has the diameter of approximately 0.15 to 1.1 inches, and the case hardness that shell has is greater than inner surface hardness approximately 10 to 25 Shore C, to define hardness gradient, preferably " positive hardness gradient ".The hardness gradient that described thermosetting outer nuclear layer preferably has is different from the hardness gradient in shell or intermediate layer.

Hollow core of the present invention is covered by least one cover layer.Intermediate layer can optionally be configured in around hollow core such as inner covering layer, has in intermediate layer the cover layer that forms around as outer cover.Although any thermoplastic disclosed herein can be applicable to inner covering layer of the present invention or outer cover, in a preferred embodiment, the cover layer of outermost is by pourable polyureas or pourable polyurethane; Pourable mixing gathers (polyurethane/urea); Form with pourable mixing poly-(urea/polyurethane).Suitable polyurethane is included in No.5, and 334,673 and 6,506, those disclosed in No. 851 United States Patent (USP)s.Suitable polyureas is included in No.5, and 484,870 and 6,835, those disclosed in No. 794 United States Patent (USP)s.These patents are incorporated herein by reference.

The product that other suitable urethane composition comprises at least one PIC and at least one curing agent.Curing agent can comprise for example one or more polyamines, one or more polyalcohols or its combination.PIC and one or more polyalcohols can be combined to form prepolymer, then by this prepolymer and the combination of at least one curing agent.Therefore, polyalcohol described herein is adapted at using in one or both of two kinds of compositions of polyurethane material (as a part for prepolymer and use in curing agent).More suitably polyurethane is described in No.7, in 331, No. 878 United States Patent (USP)s, its full content is incorporated herein by reference.

The obtainable any PIC of those of ordinary skills is all applicable to used according to the invention.Exemplary PIC includes but not limited to 4,4'-methyl diphenylene diisocyanate (MDI); Polymeric MDI; The liquid MDI of carbodiimide modified; 4,4'-dicyclohexyl methyl hydride diisocyanate (H ₁₂mDI); P-phenylene vulcabond (PPDI); M-phenylene vulcabond (MPDI); Toluene di-isocyanate(TDI) (TDI); 3,3 '-dimethyl-4,4 '-diphenylene vulcabond; IPDI; 1,6-hexamethylene diisocyanate (HDI); Naphthalene diisocyanate; XDI; P-tetramethylxylene diisocyanate; M-tetramethylxylene diisocyanate; Ethylidene diisocyanate; Propylidene-1,2-vulcabond; Tetramethylene-Isosorbide-5-Nitrae-vulcabond; Cyclohexyl diisocyanate; Dodecane-1,12-vulcabond; Cyclobutane-1,3-vulcabond; Cyclohexane-1,3-vulcabond; Cyclohexane-Isosorbide-5-Nitrae-vulcabond; 1-NCO-3,3,5-trimethyl-5-NCO hexahydrotoluene; Methyl cyclohexylidene vulcabond; The triisocyanate of HDI; 2,4,4-trimethyl-1, the triisocyanate of 6-hexane diisocyanate; Aphthacene vulcabond; Naphthalene diisocyanate; Anthracene vulcabond; The isocyanuric acid ester of toluene di-isocyanate(TDI); The uretdione of hexa-methylene two isocyanic acids; And composition thereof.The known PIC of those of ordinary skills has an isocyanate groups, for example di-isocyanate, tri-isocyanate and the four-isocyanates of surpassing.Preferably, PIC comprises MDI, PPDI, TDI or its mixture, and more preferably, PIC comprises MDI.Be to be understood that, term MDI comprises 4 as used herein, the liquid MDI of 4'-methyl diphenylene diisocyanate, polymeric MDI, carbodiimide modified, and composition thereof, and, in addition, the vulcabond adopting can be " low free monomer ", and those of ordinary skills are interpreted as " dissociating " the monomeric diisocyanate base with reduced levels, are conventionally less than approximately 0.1% free monomer NCO.The example of " low free monomer " vulcabond includes, but not limited to low free monomer MDI, low free monomer TDI and low free monomer PPDI.Described at least one PIC should have and is less than approximately 14% unreacted NCO group.Preferably, described at least one PIC has and is not more than about 8.0%NCO, more preferably no more than approximately 7.8%, and is most preferably not more than about 7.5%NCO, and normally used NCO level is approximately 7.2% or 7.0% or 6.5% NCO.

The obtainable any polyalcohol of those of ordinary skills is applicable to used according to the invention.Exemplary polyalcohol includes, but are not limited to PPG, hydroxy-end capped polybutadiene (comprising part/complete all hydrogenated derivative), PEPA, polycaprolactone polyol and polycarbonate polyol.In a preferred embodiment, polyalcohol comprises PPG.Example include, but not limited to the sub-propane diols of polytetramethylene ether diol (PTMEG), polyethylene glycol propane diols, polyoxy, and composition thereof.Hydrocarbon chain can have saturated or unsaturated bond and replacement or unsubstituted aromatic series and cyclic group.Preferably, polyalcohol of the present invention comprises PTMEG.

In another embodiment, polyurethane material comprises PEPA.Suitable PEPA includes, but not limited to polyethylene glycol adipate glycol; Polybutylene glyool adipate; Polyethylene glycol adipate propylene glycol ester glycol; O-phthalic acid ester-1,6-hexylene glycol; Poly-(adipic acid hexylene glycol ester) glycol; And composition thereof.Hydrocarbon chain can have saturated or unsaturated bond or replacement or unsubstituted aromatic series and cyclic group.

In another embodiment, material of the present invention comprises polycaprolactone polyol.Suitable polycaprolactone polyol comprises, but be not limited to, the polycaprolactone that the polycaprolactone that the polycaprolactone that the polycaprolactone that the polycaprolactone that 1,6-hexylene glycol causes, diethylene glycol (DEG) cause, trimethylolpropane cause, neopentyl glycol cause, BDO cause, and composition thereof.Hydrocarbon chain can have aromatic series saturated or unsaturated key or replacement or unsubstituted and cyclic group.

In another embodiment still, polyurethane material of the present invention comprises polycarbonate polyol.Suitable Merlon includes, but not limited to poly-carbonic acid O-phthalic ester and poly-(carbonic acid hexylene glycol ester) glycol.Hydrocarbon chain can have aromatic series saturated or unsaturated key or replacement or unsubstituted and cyclic group.In one embodiment, the molecular weight of polyalcohol is approximately 200 to approximately 4000.

Polyamine curing agent is also applicable in urethane composition of the present invention, and has been found that anti-cutting, shear resistant and the impact resistance of improving gained ball.Preferred polyamine curing agent includes, but not limited to 3,5-dimethyl disulfide for-2,4-toluenediamine and isomers thereof; 3,5-diethyl Toluene-2,4-diisocyanate, 4-diamines and isomers thereof, such as 3,5-diethyl Toluene-2,4-diisocyanate, 6-diamines; 4,4 '-bis--(second month in a season-butyl is amino)-diphenyl methane; Isosorbide-5-Nitrae-bis--(second month in a season-butyl is amino)-benzene, 4,4 '-methylene-bis--(2-chloroaniline); 4,4 '-methylene-bis--(3-chloro-2,6-diethyl aniline); Polytetramethylene oxide-bis--Para-Aminobenzoic; N, N'-dialkyl group diamines diphenyl methane; P, p'-methylene dianiline (MDA); M-phenylene diamine (MPD); 4,4 '-methylene-bis--(2-chloroaniline); 4,4 '-methylene-bis--(2,6-diethylaniline); 4,4 '-methylene-bis--(2,3-dichloroaniline); 4,4 '-diaminourea-3,3 '-diethyl-5,5 '-dimethyl diphenylmethane; 2,2 ', 3,3 '-tetrachloro diaminodiphenyl-methane; Trimethylene two-Para-Aminobenzoic ester; And composition thereof.Preferably, curing agent of the present invention comprises that 3,5-dimethyl disulfide is for-2,4-toluenediamine and isomers thereof, such as 300, from Albermarle Corporation, (Baton Rouge, LA is commercially available to be obtained.Suitable polyamines (comprising primary amine and secondary amine) curing agent preferably has approximately 64 to approximately 2000 molecular weight.

Can be by glycol, triol, tetrol or hydroxy-end capped curing agent, at least one joins in aforesaid urethane composition.Suitable glycol, triol and tetrol group comprise ethylene glycol; Diethylene glycol; Polyethylene glycol; Propane diols; Polypropylene glycol; Lower molecular weight polytetramethylene ether diol; 1,3-pair (2-hydroxyl-oxethyl] benzene; 1,3-pair-[2-(2-hydroxyl-oxethyl) ethyoxyl] benzene; 1,3-pair-2-[2-(2-hydroxyl-oxethyl) ethyoxyl] and ethyoxyl } benzene; BDO; 1,5-PD; 1,6-hexylene glycol; Resorcinol-bis--(beta-hydroxy ethyl) ether; Quinhydrones-bis--(beta-hydroxy ethyl) ether; And composition thereof.Preferred hydroxy-end capped curing agent comprises two (2-hydroxyl-oxethyl) benzene of 1,3-; 1,3-pair-[2-(2-hydroxyl-oxethyl) ethyoxyl] benzene; 1,3-pair-2-[2-(2-hydroxyl-oxethyl) ethyoxyl] and ethyoxyl } benzene; BDO, and composition thereof.Preferably, to have scope be approximately 48 to 2000 molecular weight to hydroxy-end capped curing agent.Should be appreciated that molecular weight is absolute weight mean molecule quantity as used herein, as those of ordinary skills, be to be understood that.

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

In a preferred embodiment of the invention, with saturated polyurethane, form one or more cover layers, preferred outer cover, and can be selected from pourable thermosetting and thermoplastic polyurethane.In this embodiment, saturated polyurethane of the present invention is gone up substantially not containing aromatic group or part.Be applicable to saturated polyurethane of the present invention and be the product of the reaction between at least one polyurethane prepolymer and curing agent that at least one is saturated.Polyurethane prepolymer is the product forming by the reaction between at least one saturated polyalcohol and vulcabond that at least one is saturated.As well known in the art, can adopt catalyst to promote curing agent and isocyanates and polyalcohol, or reacting between curing agent and prepolymer.

In addition, polyurethane can be substituted by polyurea materials or mix with it.Polyureas is significantly different from urethane composition.It is natural saturated that composition based on polyureas is preferably.Polyurea composition can form by isocyanates with the product of the crosslinked polyamines prepolymer of curing agent.For example, can be prepared by least one isocyanates, at least one polyetheramine and at least one two polyol curing agent or at least one diamine curing agent based on polyureas of the present invention.

Although any embodiment of the application can have any known depression number and pattern, the number that preferably caves in is 252 to 456, and is more preferably 330 to 392.Depression can comprise disclosed any width, the degree of depth and corner angle in prior art, and pattern can comprise a plurality of depressions with different in width, the degree of depth and corner angle.The die parting line configuration of described pattern can be straight line or staggered wave die parting line (SWPL).Most preferably, depression number is 330,332 or 392, and comprises 5 to 7 kinds of depression sizes, and die parting line is SWPL.

In any these embodiments, individual layer endorses to replace with two-layer core or more multi-layered core, and wherein at least one stratum nucleare has negative hardness gradient.Embodiment is different from operation, unless or separately specifically noted, all number ranges, amount, value and percentage are such as those number ranges, amount, value and percentage read like with regard to the amount of other things in the amount with regard to material and description are as having above term " about " modifies, even if term " about " may not can be occurred together with described value, amount or scope clearly.Therefore, unless the contrary indication, otherwise in description and appended claim, listed numerical parameter is approximation, the character that it can the expectation of desired acquisition according to the present invention and changing.At least, and do not attempt, by the scope that should be used for limiting claim of identical instruction, each numerical parameter should at least be explained according to given significant digits with by using the common technology of rounding up.

Although provide wide in range number range of enclosing of the present invention and parameter, be similar to, the numerical value providing in specific embodiment as far as possible accurately provides.Yet any numerical value itself must comprise some error causing due to the standard deviation existing in their each experimental measurement.And, when the application provides various number range, can use any combination (comprising cited value) of any these values.

Although be that illustrative embodiments of the present invention disclosed herein meets above-mentioned object apparently, should be appreciated that, those skilled in the art can expect many improvement and other embodiment.Therefore, be to be understood that appended claim is intended that covering all these improvement and embodiment within the spirit and scope of the present invention.

Claims

1. the golf that comprises hollow core, described golf comprises:

Spherical inner core shell, it is formed by the first material, and described shell has outer surface, inner surface and internal diameter to limit hollow centre;

Outer nuclear layer, is configured in around described shell, and described outer nuclear layer comprises the second material;

Inner covering layer, is configured in around described outer nuclear layer, and described inner covering layer comprises ionomer polymeric material; With

Outer cover, is configured in around described inner covering layer, and described outer covering comprises that polyureas or polyurethane and the hardness having are less than the hardness of described inner covering layer;

Wherein said hollow centre has the diameter of approximately 0.15 to 1.1 inches, and described shell has the first hardness gradient, and described outer nuclear layer has the second hardness gradient that is different from the first hardness gradient.

2. golf as claimed in claim 1, wherein said the first and second materials are thermoplastic.

3. golf as claimed in claim 2, wherein said the first hardness gradient is the positive hardness gradient that is at most 5 Shore C.

4. golf as claimed in claim 3, wherein said the second hardness gradient is positive hardness gradient or negative hardness gradient.

5. golf as claimed in claim 1, wherein said the first material is heat cured, and described the second material is thermoplastic.

6. golf as claimed in claim 5, wherein said the first hardness gradient is the positive hardness gradient of approximately 3 to 25 Shore C.

7. golf as claimed in claim 1, wherein said the first material is thermoplastic, and described the second material is heat cured.

8. golf as claimed in claim 7, wherein said the first hardness gradient is the positive hardness gradient that is at most 5 Shore C.

9. golf as claimed in claim 8, wherein said the second hardness gradient is the positive hardness gradient of approximately 3 to 25 Shore C.

10. golf as claimed in claim 1, wherein said the first material is heat cured, and described the second material is heat cured.

11. golf as claimed in claim 1, wherein said golf has the first volume, and described hollow centre has 2% to 30% the second volume that is about the first volume.

12. golf as claimed in claim 1, wherein, when the incidence rate with 125ft/s is measured, described spherical inner core shell has the coefficient of resilience that is less than approximately 0.700.

13. golf as claimed in claim 1, wherein said outer nuclear layer has the coefficient of resilience 10-50% that the coefficient of resilience of measuring with the incidence rate of 125ft/s exceeds the described kernel shell of measuring with the incidence rate of 125ft/s.