CN102166404B - Multilayer core golf ball - Google Patents

Abstract

The present invention relates to multilayer core golf ball, i.e. comprise the golf of multilayer core and shell.Described multilayer core comprises the intermediate core layer that at least one of which is formed by metal composites, composite or inorganic/organic blend compositions.

Description

Multilayer core golf ball

Cross reference related application

The application is the part continuation application of 12/407,856 applications submitted on March 20th, 2009, 12/407,856 application is the United States Patent (USP) of the Application No. 11/972,240 that on January 10th, 2008 submits to The part continuation application of application, here by introducing the full content including above-mentioned application in.

Technical field

This patent disclosure relates generally to golf, and systems there is the golf of multilayer core Ball, described multilayer core comprises at least one of which by metal composites, composite or inorganic/organic The intermediate core layer that blend compositions is formed.

Background technology

The golf with multilayer core is known.Such as, United States Patent (USP) 6,852,044 discloses tool Have the golf of multilayer core, described multilayer core have by relative stiffness outer layer core surround the softest , the inner core of low ball hardness (compression).United States Patent (USP) 5,772,531 discloses a kind of solid Gao Er Husband's ball, it comprises: have the solid core of the three-decker being made up of internal layer, intermediate layer and outer layer, and For being coated with the shell of this solid core.The U.S. Patent application of Publication No. 2006/0128904 also discloses many The golf of layer core.Other examples of multilayer core can be, such as, and United States Patent (USP) 5,743,816, 6,071,201、6,336,872、6,379,269、6,394,912、6,406,383、6,431,998、6,569,036、 6,605,009、6,626,770、6,815,521、6,855,074、6,913,548、6,981,926、6,988,962、 7,074,137, obtain in 7,153,467 and 7,255,656.

The invention provides a kind of new multilayer core golf ball structure, it includes by metal composites, answers The intermediate core layer that condensation material compositions or inorganic/organic blend compositions are formed.

Summary of the invention

In one embodiment, the present invention relates to comprise inner core, intermediate core layer, outer sandwich layer and shell Golf.Inner core comprises the center formed by the first thermoset composition, and has 1.000 inches To the diameters of 1.580 inches, the central hardness and 50 of 40 Shore C hardness to 70 Shore C hardness Shore C hardness is to the case hardness of 95 Shore C hardness.Intermediate core layer has 0.010 inch to 0.070 The thickness of inch, the outer surface hardness of 65 Shore D hardness to 95 Shore D hardness, and by selected from gold The compositions belonging to compositions, composite and inorganic/organic blend compositions is formed.Outer sandwich layer Have outside thickness and the 45 Shore C hardness to 90 Shore C hardness of 0.010 inch to 0.075 inch Case hardness, and formed by the second thermoset composition.Shell has 0.010 inch to 0.050 inch Thickness, and formed by the compositions that material hardness is 30 Shore D hardness to 65 Shore D hardness.

In another embodiment, the present invention relates to comprise inner core, intermediate core layer, outer sandwich layer and shell Golf.Inner core comprises the center formed by the first thermoplastic compounds, and has 1.000 inches To the diameter of 1.580 inches, the central hardness of 40 Shore C hardness to 70 Shore C hardness, and 50 Shore C hardness is to the case hardness of 95 Shore C hardness.Intermediate core layer has 0.010 inch to 0.070 The thickness of inch, the outer surface hardness of 65 Shore D hardness to 95 Shore D hardness, and by selected from gold The compositions belonging to compositions, composite and inorganic/organic blend compositions is formed.Outer sandwich layer There is the thickness of 0.010 inch to 0.075 inch, outside 45 Shore C hardness to 90 Shore C hardness Case hardness, and formed by the second thermoplastic compounds.The thickness of shell be 0.010 inch to 0.050 Inch, and formed by the compositions that material hardness is 30 Shore D hardness to 65 Shore D hardness.

In another embodiment, the present invention relates to comprise the golf of core and shell.Core by inner sandwich layer, Intermediate core layer, the first outer sandwich layer and the second outer sandwich layer composition.Inner sandwich layer is formed by the first thermoplastic compounds, And there is the diameter of 1.000 inches to 1.580 inches, 40 Shore C hardness are to 70 Shore C hardness Central authorities' hardness, and 50 Shore C hardness are to the case hardness of 95 Shore C hardness.Intermediate core layer has There are thickness, the surface of 65 Shore D hardness to 95 Shore D hardness of 0.010 inch to 0.070 inch Hardness, and by selected from metal composites, composite and the group of inorganic/organic blend compositions Compound is formed.First outer sandwich layer is formed by the second thermoplastic compounds.Second outer sandwich layer is by thermosetting composition Thing is formed, and has thickness, the 45 Shore C hardness to 90 Shore C of 0.010 inch to 0.075 inch The case hardness of hardness.The thickness of shell is 0.010 inch to 0.050 inch, and by material hardness is The compositions of 30 Shore D hardness to 65 Shore D hardness is formed.

Accompanying drawing explanation

Fig. 1 is the profile of the golf according to one embodiment of the present invention.

Detailed description of the invention

Disclose the golf of the shell with multilayer core and this core of encapsulating.Fig. 1 shows according to the present invention The golf 30 of a kind of embodiment, it includes inner core 32, intermediate core 34, outer core 36 and shell 38. Although Fig. 1 is shown that simple layer, but in inner core 32, intermediate core 34, outer core 36 and shell 38 Any one or more can be made up of one layer, two-layer or multilamellar.

In specific embodiment, each in inner core 32, intermediate core 34, outer core 36 and shell 38 Individual is all simple layer.

In another specific embodiment, inner core 32 is made up of two-layer, and intermediate core 34, outer core 36 and shell 38 in each be simple layer.

In another specific embodiment, shell 38 is made up of two-layer, and intermediate core 34, outer core 36 It is simple layer with each in shell 38.

In another specific embodiment, inner core 32 and shell 38 are formed by two-layer, and intermediate core 34 and outer core 36 in each be simple layer.

The multilayer core of the present invention includes inner core, intermediate core and outer core.The overall diameter of this multilayer core is (the most also Refer to the external diameter of outer sandwich layer) it is 1.000 or 1.300 or 1.400 or 1.500 or 1.580 or 1.600 at lower limit Or 1.610 or 1.620 inches and the upper limit be 1.600 1.610 or 1.620 1.630 or 1.640 or In the range of 1.650 or 1.660 inches, wherein the upper limit (such as, is limited to 1.610 English instantly more than lower limit Time very little, the upper limit is 1.620,1.630,1.640,1.650 or 1.660 inches).Specific embodiment party In formula, the overall diameter of multilayer core is 1.450 inches or 1.500 inches or 1.510 inches or 1.530 inches Or 1.550 inches or 1.570 inches or 1.580 inches or 1.590 inches or 1.600 inches or 1.610 Inch or 1.620 inches.

Inner core is made up of single inner sandwich layer (referred to herein as center), or by center and additional inner core Layer composition；Or it is made up of center and two or more additional inner sandwich layers.The overall diameter of inner sandwich layer is 0.500 inch or higher, or 1.000 inches or higher, or 1.250 inches or higher, or 1.300 Inch or higher, or 1.350 inches or higher, or 1.390 inches or higher, or 1.400 Inch or higher, or 1.425 inches or higher, or 1.450 inches or higher, or it is overall Diameter within the range having a lower limit of 0.250 0.500 or 0.750 1.000 or 1.250 1.300 or 1.325 or 1.350 or 1.390 or 1.400 or 1.440 or 1.450 inches and the upper limit are 1.450 or 1.460 or 1.475 Or in the range of 1.490 or 1.500 or 1.520 or 1.550 or 1.580 or 1.600 inches.

The central hardness of inner core 20 or 25 or 30 or 35 or 40 or 45 or 50 or 55 Xiao within the range having a lower limit of Family name's C hardness and the upper limit are in the range of 60 or 65 or 70 or 75 or 90 Shore C hardness.Inner core Outer surface hardness 20 or 50 or 70 or 75 Shore C hardness and the upper limit within the range having a lower limit of be 75 or 80 or In the range of 85 or 90 or 95 Shore C hardness.Inner core has a negative hardness gradient, zero hardness gradient, Or the positive hardness gradient of up to 45 Shore C hardness, or from 10 Shore C hardness to 45 Shores The positive hardness gradient of C hardness.In specific embodiment, the center that inner core is formed by zero gradient formula Composition, such as such as United States Patent (USP) 7,537,530 and 7, disclosed in 537,529, incorporated herein by by it Complete disclosure include in.Total ball hardness of inner core is 90 or lower, or 80 or lower, or 70 Or lower, or 60 or lower, or 50 or lower, or 40 or lower, or 20 or lower, or ball Hardness within the range having a lower limit of 10 20 or 30 35 or 40 50 or 60 and the upper limit be 40 or 50 or 60 Or in the range of 70 or 80 or 90, wherein the upper limit more than lower limit (such as, when being instantly limited to 50, its The upper limit is 60,70,80 or 90).

Each inner sandwich layer is formed by thermosetting or thermoplastic polymer composition.In specific embodiment, The center that inner core is formed by thermoset composition forms.In another specific embodiment, inner core is by warm The center composition that thermoplastic polymer composition is formed.In another specific embodiment, inner core is by center Forming with additional inner sandwich layer, each of which is by identical or different thermoset composition shapes Become.In another specific embodiment, inner core is made up of center and additional inner sandwich layer, every in them One is formed by identical or different thermoplastic polymer composition.At another specific embodiment In, inner core is made up of center and additional inner core, and wherein said center or additional inner sandwich layer are by thermosetting composition Another of thing formation and described center or additional inner sandwich layer is formed by thermoplastic polymer composition.? In another specific embodiment, inner core is by center, the first additional inner sandwich layer and the second additional inner sandwich layer group Become, wherein identical or different from other inner sandwich layer compositions each of in inner sandwich layer compositions.

Including rubber composition for forming the suitable thermoset compositions of inner sandwich layer, it comprises basis rubber Glue, initiator, coagent, and optionally comprise zinc oxide, zinc stearate or stearic acid, antioxygen One or more in agent and softening accelerator (soft and fast agent).Suitable base rubber bag Include natural and synthetic rubber, include but not limited to, polybutadiene, polyisoprene, ethylene propylene rubber (" EPR "), SBR styrene butadiene rubbers, styrene block copolymer rubber (as SI, SIS, SB, SBS, SIBS etc., wherein " S " is styrene, and " I " is isoprene, and " B " is butadiene), butyl rubber, halogen Change butyl rubber, polystyrene elastomers, polyethylene elastomer, polyurethane elastomer, SPUA, The elastomer of metallocene catalyst and plastic body, isobutene. and to the copolymer of ring-alkylated styrenes, isobutene. and To the copolymer of halogenated copolymers, butadiene and acrylonitrile of ring-alkylated styrenes, polychlorobutadiene, propylene Acid alkyl ester rubber, chlorination isoprene rubber, Chlorination of Acrylonitrile isoprene rubber, and they (such as polybutadiene and the combination of other thermosets less amount of, be somebody's turn to do in the combination of two or more Thermosets is selected from cis-polyisoprene, trans-polyisoprene, natural gum, polychlorobutadiene, gathers Norborene, polyoctenamer, polypenthylene, butyl rubber, EPR, EPDM, styrene-butadiene and class As thermosets).Preferably diene rubber, particularly polybutadiene (include having at least 40% cis The 1，4-polybutadiene of structure), styrene-butadiene, and the mixing of polybutadiene and other elastomers Thing, present in it, the amount of polybutadiene is at least the 40% of the total polymer weight of mixture.The most excellent The polybutadiene of choosing includes that neodymium is catalyzed high-cis polybutadiene, and cobalt, nickel or the polybutadiene of lithium catalysis. The suitable example of commercially available polybutadiene includes, but not limited to Buna CB neodymium catalysis height Cis-polybutadiene rubber, such as Buna CB 23, and Cobalt catalysis cis-rich polybutadiene rubber, As can be from Company trade obtains With 221；Can be from The Dow SE BR-1220 commercially-available for Chemical Company；Can be from Polimeri Commercially-available 's BR 40 and BR 60；Can be commercially-available from UBE Industries, Inc. 's Rubber；Can be from the commercially-available BR of Japan Synthetic Rubber Co., Ltd. 01；With can from commercially-available for Karbochem Neodene neodymium catalysis cis-rich polybutadiene rubber, as Neodene BR40。

Suitable initiator includes organic peroxide, can produce the high-energy radiation source of free radical, and it Combination.The high-energy radiation source that can produce free radical includes but not limited to, electron beam, ultraviolet spoke Penetrate, gamma radiation, X-radiation, infrared radiation, heat and combinations thereof.Suitable is organic Peroxide includes but not limited to, cumyl peroxide；4,4-bis-(tert-butyl hydroperoxide) n-butyl pentanoate； 1,1-bis-(tert-butyl hydroperoxide) 3,3,5-trimethyl-cyclohexane；2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) Hexamethylene；Di-t-butyl peroxide；Di t-amyl peroxide；Tert-butyl peroxide；Tert-butyl peroxide Isopropylbenzene；2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexin-3；Two (2-tert-butyl-peroxy isopropyls Base) benzene；Dilauroyl peroxide；Dibenzoyl peroxide；T-butyl hydroperoxide；Peroxidating Laurel Base；Benzoyl peroxide；And combinations thereof.The example bag of available commercial suitable peroxide Include but be not limited to, can be commercially-available from Akzo Nobel BC cumyl peroxide, With can be from RT Vanderbilt Company, Inc. is commercially-available Peroxide, as ANS benzoyl peroxide, 2311,1-bis-(tert-butyl hydroperoxide) 3,3,5-trimethyl-cyclohexane andDouble (tert-butyl peroxide) n-butyl pentanoate of 230-XL 4,4-.Peroxide initiator reagent is usual It is present in rubber composition with following amount: the amount of every 100 parts of base rubber at least 0.05 weight portions, or The most every 100 parts by weight of base rubber 0.05 weight portions of person or 0.1 weight portion or 0.8 weight portion or 1 weight portion or 1.25 weight portions or 1.5 weight portions and the upper limit are every 100 parts by weight of base rubber 2.5 weights Measure in the range of part or 3 weight portions or 5 weight portions or 6 weight portions or 10 weight portions or 15 weight portions Amount.

Coagent is generally and peroxide is used together to increase solid state.Suitable coagent bag Include but be not limited to, the slaine of unsaturated carboxylic acid, unsaturated ethylene alkenyl compound and polyfunctional monomer (as Trimethylol-propane trimethacrylate), phenylene BMI and combinations thereof.Suitable The object lesson of suitable slaine includes but not limited to, acrylic acid, diacrylate, methacrylic acid and two One or more slaines of methacrylic acid, wherein metal selected from magnesium, calcium, zinc, aluminum, lithium, nickel and Sodium.In specific embodiment, coagent selected from acrylic acid, diacrylate, methacrylic acid and Dimethacrylate and the zinc salt of their mixture.In another specific embodiment, activity helps Agent is dizinc acrylate resin.When coagent is dizinc acrylate resin and/or zinc dimethacrylate, this activity Auxiliary agent is typically with the most every 100 parts by weight of base rubber 1 or 5 or 10 or 15 or 19 or 20 Weight portion and the upper limit are every 100 parts by weight of base rubber 24 or 25 or 30 or 35 or 40 or 45 or 50 Or the amount that 60 in the range of weight portion is contained in rubber composition.When using one or more activity relatively When low coagent such as monomethacrylate zinc and various liquid propene hydrochlorate and methacrylate, live The consumption of the coagent that property is relatively low can be with dizinc acrylate resin and the amount of zinc dimethacrylate coagent Identical or higher.Can obtain the ball hardness of needs by adjusting cross-linking amount, cross-linking amount can be such as Realized by the type and amount changing coagent.

Rubber composition optionally comprises firming agent.Suitable firming agent includes but not limited to, sulfur, N- Oxygen diethylidene-2-[4-morpholinodithio sulfenamide, N, N-di-o-tolylguanidine, dimethyl dithiocarbamate bismuth, N-cyclohexyl-2-[4-morpholinodithio sulfenamide, N, N-diphenylguanidine, 4-morpholinyl-2-[4-morpholinodithio disulphide, Dipentamethylenethiuram hexasulfide, thiuram-disulfide, mercaptobenzothiazoler, sulfenamide, two sulfur For carbaminate, thiuramsulfides, guanidine, thiourea, xanthates, dithiophosphates, aldamine, Dibenzothiazyl disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide and they Combination.

Rubber composition optionally comprises one or more antioxidants.Antioxidant is can to suppress or anti- The only compound of rubber oxidative degradation.Some antioxidants also serve as free radical scavenger；Therefore, when anti- When oxidant is contained in rubber composition, the consumption of initiator can be high or more as amount disclosed herein High.Suitable antioxidant includes, such as, and dihydroquinoline antioxidant, amine antioxidants and phenols Antioxidant.

Rubber composition also can comprise one or more fillers to adjust density and/or the proportion of core.Example Filler include deposit aqueous silicon dioxide, clay, Talcum, asbestos, glass fibre, aramid fiber, Muscovitum, calcium metasilicate, zinc sulfate, barium sulfate, zinc sulfide, Griffith's zinc white., silicate, carborundum, silicon Diatomaceous earth, polrvinyl chloride, carbonate (such as, calcium carbonate, zinc carbonate, brium carbonate and magnesium carbonate), metal (example As, titanium, tungsten, aluminum, bismuth, nickel, molybdenum, ferrum, lead, copper, boron, cobalt, beryllium, zinc and stannum), metal Alloy (such as, steel, pyrite, bronze, boron carbide whisker and tungsten carbide whisker), metal-oxide are (such as, Zinc oxide, stannum oxide, ferrum oxide, calcium oxide, aluminium oxide, titanium dioxide, magnesium oxide and zirconium oxide), Particulate carbonaceous material (such as, graphite, white carbon black, flocking, bitumen, cellulose fluff and leather fiber), Microsphere (such as, glass and pottery), flying dust, again abrasive material (such as, pulverize and the core material that reclaims), Nano filling, and above two or more kinds of combinations.Microparticle material present in rubber composition Measure the most every 100 parts by weight of base rubber 5 weight portions or 10 weight portions and the upper limit is every Amount in the range of 100 parts by weight of base rubber 30 weight portions or 50 weight portions or 100 weight portions.Fill out Material material can be double-functional packing, such as zinc oxide (it can be as filler/plumper) and titanium dioxide (its Can be as filler/brightener material).

Rubber composition can also comprise selected from processing aid, processing oil, plasticizer, coloring agent, fluorescence Agent, chemical blowing and foaming agent, defoamer, stabilizer, softening agent, anti-impact modifier, free radical One or more additives of scavenger, accelerator, antiscorching agent etc..Add present in rubber composition The most every 100 parts by weight of base rubber 0 weight portions of amount of agent and the upper limit are every 100 weight In the range of part base rubber 20 weight portion or 50 weight portions or 100 weight portions or 150 weight portions.

Rubber composition optionally comprises softening accelerator.Preferably, rubber composition contains 0.05phr Softening accelerator to 10.00phr.In one embodiment, accelerator is softened with within the range having a lower limit of 0.05 Or 0.10 or 0.20 or 0.50phr and in the range of the upper limit is 1.00 or 2.00 or 3.00 or 5.00phr Amount exists.In another embodiment, accelerator is softened with within the range having a lower limit of 2.00 or 2.35phr and the upper limit It is that the amount in the range of 3.00 or 4.00 or 5.00phr exists.In another optional high concentration embodiment, Soften accelerator with within the range having a lower limit of 5.00 or 6.00 or 7.00phr and the upper limit be 8.00 or 9.00 or Amount in the range of 10.00phr exists.In another embodiment, the accelerator amount with 2.6phr is softened Exist.

Suitable softening accelerator includes but not limited to, organic sulfur and the organosulfur compound containing metal；Have Organic sulfur compound, including mono-, di-and polysulfide, mercaptan and sulfhydryl compound；Inorganic sulphide chemical combination Thing；Organosulfur compound and the blend of inorganic sulphide compounds；The compound of Group VIA；Not sulfur-bearing Or the replacement of metal and unsubstituted aromatic organic compound；Aromatic organometallic compound；Hydroquinone；Benzene Quinone；Green hydroquinone.；Catechol；Resorcinol；And combinations thereof.

Here, " organosulfur compound " refers to any compound containing carbon, hydrogen and sulfur, and wherein sulfur is straight Connect and be bonded at least 1 carbon.Here, term " sulphur compound " refers to such compound, and it is unit Element sulfur, polymerised sulphur (polymeric sulfur) or combinations thereof.Should be further understood that, term " unit Element sulfur " refer to S₈Circulus, and " polymerised sulphur " be comprise relative to elementary sulfur at least one add The structure of sulfur.

Be especially suitable as softening accelerator is the organosulfur compound with below general formula:

Wherein, R₁-R₅Can be C₁-C₈Alkyl；Halogen；Mercapto (-SH), Carboxylation base；Sulphur Change base；And hydrogen；With random order；And can also be phenyl-pentafluoride thiophenol；2-fluoro thiophenol；3-fluorobenzene Thiophenol；4-fluoro thiophenol；2,3-fluoro thiophenols；2,4-fluoro thiophenols；3,4-fluoro thiophenols；3,5-fluorobenzene sulfur Phenol；2,3,4-fluoro thiophenols；3,4,5-fluoro thiophenols；2,3,4,5-phenyl tetrafluoride thiophenols；2,3,5,6-phenyl tetrafluoride sulfur Phenol；4-chlorine phenyl tetrafluoride thiophenol；Reptazin；2-chlorothio-phenol；3-chlorothio-phenol；4-chlorothio-phenol； 2,3-chlorothio-phenols；2,4-chlorothio-phenols；3,4-chlorothio-phenols；3,5-chlorothio-phenols；2,3,4-chlorothio-phenols； 3,4,5-chlorothio-phenols；2,3,4,5-tetrachlorobenzene thiophenols；2,3,5,6-tetrachlorobenzene thiophenols；Phenyl-pentabromide thiophenol；2- Bromo thiophenol；3-bromo thiophenol；4-bromo thiophenol；2,3-bromo thiophenols；2,4-bromo thiophenols；3,4-bromines Phenylmercaptan.；3,5-bromo thiophenols；2,3,4-bromo thiophenols；3,4,5-bromo thiophenols；2,3,4,5-tetrabromo-benzene sulfur Phenol；2,3,5,6-tetrabromo-benzene thiophenols；Pentaiodobenzene thiophenol；2-iodobenzene thiophenol；3-iodobenzene thiophenol；4-iodobenzene sulfur Phenol；2,3-iodobenzene thiophenols；2,4-iodobenzene thiophenols；3,4-iodobenzene thiophenols；3,5-iodobenzene thiophenols；2,3,4-iodobenzenes Thiophenol；3,4,5-iodobenzene thiophenols；2,3,4,5-tetraiodo-benzene thiophenols；2,3,5,6-tetraiodo-benzene thiophenols；Their zinc Salt；Their non-metal salt, such as, the ammonium salt of reptazin；Reptazin magnesium；Pentachlorobenzene sulfur Phenol cobalt；And combinations thereof.Preferably, benzene halide thiol compounds is reptazin, and it can be from Commercial in a pure form or trade name A95 (the sulfuration containing carrier based on clay Compound, reptazin loading capacity is 45%) obtain. A95 can be from Ohio The Struktol Company of America of Stow is commercially-available.PCTP can be in a pure form from adding The eChinachem in the San Francisco in Li Funiya state is commercially-available, and in a salt form from Jia Lifuni The eChinachem in the San Francisco in sub-state is commercially-available.Most preferably, benzene halide thiol compounds is five The zinc salt of chlorothio-phenol, it can be commercially-available from the eChinachem in San Francisco of California. Suitable organosulfur compound be disclosed in further such as United States Patent (USP) 6,635,716,6,919,393, 7,005,479 and 7, in 148,279, include in incorporated herein by by their full content.

Suitable containing metal organosulfur compound including but not limited to, diethyldithiocar bamic acid, two Diamyl disulfide for carbamic acid, the cadmium of dimethyl dithiocarbamic acid, copper, lead and tellurium analog, and Combinations thereof.Other example is in United States Patent (USP) 7, disclosed in 005,479, incorporated herein by by it Full content is included in.

Suitable disulfide includes but not limited to 4,4 '-Diphenyl disulfide ether；4,4 '-xylyl disulfide； 2,2 '-benzamido Diphenyl disulfide ether；Double (2-aminophenyl) disulfide；Double (4-aminophenyl) two sulfur Ether；Double (3-aminophenyl) disulfide；2,2 '-bis-(4-amino naphthyl) disulfides；2,2 '-bis-(3-amino naphthyls) Disulfide；2,2 '-bis-(4-amino naphthyl) disulfides；2,2 '-bis-(5-amino naphthyl) disulfides；2,2 '-bis-(6- Amino naphthyl) disulfide；2,2 '-bis-(7-amino naphthyl) disulfides；2,2 '-bis-(8-amino naphthyl) disulfides； 1,1 '-bis-(2-amino naphthyl) disulfide；1,1 '-bis-(3-amino naphthyl) disulfide；1,1 '-bis-(3-amino naphthyls) Disulfide；1,1 '-bis-(4-amino naphthyl) disulfide；1,1 '-bis-(5-amino naphthyl) disulfide；1,1 '-bis-(6- Amino naphthyl) disulfide；1,1 '-bis-(7-amino naphthyl) disulfide；1,1 '-bis-(8-amino naphthyl) disulfide； 1,2 '-diaminostilbene, 2 '-dithio dinaphthyl；2,3 '-diaminostilbene, 2 '-dithio dinaphthyl；Double (4-chlorphenyl) two sulfur Ether；Double (2-chlorphenyl) disulfide；Double (3-chlorphenyl) disulfide；Double (4-bromophenyl) disulfide；Double (2- Bromophenyl) disulfide；Double (3-bromophenyl) disulfide；Double (4-fluorophenyl) disulfide；Double (4-iodophenyls) two Thioether；Double (2,5-Dichlorobenzene base) disulfide；Double (3,5-Dichlorobenzene base) disulfide；Double (2,4-Dichlorobenzene base) Disulfide；Double (2,6-Dichlorobenzene base) disulfide；Double (2,5-dibromo phenyl) disulfide；Double (3,5-dibromobenzenes Base) disulfide；Double (2-chloro-5-bromophenyl) disulfide；Double (2,4,6-trichlorophenyl) disulfide；Double (2,3,4,5,6- Five chlorophenyl) disulfide；Double (4-cyano-phenyl) disulfide；Double (2-cyano-phenyl) disulfide；Double (4-nitre Base phenyl) disulfide；Double (2-nitrobenzophenone) disulfide；2,2 '-dithiobenzoic acid ethyl ester；2,2 '-two sulfur For essence of Niobe；2,2 '-dithiobenzoic acid；4,4 '-dithiobenzoic acid ethyl ester；Double (4-acetylbenzenes Base) disulfide；Double (2-acetylphenyl) disulfide；Double (4-Fonnylphenyl) disulfide；Double (4-amino Formylphenyl) disulfide；1,1 '-dinaphthyl disulfide；2,2 '-dinaphthyl disulfide；1,2 '-dinaphthyl two sulfur Ether；2,2 '-bis-(1-chlorine dinaphthyl) disulfides；2,2 '-bis-(1-bromonaphthalene base) disulfides；1,1 '-bis-(2-chloronaphthyl, methylnaphthyl) Disulfide；2,2 '-(1-cyanonaphthyl) disulfides；2,2 '-bis-(1-acetyl group naphthyl) disulfides etc.；And it Combination.

Suitable inorganic sulphide compounds includes but not limited to, titanium sulfide, Manganese monosulfide., and ferrum, calcium, The sulfide analog of cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, stannum and bismuth.

The compound of suitable Group VIA includes but not limited to, elementary sulfur and polymerised sulphur, as can be from Russia's last of the twelve Earthly Branches The Elastochem of Russia state Chardon, commercially-available for Inc. those；Sulfur catalyst compound, including PB (RM-S)-80 elementary sulfur and PB (CRST)-65 polymerised sulphur, both of which can be from Elastochem, Inc. Obtain；Tellurium catalyst, as And selenium catalyst, as Both of which can With from RT Vanderbilt Company, Inc. is commercially-available.

Suitable not sulfur-bearing or the replacement of metal and unsubstituted aromatics organic component include but not limited to, 4,4 '- Dibenzenyl, diphenyl diimide and combinations thereof.The preferred scope of size of aromatic organic radicals is at C₆Extremely C₂₀, and more preferably C₆To C₁₀。

Suitable replacement and unsubstituted aromatic organometallic compound include but not limited to have formula (R₁)_x-R₃-M-R₄-(R₂)_yThose, wherein R₁And R₂It is respectively hydrogen or substituted or unsubstituted C_1-20Straight chain, branched or cyclic alkyl, alkoxyl or alkylthio group, or be monocycle, multi-ring, The C of condensed ring₆To C₂₄Aryl；X and y is the integer of 0 to 5 respectively；R₃And R₄It is respectively selected from list Ring, multi-ring, the C of condensed ring₆To C₂₄Aryl；M includes azo group or metal component.Excellent Selection of land, R₃And R₄It is respectively selected from C₆To C₁₀Aryl, be more preferably selected from phenyl, benzyl, naphthalene Base, phenylamino and benzothiazolyl.Preferably, R₁And R₂It is respectively selected from replacement and unsubstituted C_1-10 Straight chain, branched and cyclic alkyl, alkoxyl and alkylthio group, and C₆To C₁₀Aryl.Work as R₁、 R₂、R₃And R₄When being replaced, replace and can include one or more of following substituent group: hydroxyl And slaine；Sulfydryl and slaine thereof；Halogen；Amino, nitro, cyano group and acylamino-；Carboxyl bag Include ester, acid and slaine thereof；Silicyl；Acrylic and slaine thereof；Sulfonyl and sulfonamide； And phosphate and phosphorous acidic group.When M is metal component, it can be the metal unit of any suitable Element.Generally this metal is transition metal, and preferably tellurium or selenium.

Suitable hydroquinone includes but not limited to, compound that following formula represents and hydrate thereof.

Wherein, R₁、R₂、R₃And R₄Separately be selected from: hydrogen, halogen group (F, CI, Br, I), Alkyl, carboxyl (-COOH) and slaine (such as ,-COO thereof^-M⁺) and ester (-COOR), acetate (-CH₂And ester (-CH COOH)₂COOR), formoxyl (-CHO), acyl group (-COR), acetyl group (-COCH₃), carbonyl halide (-COX), sulfonic group (-SO₃And ester (-SO H)₃R), halosulfonyl groups (-SO₂X), sulfino (-SO₂H), alkyl sulphinyl (-SOR), carbamoyl (-CONH₂)、 Halogenated alkyl, cyano group (-CN), alkoxyl (-OR), hydroxyl (-OH) and slaine (such as ,-O thereof^-M⁺)、 Amino (-NH₂), nitro (-NO₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as benzene oxygen Base etc.), aryl alkyl [such as, cumenyl (-C (CH₃)₂Phenyl)；Benzyl (-CH₂Phenyl)], sub- Nitro (-NO), acetylamino (-NHCOCH₃), vinyl (-CH=CH₂).Particularly preferred hydroquinone bag Include the compound and hydrate thereof represented by above formula, wherein R₁, R₂, R₃And R₄Separately it is selected from: Slaine (the e.g. ,-COO of carboxyl^-M⁺), acetate (-CH₂And ester (-CH COOH)₂COOR), hydroxyl Base (-OH), slaine (the such as ,-O of hydroxyl^-M⁺), amino (-NH₂), nitro (-NO₂), aryl (example As, phenyl, tolyl etc.), aryloxy group (such as, phenoxy group etc.), aryl alkyl [such as, isopropylbenzene Base (-C (CH₃)₂Phenyl), benzyl (-CH₂Phenyl)], nitroso-group (-NO), acetylamino (-NHCOCH₃)、 Vinyl (-CH=CH₂).The example of particularly suitable hydroquinone includes 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-double amyl hydroquinone；With 2-(2-chlorphenyl) hydroquinone hydrate.Particularly preferably hydrogen Quinone and four chlorohydroquinones, be more particularly preferably 2-(2-chlorphenyl) hydroquinone hydrate.Suitable hydroquinone enters One step is disclosed in the U.S. Patent application of such as Publication No. 2007/0213440, incorporated herein by inciting somebody to action Entire contents is included in.

Suitable benzoquinone includes compound and the hydrate thereof that following molecular formula represents.

Wherein, R₁、R₂、R₃And R₄Separately be selected from: hydrogen, halogen group (F, CI, Br, I), Alkyl, carboxyl (-COOH) and slaine (such as ,-COO thereof^-M⁺) and ester (-COOR), acetate (-CH₂And ester (-CH COOH)₂COOR), formoxyl (-CHO), acyl group (-COR), acetyl group (-COCH₃), carbonyl halide (-COX), sulfonic group (-SO₃And ester (-SO H)₃R), halosulfonyl groups (-SO₂X), sulfino (-SO₂H), alkyl sulphinyl (-SOR), carbamoyl (-CONH₂)、 Halogenated alkyl, cyano group (-CN), alkoxyl (-OR), hydroxyl (-OH) and slaine (such as ,-O thereof^-M⁺)、 Amino (-NH₂), nitro (-NO₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as benzene oxygen Base etc.), aryl alkyl [such as, cumenyl (-C (CH₃)₂Phenyl)；Benzyl (-CH₂Phenyl)], sub- Nitro (-NO), acetylamino (-NHCOCH₃), vinyl (-CH=CH₂).Particularly preferred benzoquinone bag Include the compound and hydrate thereof represented by above formula, wherein R₁、R₂、R₃And R₄Separately it is selected from: Slaine (the such as ,-COO of carboxyl^-M⁺), acetate (-CH₂And ester (-CH COOH)₂COOR)、 Hydroxyl (-OH), slaine (the such as ,-O of hydroxyl^-M⁺), amino (-NH₂), nitro (-NO₂), aryl (example As, phenyl, tolyl etc.), aryloxy group (such as, phenoxy group etc.), aryl alkyl [such as, isopropylbenzene Base (-C (CH₃)₂Phenyl), benzyl (-CH₂Phenyl)], nitroso-group (-NO), acetylamino (-NHCOCH₃)、 Vinyl (-CH=CH₂).More particularly preferably methyl-p-benzoquinone and chloranil.Suitable benzoquinone enters One step is disclosed in the U.S. Patent application of such as Publication No. 2007/0213442, incorporated herein by inciting somebody to action Entire contents is included in.

Suitable green hydroquinone. includes but not limited to compound and the hydrate thereof that following molecular formula represents.

Wherein, R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Separately it is selected from: hydrogen, halogen Group (F, CI, Br, I), alkyl, carboxyl (-COOH) and slaine (such as ,-COO thereof^-M⁺) and Ester (-COOR), acetate (-CH₂And ester (-CH COOH)₂COOR), formoxyl (-CHO), acyl group (-COR), acetyl group (-COCH₃), carbonyl halide (-COX), sulfonic group (-SO₃And ester (-SO H)₃R)、 Halosulfonyl groups (-SO₂X), sulfino (-SO₂H), alkyl sulphinyl (-SOR), carbamoyl (-CONH₂), halogenated alkyl, cyano group (-CN), alkoxyl (-OR), hydroxyl (-OH) and slaine (example thereof As ,-O^-M⁺), amino (-NH₂), nitro (-NO₂), aryl (such as, phenyl, tolyl etc.), virtue oxygen Base (such as phenoxy group etc.), aromatic alkyl [such as, cumenyl (-C (CH₃)₂Phenyl)；Benzyl (-CH₂ Phenyl)], nitroso-group (-NO), acetylamino (-NHCOCH₃), vinyl (-CH=CH₂).The most excellent The green hydroquinone. of choosing includes compound and the hydrate thereof represented by above formula, wherein R₁、R₂、R₃、R₄、 R₅、R₆、R₇And R₈Separately it is selected from: slaine (the such as ,-COO of carboxyl^-M⁺), acetate (-CH₂And ester (-CH COOH)₂COOR), slaine (the such as ,-O of hydroxyl (-OH), hydroxyl^-M⁺)、 Amino (-NH₂), nitro (-NO₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as, benzene Epoxide etc.), aryl alkyl [such as, cumenyl (-C (CH₃)₂Phenyl), benzyl (-CH₂Phenyl)], Nitroso-group (-NO), acetylamino (-NHCOCH₃), vinyl (-CH=CH₂).Particularly preferred quinone hydrogen Quinone also includes the wherein R represented by above formula₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Chemical combination for hydrogen Thing.Suitable green hydroquinone. is public in the U.S. Patent application of such as Publication No. 2007/0213441 further Open, include in incorporated herein by by entire contents.

Suitable catechol includes compound and the hydrate thereof that following molecular formula represents:

Wherein, R₁、R₂、R₃And R₄Separately be selected from: hydrogen, halogen group (F, CI, Br, I), Alkyl, carboxyl (-COOH) and slaine (such as ,-COO thereof^-M⁺) and ester (-COOR), acetate (-CH₂And ester (-CH COOH)₂COOR), formoxyl (-CHO), acyl group (-COR), acetyl group (-COCH₃), carbonyl halide (-COX), sulfonic group (-SO₃And ester (-SO H)₃R), halosulfonyl groups (-SO₂X), sulfinyl group (-SO₂H), alkyl sulphinyl (-SOR), carbamoyl (-CONH₂)、 Halogenated alkyl, cyano group (-CN), alkoxyl (-OR), hydroxyl (-OH) and slaine (such as ,-O thereof^-M⁺)、 Amino (-NH₂), nitro (-NO₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as benzene oxygen Base, etc.), aromatic alkyl [such as, cumenyl (-C (CH₃)₂Phenyl)；Benzyl (-CH₂Phenyl)], Nitroso-group (-NO), acetylamino (-NHCOCH₃), vinyl (-CH=CH₂).Suitable catechol Further disclosed in the U.S. Patent application of such as Publication No. 2007/0213144, incorporated herein by Entire contents is included in.

Suitable resorcinol includes compound and the hydrate thereof that following molecular formula represents:

Wherein, R₁、R₂、R₃And R₄Separately be selected from: hydrogen, halogen group (F, CI, Br, I), Alkyl, carboxyl (-COOH) and slaine (such as ,-COO thereof^-M⁺) and ester (-COOR), acetate (-C1H₂And ester (-CH COOH)₂COOR), formoxyl (-CHO), acyl group (-COR), acetyl group (-COCH₃), carbonyl halide (-COX), sulfonic group (-SO₃And ester (-SO H)₃R), halosulfonyl groups (-SO₂X), sulfino (-SO₂H), alkyl sulphinyl (-SOR), carbamoyl (-CONH₂)、 Halogenated alkyl, cyano group (-CN), alkoxyl (-OR), hydroxyl (-OH) and slaine (such as ,-O thereof^-M⁺)、 Amino (-NH₂), nitro (-NO₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as benzene oxygen Base etc.), aromatic alkyl [such as, cumenyl (-C (CH₃)₂Phenyl)；Benzyl (-CH₂Phenyl)], sub- Nitro (-NO), acetylamino (-NHCOCH₃), vinyl (-CH=CH₂).Particularly preferably between 2-nitro Benzodiazepines.Suitable resorcinol is further in the United States Patent (USP) Shen of such as Publication No. 2007/0213144 Disclosed in please, include in incorporated herein by by entire contents.

When rubber composition includes one or more hydroquinone, benzoquinone, green hydroquinone., catechol, isophthalic two When phenol or combinations thereof, it is present in the hydroquinone in described compositions, benzoquinone, green hydroquinone., catechol And/or resorcinol total amount is typically every 100 parts of base rubber at least 0.1 weight portions or at least 0.15 Weight portion or at least 0.2 weight portion, or be 0.1 weight portion of the most every 100 parts of base rubber Or 0.15 weight portion or 0.25 weight portion or 0.3 weight portion or 0.375 weight portion and the upper limit be every 100 parts 0.5 weight portion of base rubber or 1 weight portion or 1.5 weight portions or 2 weight portions or the model of 3 weight portions Enclose interior amount.

In specific embodiment, soften accelerator selected from reptazin zinc, reptazin, two Tolyl disulfide, Diphenyl disulfide ether, dixylyl disulfide, 2-nitro-resorcinol and they Combination.

The proper types of base rubber, initiator, coagent, filler and additive and amount are more completely In such as United States Patent (USP) 6,566,483,6,695,718,6,939,907,7,041,721 and 7,138,460 Describe, include in incorporated herein by by entire contents.Particularly suitable diene rubber compsns is further Disclosed in the U.S. Patent application of such as Publication No. 2007/0093318, incorporated herein by it is complete Portion's content is included in.

Be also suitable for formation inner sandwich layer is from poly-selected from polyurethane, polyureas, carbamate ionomer, urea Thing, epoxy resin, polyamide, polyester, urethane acrylate, polyurea acrylic ester, propylene oxide Acid esters, silicone, polyimides and their blend of two or more and the thermosetting group of copolymer Compound.

Including but not limited to for forming the suitable thermoplastic polymer composition of inner sandwich layer, part is with complete The full ionomer neutralized and their blend, including the blend of the ionomer that HNP neutralizes with part (as disclosed in the U.S. Patent application in Publication No. 2006/0128904), HNP and extra heat Plasticity and thermosets (such as acid copolymer, engineered thermoplastic materials, HNP based on fatty acid/salt, The polymeric material of polybutadiene, polyurethane, polyureas, polyester, thermoplastic elastomer (TPE) and other routines) Blend, and particularly such as United States Patent (USP) 6,653,382,6,756,436,6,777,472, 6,894,098, the ionomer compositions disclosed in 6,919,393 and 6,953,820.Suitable HNP combination Thing be also included within such as United States Patent (USP) 6,653,382,6,756,436,6,777,472,6,894,098, Those disclosed in 6,919,393 and 6,953,820.Whole incorporated herein by by above-mentioned all documents Content is included in.

Be also suitable for formation intermediate core layer is the graft copolymer of ionomer and polyamide；And it is following non- The polymer of ionomer (include its homopolymer and copolymer, and they with at least one be grafted or The functional group of copolymerization is (such as maleic anhydride, amine, epoxy radicals, isocyanate group, hydroxyl, sulfonic group, phosphonate group Deng) compatible derivant): polyester, particularly with compatible group as sulfonic group or phosphonate group modified, Including modified poly-(PETP), modified poly-(butylene terephthalate), modified Poly-(p-phthalic acid 1,2-propylene diester), modified poly-(p-phthalic acid 1,3-propylene diester), modified poly-(ring Alkanoic acid second diester), and in United States Patent (USP) 6,353,050,6,274,298 and 6, disclosed in 001,930 Those, and the blend of they two or more；Polyamide, polyamide-ether and polyamide-ester, And in United States Patent (USP) 6,187,864,6,001,930 and 5, those disclosed in 981,654, and they The blend of two or more；Thermosetting and thermoplastic polyurethane, polyureas, polyurethane-polyurea Blend, and their two kinds or more kinds of blends；Fluoropolymer, such as United States Patent (USP) 5,691,066,6,747,110 and 7, disclosed in 009,002, and their two kinds or more kinds of being total to Mixed thing；Non-ionomeric acid polymer, such as E/Y-and E/X/Y-type copolymer, wherein E be alkene (such as, Ethylene), Y is carboxylic acid, such as acrylic acid, methacrylic acid, butenoic acid, maleic acid, anti-butylene Diacid or itaconic acid, X is the vinyl esters softening comonomer such as aliphatic carboxylic acid, wherein said acid tool Having 2-10 carbon, the carbon number of alkyl is the alkyl ether of 1-10, and alkyl alkylacrylate, such as alkane The carbon number of base is the alkyl methacrylate of 1-10；And their two kinds or more kinds of blends； Metallocene catalyzed polymers, as by United States Patent (USP) 6,274,669,5,919,862,5,981,654 Hes Those disclosed in 5,703,166, and their two kinds or more kinds of blends；Polystyrene, Such as poly-(styrene-co maleic anhydride), acrylonitrile-butadiene-styrene (ABS), poly-(styrene-sulphonic acid ester), Polyvinylstyrenes, and their two kinds or more kinds of blends；Polypropylene and polyethylene, special It not polypropylene and the polyethylene of grafting of the grafting modified with functional group's (such as maleic anhydride of sulfonic acid), with And their two kinds or more kinds of blends；Polrvinyl chloride and the polrvinyl chloride of grafting, and they Two kinds or more kinds of blends；Polyvinyl acetate, preferably has the second of less than about 9% weight Vinyl acetate, and their two kinds or more kinds of blends；Merlon, polycarbonate/acrylonitrile The blend of nitrile-butadiene-styrene, the blend of Merlon/polyurethane, being total to of polycarbonate/polyester Mixed thing, and their two kinds or more kinds of blends；Polyvinyl alcohol, and they two kinds or The blend that person is more kinds of；Polyethers, such as poly (arylene ether), polyphenylene ether, alkenyl arene and vinyl Aromatic hydrocarbons and the block copolymer of polyesteramide (amic ester)；With their two kinds or more kinds of being blended Thing；Polyimides, polyether-ketone, polyamidoimide, and their two kinds or more kinds of blends； Polycarbonate/polyester copolymer and blend；And two or more group any of above-mentioned polymer Close.What other were suitable is the heat disclosed in United States Patent (USP) 5,919,100,6,872,774 and 7,074,137 Plastic composition.Include in incorporated herein by by the full content of above-mentioned document.

The example of available commercial suitable thermoplastic includes but not limited to: Thermoplastic poly Ether block amides, can be commercially-available from Arkema Inc.； Ionomer resin, Hold Plasticity polyester elastomer, and with trade name HPF1000 and HPF 2000 sell from poly-material Material, they can be commercially-available from E.I.du Pont de Nemours and Company； From Polymers, can be commercially-available from ExxonMobil Chemical Company； IO ionomer Ethylene acrylic acid co polymer, can be commercially-available from The Dow Chemical Company； Ionomer resin, can be commercially-available from A.Schulman Inc.； Heat based on polyurethane Thermoplastic elastic, can be commercially-available from BASF；And Polycarbonate/polyester blend, Can be commercially-available from SABIC Innovative Plastics.Thermoplastic compounds can use thermosetting diene Compositions-treated or flowing when blending to reduce or to prevent molded (overmolding).Optional place Reason be additionally may included in molding forward direction material in add peroxide, or with such as crosslinker solution, electron beam, Gamma radiation, isocyanates or amine aqueous solution etc. carry out moulding post processing.When the outer sandwich layer of thermosetting can make When molding about 5 to 30 minutes thereon at a temperature of the crosslinking of this layer, this temperature is typically 280 °F To 360 °F, this process is possible to prevent intermediate layer fusing and flowing or stitches (equator) place in a mold " leak ".

Except above-mentioned material, inner sandwich layer can include the layer that at least one of which is formed by low shape-changing material, described Low shape-changing material is selected from metal, rigidity plastics, uses high intensity organic or inorganic filler or fibre-reinforced poly- Compound, and their blend and complex.Suitable low deformable material is additionally included in Publication No. Those disclosed in the U.S. Patent application of 2005/0250600, disclosed incorporated herein by including it in Full content.

The other materials suitably forming inner sandwich layer includes United States Patent (USP) 7, the core composition disclosed in 300,364, It is incorporated by reference herein its full content disclosed.Such as, suitable inner sandwich layer material includes with organic The HNP that fatty acid and salt, metal cation or a combination of both neutralize.Except with organic fatty The HNP that acid and salt thereof neutralize, inner sandwich layer compositions may also include at least one swelling index at least about 40 Elastomeric material.Preferably swelling index at least about 50.Produce resilience golf and be therefore applicable to The polymer of the present invention includes but not limited to can be from Corporation is commercially-available CB23, CB22, can be from BR60 commercially-available for Enichem, and can be from Goodyear Corp. Commercially-available 1207G.Additionally, the rubber such as polybutadiene in golf prepared in accordance with the present invention Typical Mooney viscosity be about 40 to about 80, the most about 45 to about 65, and most preferably About 45 to about 55.Mooney viscosity is typically measured according to ASTM-D1646.

Inner core is encapsulated by intermediate core, and intermediate core is monolayer, bilayer or multilamellar, and preferably gross thickness Within the range having a lower limit of 0.005 or 0.010 or 0.020 or 0.025 or 0.035 or 0.040 or 0.045 inch and on It is limited in the range of 0.045 or 0.050 or 0.060 or 0.070 or 0.080 or 0.090 or 0.100 inch.

The outer surface hardness of intermediate core is 40 Shore C hardness or bigger, or 70 Shore C hardness or Bigger, or 80 Shore C hardness or bigger, or 85 Shore C hardness or bigger, or 89 Xiao Family name's C hardness or bigger, or 90 Shore C hardness or bigger, or 95 Shore C hardness or bigger, Or 63 Shore D hardness or bigger, or 65 Shore D hardness or bigger, or 70 Shore D are hard Degree or bigger, or 75 Shore D hardness or bigger, or 80 Shore D hardness or bigger, or 85 Shore D hardness or bigger, or 90 Shore D hardness or bigger, or 95 Shore D hardness or Bigger, or the hardness of outer surface 40 or 45 or 50 or 80 or 85 or 89 Shore C within the range having a lower limit of are hard Degree and the upper limit are that in the range of 80 or 85 or 90 or 93 or 95 Shore C hardness, wherein the upper limit is more than Lower limit (such as, when being instantly limited to 85, the upper limit is 90,93 or 95).Intermediate core preferably has lower limit 20 or 30 35 or 40 45 or 50 55 or 57 58 or 60 63 or 65 or 66 or 70 or 75 and the upper limit be 60 65 or 66 70 or 72 75 or 80 85 or 90 or 93 or The Shore D outer surface hardness of 95, wherein the upper limit more than lower limit (such as, when being instantly limited to 65, the upper limit It is 66,70,72,75,80,85,90,93 or 95).

Intermediate core includes that at least one of which is by metal composites, composite or inorganic/organic blending The layer that compositions is formed.

Suitable metal material includes but are not limited to, aluminum, pyrite, chromium, copper, ferrum, lead, magnesium, molybdenum, Nickel, nickel-silver, niobium, silver, steel, tantalum, stannum, titanium, titanium/nickel alloy, tungsten, vanadium and zinc.Preferably steel, Titanium, chromium, nickel and their alloy, include but are not limited to, Nitinol, cu-zn-al alloy and copper aluminum Nickel alloy.Suitable metal is also in United States Patent (USP) 6,004,225 and 6, disclosed in 142,887, here by Quote and include its full content disclosed in.

Suitable composite includes matrix material and the filament material embedded in matrix material.Matrix material Can be molded into around filament material so that filament material is embedded in matrix material.This embodiment party In formula, matrix material can be thermosetting or thermoplastic polymer.Suitable thermoset copolymer material bag Include but be not limited only to, unsaturated polyester resin, vinyl ester, epoxy resin, phenolic resin, poly-ammonia Ester, polyureas, polyimide resin and polybutadiene.Suitable thermoplastic includes but not only limits In, polyethylene, polystyrene, polypropylene, thermoplastic polyester, acronitrile-butadiene-styrene (ABS), Acetal, polyamide (including semicrystalline polyamides), Merlon (PC), shape-memory polymer, poly- Vinyl chloride (PVC), polyurethane, trans polybutadiene, liquid crystalline polymers, polyether-ketone (PEEK), Biological (maleimide) and polysulfone resin.Matrix material can also be silicone material, such as silicone polymer Thing, silicone elastomer, silicone rubber, silicone resin, or low-molecular-weight silicone fluid, thermoplastic silicones Urethane copolymers and various deformation etc..Silicone polymer includes that silicone homopolymer, silicone are random Copolymer and silicone organic (block) copolymer.Silicone elastomer is defined as high molecular weight linear polymer, Usually polydimethylsiloxane.Silicone rubber include colloid that available commercial colloid, filler strengthen, Dispersion and compound that is uncatalyzed and that be catalyzed.Silicone resin contains Si atom, its do not contain or Comprise only a kind of organic substituent；Therefore the chemical combination that they cross-linking one-tenth are harder and more more rigid than elastomer Thing.The silicone fluid of low-molecular-weight includes oligomer.Silicone material is further in such as United States Patent (USP) 6,162,134 and 6, disclosed in 159,110, incorporated herein by including its full content disclosed in.Matrix Material can also be formed by ionomer, and described ionomer comprises the polymer of height neutralization or it is with upper State the blend of one or more of matrix material.The concrete formula of these materials can include additive, fill out Material, inhibitor, catalyst and accelerator, and depend on the curing system of the Performance Characteristics of needs.Base Body material can be the blend of at least one polymer or polymer.In one preferred embodiment In, matrix material is nylon, and it can be with the title of Ultramid from the Pa Xipani city of New Jersey BASF is commercially-available.

Suitable filament material includes but are not limited to, polymer material, the fiber of glass material and metal Fiber.Filament material can be made up of the tow or fiber with different physical propertys, to obtain needs Stretch and elongation characteristics.Suitable polymer filaments material includes but are not limited to, polyethers urea, asPoly-(ester-urea), polyester block copolymer is such as Poly-(propylene), polyethylene, poly- Amide, acrylic resin, polyketone, poly-(PETP) as Poly-to benzene Dioctyl phthalate terephthaldehyde's ester is such as Poly-(acrylonitrile) as Trans diaminourea bicyclo- Hexyl methane and dodecanedicarboxylic acid are such as Poly terephthalic acid dipropyl, as Harris etc. exists United States Patent (USP) 6,232, disclosed in 400, and With Permissible Commercially-available from E.I.DuPont de Nemours&Co..Can also use from Honeywell company 's Suitable filaments of glass material includes but are not limited to Corning Corporation'sSuitable filament material includes but are not limited to by marmem (" SMA ") Those made.The example of SMA material includes but are not limited to, Ag-Cd, Cu-Al-Ni, Cu-Sn, Cu-Zn, Cu-Z-X (X=Si, Sn, Al), In-Ti, Ni-Al, Ni-Ti, Fe-Pt, Mn-Cu and Fe-Mn-Si.Filament material can include the fiber that at least some SMA is formed, and can include being SMA Fiber, the fiber containing some or all non-shape memory alloy materials, or filament material can be included SMA fiber and the blend of non-SMA fiber can be included.Such as, filament material can include Ni-Ti SMA fiber and non-SMA fiber, such as carbon/epocel, with only there is the compound of non-SMA fiber Material is compared provides the hot strength strengthened.

Composite is further in such as United States Patent (USP) 6, disclosed in 899,642, incorporated herein by including in Its full content disclosed.

Be also suitably for formation intermediate core layer is in United States Patent (USP) 6, the composite disclosed in 629,898, this In by quote include in its disclose full content.

Suitable inorganic/organic blend compositions include but not limited to, and glass ionomer, resin change Property glass ionomer, fatty acid modified glass ionomer, ceramers (ormocer), inorganic organic Material, silicon ionomer, dental cement or restorative compositions, polymerizable cement, ionomer cementation Agent, burning polymer composites, ionomer cement, fluoroaluminosilicate glass, fluorine silicon aluminum acid Salt glass powder, polyalkenes acid esters (polyalkenoate) cement, flexible composite and they be total to Mixed thing.Inorganic/organic blend compositions is further in such as United States Patent (USP) 6,793,592,7,037,965 With 7, disclosed in 238,122, incorporated herein by including its full content disclosed in.

The most suitably form intermediate core layer improves gluing between each layer for comprising when being exposed to sensing heating The compositions of multiple sensors of knot.Sensor is preferably metal, more preferably magnetic material, most preferably For ferromagnetic material.Suitable sensor includes ferrum, iron containing compounds, cobalt nickel, strontium, gadolinium, SrFe₁₂O₁₉、 Co₂Ba₂Fe₁₂O₂₂、Fe₃O₄(44 microns), Fe₃O₄(840 microns), Fe₂O₃, iron-based steel (such as S45C And S55C) and pre-hardening steel (such as NAK steel).The compositions comprising sensor can comprise further Non magnetic filler, fiber, thin slice, filament, metal, pottery, graphite, glass, boron or Kevlar. Sensor can be to be the form of the polygon screen cloth of continuous print, such as triangle, square, pentagon, hexagon And tetragon.Additionally, sensor can be to be following form: discrete filler, chopped fiber, long fibre, Thin slice, spheroid, micron particle, nano-particle, nanotube or Nano capsule.In one embodiment, Sensor mixes with thermoplasticity polymer matrix or thermosetting polymer matrix.Mixture can apply sense At least one surface being applied to adjacent layer before should be heated.In another embodiment, sensor is being executed Add sensing heating so that can cast layer solidification before join can cast layer, such as polyureas, polyurethane or classification Resin (staged resin) thin film or material.Additionally, sensor can sensing heating before join with Can the adjacent layer of cast layer, solidify the layer that can cast in an indirect manner.In another embodiment, Intermediate core includes that at least one of which comprises the thermoplastic layer of thermal response material and sensor.Thermal response material is in sense React with himself when should heat, or react with thermoplastic layer.Or, comprise the aqueous vapor resistance of sensor Barrier (being further illustrated below) is formed between shell and core, and is heating and curing by sensing.Sensor The part that circumference increases the weight of the densified thin layer (being further illustrated below) of golf can also be formed.Bag Compositions containing multiple sensors is further in such as United States Patent (USP) 7, disclosed in 377,863, here by Quote and include its full content disclosed in.

Or, intermediate core includes the layer that at least one of which is formed by pottery.Suitable pottery includes but not only limits In, silicon dioxide, soda-lime, lead silicate, borosilicate, boroalumino silicate, aluminosilicate and each Plant glass ceramics.The ceramic matrix composite being also suitable for comprises, such as, with silicon carbide fibre or whisker The various potteries (such as, aluminium oxide) strengthened.Suitable also having wherein is dispersed with multidirectional continuous ceramic fiber Ceramic composite.Suitable ceramic material is further in such as United States Patent (USP) 6, disclosed in 142,887, Incorporated herein by including its full content disclosed in.

Except formed by metal composites, composite or inorganic/organic blend compositions Layer, intermediate core can include by selected from the thermosetting of those or heat for forming inner sandwich layer disclosed above The layer that plastic composition is formed.

In certain embodiments, intermediate core comprises by metal composites, composite or nothing The first intermediate core layer that machine/organic blend compositions is formed, and be arranged on around the first intermediate core layer attached Adding intermediate core layer, the most additional intermediate core layer is by selected from the thermosetting composition in addition to those of diene rubber The compositions of thing is formed.In particular aspects preferably, non-diene thermoset composition is selected from poly- Urethane, polyureas, carbamate ionomer, urea ionomer, epoxy resin, polyamide, polyester, poly- Urethane acrylate, polyurea acrylic ester, epoxy acrylate, silicone, polyimides and they The blend of two or more and copolymer.Particularly preferably heat-curable urethane, polyureas and they The blend of two or more and copolymer.That non-diene thermoset composition preferably can be cast or Can reaction injection molding(RIM).When the outer sandwich layer of thermosetting molds about at a temperature of this layer of crosslinking thereon can make When 5 to 30 minutes, this temperature is typically 280 °F to 360 °F, these compositionss can prevent fusing and Flowing or in a mold seam (equator) place " leak ".

Intermediate core is encapsulated with outer core, and outer core is monolayer, bilayer or multilamellar, and preferably gross thickness exists Lower limit is 0.005 or 0.010 or 0.020 or 0.025 or 0.030 or 0.035 inch and the upper limit is 0.035 Or 0.040 or 0.045 or 0.060 or 0.070 or 0.075 or 0.080 or 0.100 or 0.150 inch In the range of.In specific embodiment, the gross thickness of outer core be 0.035 inch or 0.040 inch or 0.045 inch or 0.050 inch or 0.055 inch or 0.060 inch or 0.065 inch.

The outer surface hardness of outer core is 25 Shore C hardness or bigger, or 45 Shore C hardness or more Greatly, or 50 Shore C hardness or bigger, or 70 Shore C hardness or bigger, or 75 Shores C hardness or bigger, or 80 Shore C hardness or bigger, or the hardness number of outer surface is within the range having a lower limit of 20 or 25 or 30 or 35 or 40 or 45 or 50 or 55 or 60 or 70 or 80 or 82 or 85 Shores C hardness and the upper limit are the model of 60 or 70 or 75 or 80 or 90 or 92 or 93 or 95 Shore C hardness In enclosing, wherein the upper limit more than lower limit (such as, when being instantly limited to 70, the upper limit is 75,80,90,92, 93 or 95).Outer sandwich layer preferably has within the range having a lower limit of 40 or 45 or 50 or 53 or 55 or 57 or 58 And the upper limit is the Shore D outer surface hardness in the range of 60 or 62 or 64 or 65 or 66 or 70.? In specific embodiment, the outer surface hardness of outer core is more than the outer surface hardness of inner core.Specific at another Embodiment in, outer core is single layer, its case hardness within the range having a lower limit of 20 or 25 or 30 or 35 Or 40 or 50 Shore C hardness and the upper limit be in the range of 60 or 70 or 80 Shore C hardness, and By selected from United States Patent (USP) 7,537,530 and 7, the rubber composition of those disclosed in 537,529 is formed, this In include in by quoting the full content disclosed.

Each outer sandwich layer is by selected from the thermosetting of those for forming inner sandwich layer disclosed above or thermoplastic Property polymer compositions formed.In certain embodiments, outer core is made up of single layer, this layer by The preferred diene rubber of thermoset composition is formed.In another particular implementation, outer core is by thermoplasticity group The simple layer composition that compound is formed.In another particular implementation, outer core is by the first outer sandwich layer and second Outer sandwich layer forms, and their each layer is formed by identical or different thermoset composition.In this enforcement In the particular aspects of mode, the first outer sandwich layer and the second outer sandwich layer are by identical or different diene rubber combination Thing is formed.In another particular aspects preferably, the first outer sandwich layer by selected from disclosed above for The non-diene thermoset composition of those forming intermediate core layer is formed, and the second outer sandwich layer is by diene rubber group Compound is formed.In another particular implementation, outer core is made up of the first outer sandwich layer and the second outer sandwich layer, Their each layer is formed by identical or different thermoplastic polymer composition.At another particular implementation In mode, outer core is made up of the first outer sandwich layer and the second outer sandwich layer, wherein the first outer sandwich layer and the second outer core One of layer is formed by thermoset composition, and the first other outer sandwich layer or the second outer sandwich layer are by thermoplasticity Polymer composition is formed.In another particular implementation, outer core is by the first outer sandwich layer, the second outer core Layer and the 3rd outer sandwich layer composition, the outer core compound of each of which and other outer core compound phase Same or different.

Each outer sandwich layer can be the compositions identical or different from for forming the compositions of inner sandwich layer. Inner sandwich layer or outer sandwich layer can farther include the sclerosing agent of 1 to 100phr.Preferably, if there is firmly Agent, sclerosing agent is present in outer core compound.Suitable sclerosing agent includes but not limited to, ionomer, Acid copolymer and terpolymer, polyamide and polyester.Sclerosing agent is further in such as United States Patent (USP) 6,120,390 and 6, disclosed in 284,840, include in incorporated herein by the full content disclosed.Also Can add trans-polyisoprene (such as, TP-301 trans-polyisoprene, can be from Kuraray Co., Ltd. is commercially-available) or trans butadiene rubber to increase the rigidity of sandwich layer and/or to improve cold forming Character, this can improve can process by being easier to the outer sandwich layer half-shell of molding in golf ball manufacturing process Property.When being contained in core compound, sclerosing agent preferably exists with the amount of 5 to 10pph.

The proportion of each sandwich layer within the range having a lower limit of 0.50 or 0.90 or 0.95 or 0.99 or 1.00 or 1.05 Or 1.10g/cc and the upper limit are 1.18 or 1.25 or 1.30 or 1.40 or the scope of 1.50 or 5.00g/cc In, or rate of specific gravity is 1.25g/cc or lower, or 1.20g/cc or lower, or 1.18g/cc or lower, Or 1.15g/cc or lower.In one embodiment, intermediate core and outer core are monolayer, and outer sandwich layer Proportion identical, substantially the same with the proportion of intermediate core layer or more than the proportion of intermediate core layer.At this In the particular aspects of embodiment, the proportion of outer sandwich layer is more than the proportion of inner sandwich layer, and outer sandwich layer is by causing Close coating compositions is formed.Densified thin layer compositions includes disclosed in such as by United States Patent (USP) 6,494,795 Those, include in incorporated herein by the full content disclosed.It is suitable for use as densified thin layer group equally Also having by United States Patent (USP) 6,149,535 and 6, the thermoplastic disclosed in 152,834 of compound, leads to here Cross and quote the full content disclosed and include in.In specific embodiment, outer core is the densification of monolayer Thin layer, preferably its proportion are 1.2 or bigger, or 1.5 or bigger, or 1.8 or bigger, or two or more, And its thickness 0.001 or 0.005 or 0.010 or 0.020 inch and the upper limit within the range having a lower limit of be 0.020 or In the range of 0.030 or 0.035 or 0.045 or 0.050 or 0.060 inch.This densified thin layer is preferably made Coat for liquid solution, dispersion, paint, unguentum, gel, fused mass etc., if any load or filling Natural or non-natural rubber latex, polyurethane, polyureas, epoxy resin, polyester, any reactivity or Non-reacted coating or cast material；Then solidify, be dried or be evaporated to equilibrium solid level.Fine and close Thin layer can also by compression or injection, RIM, cast, spray, impregnate, powder coating or at inner core Any means of upper deposition material are formed.Densified thin layer can also be for being loaded with increasing the filler of proportion, fibre Dimension, thin slice or the thermoplastic polymer of granule so that it can be coated with as shallow layer, and satisfied before State preferred specific gravity balance.One particular instance of densified thin layer, it is used with tungsten powder by soft polybutadiene Compression moulding prepares, and its thickness is 0.021 inch to 0.025 inch, and proportion is 1.31, and Shore C Hardness is about 72.For reactive fluid system, suitable material includes that any reaction forms the material of solid Material, such as epoxy resin, styrenated polyester, polyurethane or polyureas, liquid polybutadiene, silicone, silicon Hydrochlorate gel, agar gel etc..Casting, RIM, impregnate and spraying is that preferably coating is reactive fine and close The method of thin layer.Non-reactive material includes the polymer of melted or flowable form, is dissolved or dispersed in The combination in any of the powder in solvent flashing.Densified thin layer is more completely in Publication No. 2005/0059510 U.S. Patent application disclosed in, include in incorporated herein by the full content disclosed.

The distribution of weight of the core disclosed here can be changed to realize some desired parameter, as rotated speed Rate, ball hardness and initial velocity.

The golf ball core of the present invention is at the coefficient of resilience (" COR ") typically 0.750 or more of 125ft/s Greatly, or 0.775 or bigger, or 0.780 or bigger, or 0.782 or bigger, or 0.785 or bigger, Or 0.787 or bigger, or 0.790 or bigger, or 0.795 or bigger, or 0.798 or bigger, or 0.800 Or bigger, or 0.810 or bigger, or 0.820 or bigger, or 0.830 or bigger, or 0.840 or more Greatly, or 0.850 or bigger.

The ball hardness of total core of golf ball core of the present invention the most within the range having a lower limit of 40 or 60 or 70 or 80 85 or 90 and the upper limit be in the range of 100 or 105 or 110 or 115.

Multilayer core disclosed herein includes inner core, intermediate core and outer core, wherein inner core, intermediate core and outer core Each may each be monolayer, double-deck or multilamellar.As such, it is contemplated that multiple cored structure, bag Include but be not limited only to following specific structure, each of which kind be expressed as inner sandwich layer/.../outermost core Layer (" ... " be intermediate layer between inner sandwich layer and outermost sandwich layer):

TS/M/TS,

TS/TP/M/TS,

TS/TP/M/TP/TS,

TS/M/TP/TS,

TP/M/TP/TS,

TP/M/TP,

TP/TS/M/TP,

TP/M/TS/TP, and

TP/TS/M/TS/TP,

Wherein, TS=thermoset composition；M=metal composites, composite or inorganic/ Organic blend compositions；With TP=thermoplastic compounds；And comprise more than one TS layer and/or In the embodiment of more than one TP layer, TS (or TP) compositions of a layer can be identical with other layer Or different TS (or TP) compositionss.

Multilayer core is encapsulated by shell, and shell can be the shell of monolayer, bilayer or multilamellar, and preferably gross thickness is at lower limit It is 0.010 or 0.015 or 0.020 or 0.025 or 0.030 or 0.040 or 0.045 inch and the upper limit is 0.030 or 0.040 or 0.045 or 0.050 or 0.055 or 0.060 or 0.070 or 0.075 or 0.080 Or 0.090 or 0.100 or 0.120 or 0.140 or 0.150 or 0.200 or 0.300 or 0.500 inch In the range of, wherein the upper limit more than lower limit (such as, when being instantly limited to 0.040, the upper limit is 0.045,0.050, 0.055、0.060、0.070、0.075、0.080、0.090、0.100、0.120、0.140、0.150、 0.200,0.300 or 0.500).

In specific embodiment, shell is single layer and its thickness within the range having a lower limit of 0.010 or 0.015 0.020 or 0.025 or 0.027 or 0.029 or 0.030 inch and the upper limit be 0.030 or 0.033 or In the range of 0.034 or 0.035 or 0.040 or 0.050 inch, and outer surface hardness within the range having a lower limit of 20 Or 30 or 35 or 40 or 45 or 50 or 52 or 55 or 58 Shore D hardness and the upper limit be 55 or 58 Or 60 or 65 or 70 in the range of Shore D hardness, wherein the upper limit (such as, is limited to instantly more than lower limit During 58 Shore D hardness, the upper limit is 60 or 65 or 70 Shore D hardness).

Shell is preferably simple layer, and it is formed by the compositions with certain material hardness, described hardness under Be limited to 30 or 35 or 40 or 45 or 50 or 52 or 55 or 58 Shore D hardness and the upper limit be 55 or In the range of 58 or 60 or 65 Shore D hardness, wherein the upper limit (such as, is limited to 58 instantly more than lower limit During Shore D hardness, the upper limit is 60 or 65 Shore D hardness).Shell compositions preferably has according to ASTM ID6272-98 code B measure within the range having a lower limit of 5,000 or 12,000psi and the upper limit be 24,000 or Flexural modulus in the range of 50,000psi.

In another specific embodiment, shell is double-deck or multilayered shell, and it includes being combined by ionomer The hypostracum of thing formation or subshell, and the shell formed by compositions based on polyurethane or polyureas Layer.The case hardness of ionomer layer is preferably 70 Shore D hardness or lower, or 65 Shore D hardness Or lower, or less than 65 Shore D hardness, or the Shore D hardness of 50 to 65, or 57 to 60 Shore D hardness, or 58 Shore D hardness, its thickness within the range having a lower limit of 0.010 or 0.020 or 0.030 Inch and the upper limit are in the range of 0.045 or 0.080 or 0.120 inch.Outer shell is preferably by casting Or can the polyurethane of reaction injection molding(RIM), polyureas or the copolymer of polyurethane/polyurea or blend be formed.Described Shell material is the most heat cured but it also may for thermoplastic.In the particular aspects of present embodiment, The material hardness of outer shell compositions is 85 Shore C hardness or lower, or 45 Shore D hardness or more Low, or 40 Shore D hardness or lower, or 25 Shore D hardness are to 40 Shore D hardness, or 30 Shore D hardness is to 40 Shore D hardness.In another particular aspects preferably, outer shell Case hardness 20 or 30 or 35 or 40 Shore D hardness and the upper limit within the range having a lower limit of are 52 or 58 or 60 Or 65 or 70 or 72 or 75 in the range of Shore D hardness.Another particular aspects preferably In, the thickness of outer shell 0.010 or 0.015 or 0.025 inch and the upper limit within the range having a lower limit of be 0.035 or In the range of 0.040 or 0.045 or 0.050 or 0.055 or 0.075 or 0.080 or 0.115 inch.

Suitable shell material includes but not limited to, the blend of polyurethane, polyureas and polyurethane/polyurea； Ionomer resin and their blend are (such as, Ionomer resin and HPF 1000 With HPF 2000, can be commercially-available from E.I.du Pont de Nemours and Company； Ionomer, can be commercially-available from ExxonMobil Chemical Company； IO is from poly- Thing ethylene acrylic acid co polymer, can be commercially-available from The Dow Chemical Company；AndIonomer resin, can be commercially-available from A.Schulman Inc.)；Polyethylene, including such as Low Density Polyethylene, linear low density polyethylene and high density polyethylene (HDPE)；Polypropylene；Rubber toughened alkene Hydrocarbon polymer；Acid copolymer, such as (methyl) acrylic acid, it does not become a part for ionomeric copolymers； Plastic body；Flexomer；Styrene/butadiene/styrene block copolymers；Styrene/ethylene-butylene / styrene block copolymer；Dynamic vulcanization elastomer；Ethylene vinyl acetate；Ethylene methyl acrylate； Corvic；Polyamide；Amide-ester elastomer, and ionomer and the graft copolymerization of polyamide Thing, including, such as, Thermoplastic polyether block's amide, can be commercially-available from Arkema Inc； The trans-polyisoprene of crosslinking and their blend；Thermoplastic elastomer (TPE) based on polyester, asCan be commercially-available from E.I.du Pont de Nemours and Company；Based on polyurethane Thermoplastic elastomer (TPE), as Can be commercially-available from BASF；Synthesis or natural Vulcanite；And combinations thereof.

Polyurethane, polyureas and polyurethane-polyurea blend (i.e. polyurethane and the blend of polyureas and copolymer) It is particularly suitable to form the shell of the present invention.When as Shell Materials, polyurethane and polyureas can be thermosetting Property or thermoplastic.Thermosets can form golf by conventional casting or reaction injection molding(RIM) technology Layers of balls.Thermoplastic can form golf ball layer by conventional compression molding or injection molding technology.

The polyurethane shell compositions of the present invention includes by least one polyisocyanates and at least one solidification Those of the product formation of agent.Firming agent can include such as, one or more diamidogen, Yi Zhonghuo Multiple polyhydric alcohol or combinations thereof.At least one polyisocyanates can be with one or more polyhydric alcohol In conjunction with forming prepolymer, then this prepolymer is combined with at least one firming agent.Thus, when described herein During polyhydric alcohol, they are suitably used in one or both components of polyurethane material, i.e. as prepolymer A part, and in firming agent.Firming agent includes polyol curatives, and it is preferably selected from: ethylene glycol； Diglycol；Polyethylene Glycol；Propylene glycol；Polypropylene glycol；The polytetramethylene ether two of low-molecular-weight Alcohol；1,3-double (2-hydroxyl-oxethyl) benzene；1,3-double [2-(2-hydroxyl-oxethyl) ethyoxyl] benzene；1,3-double { 2-[2-(2- Hydroxyl-oxethyl) ethyoxyl] ethyoxyl } benzene；BDO；1,5-PD；1,6-hexanediol；Isophthalic Diphenol-two (beta-hydroxy ethyoxyl) ether；Hydroquinone-two (beta-hydroxy ethyl) ether；Trimethylolpropane；And they Combination.

The polyurethane shell compositions that the present invention is suitable also include by least one isocyanates and at least one Those of the product formation of firming agent, or by least one isocyanates, at least one polyhydric alcohol Those formed with the product of at least one firming agent.Preferably isocyanates includes selected from following Those: 4,4 '-methyl diphenylene diisocyanate, poly-4,4 '-methyl diphenylene diisocyanate, carbon two are sub- The liquid 4 that amine is modified, 4 '-methyl diphenylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanate, To phenylene vulcabond, toluene di-isocyanate(TDI), isophorone diisocyanate, to methyl dimethoxy Phenylene diisocyanate, a methylxylene diisocyanate, adjacent methylxylene diisocyanate and they Combination.Preferably polyhydric alcohol includes selected from following those: polyether polyol, hydroxy-end capped poly-fourth Diene, PEPA, polycaprolactone polyol, polycarbonate polyol and combinations thereof. Preferably firming agent includes polyamine curing agent, polyol curatives and combinations thereof.The most Unit's amine hardener.Preferably polyamine curing agent includes, such as, 3,5-dimethyl sulphur-based-2,4-toluenediamine Or its isomer；3,5-diethyltoluene-2,4-diamidogen or its isomer；4,4 '-bis-(Zhong Ding amino)-diphenyl Methane；Isosorbide-5-Nitrae-bis-(Zhong Ding amino) benzene, 4,4 '-methylene-bis-(2-chloroaniline)；4,4 '-methylene-bis-(3-chloro-2,6- Diethylaniline)；Two para-amino benzoic acid 1,3-PD esters；Polytetramethylene ether-two p-aminophenyl first Acid esters；N, N '-dialkyl group MDA；P, p '-methylene dianiline (MDA)；Phenylenediamine；4,4 '-methylene Base-bis-(2-chloroaniline)；4,4 '-methylene-bis-(2,6-diethylaniline)；4,4 '-diaminourea-3,3 '-diethyl -5,5 '-dimethyl diphenyl methane；2,2 ', 3,3 '-tetrachloro MDA；4,4 '-methylene-bis-(3-chloro-2,6- Diethylaniline)；And combinations thereof.

The present invention is not limited to use specific polyisocyanates in shell compositions.Suitable polyisocyanic acid Ester includes but not limited to, 4, and 4 '-methyl diphenylene diisocyanate (" MDI "), polymeric MDI, carbon two are sub- The modified liquid MDI of amine, 4,4 '-dicyclohexyl methyl hydride diisocyanate (" H₁₂MDI "), to phenylene two Isocyanates (" PPDI "), toluene di-isocyanate(TDI) (" TDI "), 3,3 '-dimethyl-4,4 '-diphenylene two is different Cyanate (" TODI "), isophorone diisocyanate (" IPDI "), cyclohexane diisocyanate (" HDI "), Naphthalene diisocyanate (" NDI ")；XDI (" XDI ")；To tetramethyl xylene two isocyanide Acid esters (p-TMXDI ")；Between tetramethylxylene diisocyanate (" m-TMXDI ")；Ethylene isocyanide Acid esters；Propylidene-1,2-diisocyanate；Tetramethylene-Isosorbide-5-Nitrae-diisocyanate；Cyclohexyl two Carbimide. Ester；1,6-hexamethylene diisocyanate (" HDI ")；Dodecane-1,12-diisocyanate；Tetramethylene .-1,3- Diisocyanate；Hexamethylene-1,3-diisocyanate；Hexamethylene-Isosorbide-5-Nitrae-diisocyanate；1-isocyanate group -3,3,5-trimethyl-5-isocyanatometyl cyclohexylamine；Methyl cyclohexane support diisocyanate；The three of HDI are different Cyanate；2,4,4-trimethyl-1, the triisocyanate of 6-hexane diisocyanate (" TMDI "), aphthacene two Isocyanates, naphthalene diisocyanate, anthracene diisocyanate；And combinations thereof.Those skilled in the art Knowing polyisocyanates and have more than one NCO, such as, two, three and four are different Cyanic acid ester group.Preferably, polyisocyanates is selected from MDI, PPDI, TDI and combinations thereof.More Preferably, polyisocyanates includes MDI.Should be appreciated that as used herein, term " MDI " includes 4,4 '-methyl diphenylene diisocyanate, polymeric MDI, the liquid MDI of carbodiimide modified and they Combination, additionally, use diisocyanate can be " low free monomer ", one of ordinary skill in the art It is understood that it has " dissociating " monomeric diisocyanate of reduced levels compared to conventional diisocyanate The compositions of base, the i.e. present invention typically has the free monomer group of less than about 0.1%." low free list Body " the example of diisocyanate include but not limited to low free monomer MDI, low free monomer TDI and Low free monomer PPDI.

At least one polyisocyanates should have the unreacted NCO group less than 14%.Preferably, At least one polyisocyanates has a NCO less than 8.5%, and more preferably 2.5% to 8.0%, very To more preferably 4.0% to 7.2%, and most preferably 5.0% to 6.5%.

The invention is not restricted to use specific polyhydric alcohol in shell compositions.In one embodiment, many The molecular weight of unit's alcohol is about 200 to about 6000.Exemplary polyhydric alcohol includes but not limited to, polyether polyols Alcohol, hydroxy-end capped polybutadiene (including the derivant partially completely hydrogenated), PEPA, poly-oneself Lactone polyols and polycarbonate polyol.Particularly preferably polytetramethylene ether diol (" PTMEG "), poly- Ethylene glycol propylene glycol, polyoxypropylene diols and combinations thereof.Hydrocarbon chain can have saturated or unsaturated bond, With replace or unsubstituting aromatic yl and cyclic group.Preferably, the polyhydric alcohol of the present invention includes PTMEG.Suitable Suitable PEPA includes but not limited to, 10PE27, poly adipate succinic acid ester, poly- Adipate glycol propylene glycol ester, phthalic acid-1,6-hexanediol ester and combinations thereof.Hydrocarbon chain can To have saturated or unsaturated bond, or substituted or unsubstituted aryl and cyclic group.Suitable poly-caproic acid Lactone polyols includes but not limited to, it is poly-that the polycaprolactone of 1,6-hexanediol initiation, diethylene glycol cause Caproic acid lactone, trimethylolpropane cause polycaprolactone, neopentyl glycol cause polycaprolactone, The polycaprolactone of BDO initiation and combinations thereof.Hydrocarbon chain can have saturated or unsaturated bond, Or replace or unsubstituting aromatic yl and cyclic group.Suitable Merlon includes but not limited to, poly-O-phthalic Acid carbonic ester.Hydrocarbon chain can have a saturated or unsaturated bond, or replaces or unsubstituting aromatic yl and cyclic group.

Polyamine fixative is also suitable for being used in the firming agent of urethane composition, and has discovered that energy Enough promote cutting resistance, shear resistant and the impact resistance of gained ball.Preferably polyamine fixative includes But it is not limited to, 3,5-dimethyl sulphur-based-2,4-toluenediamine and isomer thereof；3,5-diethyltoluene-2,4-diamidogen And isomer, such as 3,5-diethyltoluene-2,6-diamidogen；4,4 '-bis-(Zhong Ding amino)-diphenyl methanes；Isosorbide-5-Nitrae- Double (Zhong Ding amino) benzene, 4,4 '-methylene-bis-(2-chloroaniline)；4,4 '-methylene-bis-(3-chloro-2,6-diethylbenzene Amine)；Polytetramethylene ether-two p-aminobenzoate；N, N '-dialkyl group MDA；P, p '- Methylene dianiline (MDA) (" MDA ")；M-diaminobenzene. (" MPDA ")；4,4 '-methylene-bis-(2-chlorobenzene Amine) (" MOCA ")；4,4 '-methylene-bis-(2,6-diethylaniline)；4,4 '-diaminourea-3,3 '-diethyl-5,5 '- Dimethyl diphenylmethane；2,2 ', 3,3 '-tetrachloro diaminodiphenyl-methane；4,4 '-methylene-bis-(3-chloro-2,6- Diethylaniline)；Two para-amino benzoic acid 1,3-PD esters；And combinations thereof.Preferably, this Bright firming agent includes 3, and 5-dimethyl sulphur-based-2,4-toluenediamine and isomer thereof, such as ETHACURE 300.Suitable polyamine fixative includes primary amine and secondary amine, and it preferably has scope about 64 to about The weight average molecular weight of 2000.

In glycol, triol, tetrol or hydroxy-end capped fixative at least one can join polyurethane In compositions.Suitable glycol, triol and four alcohol groups include ethylene glycol；Diethylene glycol；Polyethylene Glycol； Propylene glycol；Polypropylene glycol；Low-molecular-weight polytetramethylene ether diol；1,3-double (2-hydroxyl-oxethyl) benzene； 1,3-double [2-(2-hydroxyl-oxethyl) ethyoxyl] benzene；1,3-double { 2-[2-(2-hydroxyl-oxethyl) ethyoxyl] ethyoxyl } Benzene；BDO；1,5-PD；1,6-hexanediol；Resorcinol-two (4-hydroxyethyl) ether；Hydrogen Quinone-two (4-hydroxyethyl) ether；And combinations thereof.The most hydroxy-end capped fixative includes ethylene glycol； Diethylene glycol；BDO；1,5-PD；1,6-hexanediol, trimethylolpropane and their group Close.Preferably, the molecular weight ranges of hydroxy-end capped fixative is about 48 to 2000.Should be appreciated that Molecular weight described here is absolute weight average molecular, and those of ordinary skill in the art are also so to manage Solve.

Hydroxy-end capped and amine fixative can include one or more saturated, undersaturated, aromatics With ring-type group.Additionally, hydroxy-end capped can include one or more halogen group with amine fixative. Urethane composition can be formed by the blend of firming agent or mixture.However, if it is desired to, poly-ammonia Ester compositions can be formed by single firming agent.

Any method that those of ordinary skill in the art know may be used to make the polyisocyanic acid of the present invention Ester, polyhydric alcohol and firming agent combine.A kind of common method, referred in the art as one step process, including Mix polyisocyanates, polyhydric alcohol and firming agent simultaneously.The method obtains the mixed of heterogeneous body (more random) Compound, and make maker relatively low to the control of the molecular structure of resulting composition.Preferably mixed method quilt It is referred to as prepolymer process.In the method, adding before firming agent, individually mixing polyisocyanates and Polyhydric alcohol.This method provide the mixture of relatively homogenizing, obtain more consistent polymer composition.

Suitable polyurethane further such as United States Patent (USP) 5,334,673,6,506,851,6,756,436, 6,867,279,6,960,630 and 7, disclosed in 105,623, whole interior incorporated herein by disclosed Accommodate into.Suitable polyureas is further in such as United States Patent (USP) 5,484,870 and 6,835,794 and application Number be 60/401,047 U.S. Patent application disclosed in, incorporated herein by the full content disclosed Include in.Suitable polyurethane-polyurea shell material includes polyurethane/polyurea blend and includes carbamate With the copolymer of urea segment, as disclosed in the U.S. Patent application of Publication No. 2007/0117923, Include in incorporated herein by the full content disclosed.

The compositions of the blend comprising ionomer or two or more ionomers is also particularly suited for being formed Shell.Preferably ionomer shell compositions includes:

A () comprises " high acid levels ionomer (high acid ionomer) " (i.e. has the acid more than 16wt% to contain Amount), as Compositions；

B (such as, () comprise the polymer of the non-ionomeric of high acid levels ionomer and maleic anhydride graftingFunctionalized polymeric) compositions.Particularly preferred high acid levels ionomer and maleic anhydride The Surlyn that blend is 84wt%/16wt% of the polymer of grafting With Be blended Thing.The blend of the polymer that high acid levels ionomer is grafted with maleic anhydride is special in the such as U.S. further Profit 6,992,135 and 6, disclosed in 677,401, includes in incorporated herein by the full content disclosed；

C () comprises 50/45/5 The combination of blend Thing, it preferably has the material hardness of 80 to 85 Shore C hardness；

D () comprises 50/25/25 The group of blend Compound, it preferably has the material hardness of about 90 Shore C hardness；

E () comprises 50/50 The compositions of blend, it preferably has There is the material hardness of about 86 Shore C hardness；

F () comprises The compositions of blend, it includes melt alternatively Flow ability modifying agent；

G () comprises the compositions of the blend of the first high acid levels ionomer and the second high acid levels ionomer, Wherein the first high acid levels ionomer neutralizes (such as by the cation different from the second high acid levels ionomer 50/50 With Blend), include one or more melts alternatively Flow ability modifying agent such as ionomer, Ethylene-acid copolymers or the terpolymer with ester；And

(h) comprise the first high acid levels ionomer and the blend of the second high acid levels ionomer and The compositions of the ethylene acid of 0-10wt%/ester ionomer, wherein the first high acid levels ionomer is with high with second The different cation of acid content ionomer neutralizes, ethylene acid/ester ionomer with the first high acid levels from poly- Thing or the identical cation of the second high acid levels ionomer neutralize or with the first and second high acid levels The different cation of ionomer neutralizes (such as 40-50wt%'s 40-50wt%'sWith 0-10wt%'s Blend).

With It is different grades of E/MAA copolymer, Wherein acid groups sodium ion part neutralizes. WithBeing different grades of E/MAA copolymer, wherein acid groups zinc ion part neutralizes.Being E/MAA copolymer, wherein acid groups lithium ion part neutralizes. It is the magnesium ionomer of very low modulus, there is medium acid content. It it is E/MAA copolymer Resin, it is nominally and prepares with the methacrylic acid of 15wt%. Ionomer, Poly- Compound and Copolymer all can obtain from E.I.du Pont de Nemours and Company business ?.

Ionomer shell compositions can be with nonionic thermoplastic resin, and specifically, this is to control The character of product processed.The example of suitable non-ionic thermal plastic resin includes but not limited to, polyurethane, poly- Ether-ether, polyamide ether, polyethers urea, thermoplastic polyether block's amide are (such as Block copolymer, Can be commercially-available from Arkema Inc.), styrene butadiene styrene block copolymer (SBS), styrene (second Alkene-butylene)-styrene block copolymer, polyamide, polyester, polyolefin (such as, polyethylene, poly-third Alkene, ethylene-propylene copolymer, polyethylene-(methyl) acrylate, polyethylene-(methyl) acrylic acid, tool There is the functionalized polymeric that maleic anhydride is grafted, Functionalized polymeric, can be from E.I.du Pont de Nemours and Company is commercially-available, the polymer of epoxy functional, elastomer (example Such as, ethylene propylene diene monomer rubber, the polyolefin of metallocene catalyst) and the grinding of thermo-setting elastomer Pulverizing end.

Ionomer golf spherical shell compositions can include flow ability modifying agent, e.g., but is not limited to, Acid copolymer resin, especially Acid copolymer resin can be from E.I.du Pont De Nemours and Company is commercially-available.

Suitable ionomer shell material further such as United States Patent (USP) 6,653,382,6,756,436, 6,894,098,6,919,393 and 6, disclosed in 953,820, whole interior incorporated herein by disclosed Accommodate into.

Shell compositions can include one or more of fillers, such as the above-mentioned rubber for the present invention be given The filler (such as, titanium dioxide, barium sulfate etc.) of glue composition, and/or additive, such as coloring agent, glimmering Photo etching, brightening agent, antioxidant, dispersant, UV absorbent, light stabilizer, plasticizer, surface Activating agent, compatilizer, foaming agent, reinforcing agent, releasing agent etc..

In specific embodiment, shell is the simple layer formed by full aliphatic polyurea.Specific at another Embodiment in, shell is by the U.S. Patent application being preferably chosen from Publication No. 2009/0011868 The simple layer that disclosed polyurea composition is formed, receives incorporated herein by the full content disclosed Enter.

Suitable shell material and structure also include, but not limited to the U.S. in Publication No. 2005/0164810 State's patent application, United States Patent (USP) 5,919,100,6,117,025,6,767,940 and 6,960,630 and disclosure Number it is those disclosed in the PCT application of WO00/23519 and WO00/29129, incorporated herein by The full content disclosed is included in.

Aqueous vapor barrier layer is set alternatively between core and shell.Aqueous vapor barrier layer is further in the such as U.S. Patent 6,632,147,6,838,028,6,932,720,7,004,854 and 7,182,702 and Publication No. 2003/0069082、2003/0069085、2003/0130062、2004/0147344、2004/0185963、 2006/0068938, disclosed in the U.S. Patent application of 2006/0128505 and 2007/0129172, here Include in by quoting the full content disclosed.

Golf ball layer be optionally non-uniform thickness except innermost layer and outermost one or more layers Layer.For purposes of this disclosure, " layer of non-uniform thickness " refers to such layer, its have projection, Net, rib etc. are positioned on this layer and the thickness of this layer are changed.The layer of non-uniform thickness preferably has One or more in below: multiple projections placed on it, multiple longitudinal net, multiple horizontal net Shape thing or multiple circle-shaped net.In the specific embodiment of one, the layer bag of non-uniform thickness Include the multiple projections being placed in its outer surface and/or inner surface.Projection can be integrally manufactured with this layer, or can It is then attached on this layer with separately fabricated.Projection can have any shape or section, including but do not limit In, trapezoidal, sinusoidal, dome-shaped, stairstepping, cylinder, cone, frustroconical, Rectangle, there is the pyramid of polygon bottom surface, truncated pyramid shape or polyhedron shape.Inner side is with outward Suitable shape that side is protruding and section are additionally included in United States Patent (USP) 6, those disclosed in 293,877, this In include in by quoting the full content disclosed.In another specific embodiment, non-homogeneous thickness The layer of degree includes the circular net in multiple inner sides and/or the outside arranged thereon.In present embodiment In particular aspects, the existence of net adds the rigidity of nonuniform thick layer.Net can be longitudinally Net, horizontal net or circle-shaped net.

The nonuniform thick layer of the golf of the present invention preferably has 0.010 or 0.015 English within the range having a lower limit of Very little thickness in the range of 0.100 or 0.150 inch, and preferably to have lower limit be 5000 or 10000psi And the upper limit is the flexural modulus in the range of 80000 or 90000psi.

The layer of non-uniform thickness is further in such as United States Patent (USP) 6,773,364 and Publication No. Disclosed in the U.S. Patent application of 2008/0248898, receive incorporated herein by the full content disclosed Enter.

Except material disclosed above, any core or shell can comprise one or more following materials: Thermoplastic elastomer (TPE), thermo-setting elastomer, synthetic rubber, TPV, copolymer ionomers, Ternary polymerization ionomer, Merlon, polyolefin, polyamide, copolyamide, polyester, polyester acyl Amine, polyetheramides, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polyarylate, polypropylene Acid esters, polyphenylene oxide, impact modification polyphenylene oxide, high-impact polystyrene, diallyl phthalate Propyl ester polymer, metallocene catalyzed polymers, styrene-acrylonitrile (SAN), olefin-modified SAN, third Alkene nitrile-styrene-acrylonitrile, phenylethylene-maleic anhydride (S/MA) polymer, styrol copolymer, sense Change styrol copolymer, functionalized styrene terpolymer, styrene copolymer, cellulose gather Compound, liquid crystal polymer (LCP), Ethylene-Propylene-Diene rubber (EPDM), ethane-acetic acid ethyenyl ester are common Polymers (EVA), ethylene propylene rubber (EPR), ethylene vinyl acetate, polyureas and polysiloxanes.It is used as In compositions disclosed herein, the suitable polyamide of additional materials also includes obtaining in the following manner Resin: (1) (a) dicarboxylic acids such as oxalic acid, adipic acid, decanedioic acid, p-phthalic acid, M-phthalic acid or Isosorbide-5-Nitrae cyclohexane dicarboxylic acid and (b) diamine such as ethylenediamine, butanediamine, pentanediamine, hexamethylene diamine or the last of the ten Heavenly stems two Amine, Isosorbide-5-Nitrae-cyclohexyl diamine or the polycondensation of m-xylene diamine；(2) cyclic lactames such as epsilon-caprolactams or ω- The ring-opening polymerisation of lauric lactam；(3) amino carboxylic acid such as 6-aminocaprolc acid, 9 aminononanoic acid, 11-amino Undecanoic acid or the polycondensation of 12-aminolauric acid；Or (4) being total to of cyclic lactames and dicarboxylic acids and diamine Poly-.The object lesson of suitable polyamide includes nylon 6, nylon66 fiber, NYLON610, nylon 11, Buddhist nun Dragon 12, the nylon of copolymerization, nylon MXD 6 and Stanyl (DSM)..

It is suitable for use as other preferred material bags of additional materials in golf compositions disclosed herein Include Skypel polyester elastomer, can be commercially-available from the SKChemicals of Korea S； Two is embedding Section and triblock copolymer, can be commercially-available from the Kuraray Corporation of Japan Kurashiki； And Diblock and triblock copolymer, can be from the Kraton in Houston city, Texas Polymers LLC is commercially-available.

Ionomer is also extremely suitable for being blended with compositions disclosed herein.Suitable ionomer include α- Alkene/copolymers of unsaturated carboxylic acids type or the ionomer resin of terpolymer type.Copolymers ionomers is led to Cross with in metal ion and alpha-olefin and there is the α of 3-8 carbon atom, in the copolymer of beta-unsaturated carboxylic acid At least part of carboxyl obtain.Terpolymer type ionomer by with in metal ion and alpha-olefin, There is the α of 3-8 carbon atom, beta-unsaturated carboxylic acid and the α with 2-22 carbon atom, beta-unsaturated carboxylic acid At least part of carboxyl in the terpolymer of ester obtains.Suitable for copolymer type and ternary polymerization The example of the alpha-olefin of thing type ionomer includes ethylene, propylene, 1-butylene and 1-hexene.Suitable is used for The example of the unsaturated carboxylic acid of copolymer type and terpolymer type ionomer includes acrylic acid, metering system Acid, ethylacrylic acid, α-chloro-acrylicacid, butenoic acid, maleic acid, fumaric acid and itaconic acid.Copolymerization Thing type and terpolymer type ionomer include having different acid contents and the ionomer of acid degree of neutralization, They are neutralized by unit price described herein or bivalent cation.Be suitable to compositions disclosed herein be blended Can include by commercially-available ionomer Ionomer resin, can be from E.I.du Pont de Nemours and Company is commercially-available, and Ionomer, can be from ExxonMobil Chemical Company is commercially-available.

Silicone material is also highly suitable for use in and is blended with compositions disclosed herein.Suitable silicone material includes Add or be added without the monomer of reinforcer, oligomer, prepolymer and polymer.Suitable silicone material A type can combine at least 1 thiazolinyl with at least 2 carbon atoms in their molecule. The example of these thiazolinyls includes but not limited to, vinyl, pi-allyl, cyclobutenyl, pentenyl, hexenyl With decene base.Alkenyl-functional groups may be located at any position of silicone structure, including an end of this structure Position or two end positions.In this component, remaining (such as, the non-thiazolinyl) organic group being bonded with silicon is independent Ground is selected from the alkyl without aliphatic unsaturation part or halohydrocarbyl.These nonrestrictive example bag Include: alkyl, such as methyl, ethyl, propyl group, butyl, amyl group and hexyl；Cycloalkyl, such as cyclohexyl and Suberyl；Aryl, such as phenyl, tolyl and xylyl；Aralkyl, such as benzyl and phenethyl； And haloalkyl, such as 3,3,3-tri-fluorinated propyl and chloromethyl.Another kind of suitable silicone material Type has the alkyl not conforming to aliphatic unsaturation part.Object lesson includes: trimethylsiloxy group end-blocking Dimethyl siloxane-methyl hexenyl silicone copolymers；The diformazan of dimethyhexenes base siloxy end-blocking Radical siloxane-methylhexenylsiloxane copolymer；Dimethyl siloxane-the first of trimethylsiloxy group end-blocking Base vinyl siloxane copolymer；Methyl phenyl siloxane-the dimethyl silica of trimethylsiloxy group end-blocking Alkane-methyl vinyl silicone copolymer；The dimethyl polysiloxane of dimethylvinylsiloxy siloxy end-blocking； The dimethyl siloxane-methyl vinyl siloxane copolymer of dimethylvinylsiloxy siloxy end-blocking；Dimethyl The methyl phenyl silicone of vinyl siloxy end-blocking；The methylbenzene of dimethyl ethenyl siloxy end-blocking Radical siloxane-dimethyl siloxane-methyl vinyl siloxane copolymer；And the copolymer listed by above-mentioned, At least one of which group is dimethyl hydroxyl siloxy.Be suitable to compositions disclosed herein be blended can The example of commercially-available silicone includes Silicone rubber, can be from state of Michigan Midland's Dow Corning Corporation is commercially-available； Silicone rubber, can be from New York The General Electric Company of Waterford is commercially-available；And Silicone, permissible Commercially-available from the Wacker Chemie AG of Germany.

Other kinds of copolymer can also join in golf compositions disclosed herein.Such as, The suitable copolymer comprising epoxy monomer includes styrene butadiene styrene block copolymer (SBS), wherein Polybutadiene block comprises epoxy radicals, and styrene isoprene styrene block copolymer (SIS), Qi Zhongju Isoprene block comprises epoxy radicals.The example of available commercial epoxy-functional copolymer includes ESBS A1005, ESBS A1010, ESBS A1020, ESBS AT018 and ESBS AT019 ring Styrene oxide-butadiene-styrene block copolymer, can be from the Daicel Chemical of Japan Industries Inc. is commercially-available.

Can be with nonionic thermoplastic resin from poly composition for form each golf ball layer of the present invention Fat is blended, and specifically, this is to control properties of product.The example of suitable non-ionic thermal plastic resin Son includes but not limited to, polyurethane, polyether ester, polyamide ether, polyethers-urea, Thermoplastic poly Ether block amides (can be commercially-available from Arkema Inc.), styrene butadiene styrene block copolymer (SBS), Styrene (Ethylene/Butylene) styrene block copolymer, polyamide, polyester, polyolefin (such as, poly-second Alkene, polypropylene, ethylene-propylene copolymer), ethylene-(methyl) acrylate, ethylene-(methyl) acrylic acid, There is the functionalized polymeric of maleic anhydride grafting and epoxidation etc., elastomer (such as, EPDM, metal The polyethylene of cyclopentadienyl catalysis) and the abrasive flour of thermo-setting elastomer.

Compositions disclosed herein can be foaming or fill with density controlling material, to provide Suitably golf Performance Characteristics.

The technique that the invention is not restricted to any specific formation golf ball layer.Should be appreciated that described each layer Can be formed by any suitable technology, including injection, compression moulding, casting and reaction injection molding(RIM).Especially, Thermosetting thin layer can be formed by the method forming sulfuration or other crosslinking rubber thin-beds of any conventional, Include but not limited to the casting of compression molding, rubber injection mold, liquid rubber and lamination.

When using injection, said composition typically can be easily supplied into the ball in the trunnion of injection machine Shape or granular form, and, said composition is 150 °F to 600 °F in temperature in injection machine, By screw melting and transmission in heating bucket under being preferably 200 °F to 500 °F.The compositions of fusing Finally being injected in the die cavity of closing, this die cavity can cool down at ambient temperature or at elevated temperatures, But typically, mould is cooled to the temperature of 50 °F to 70 °F.1 second is stopped to 300 in the mould closed Second, after preferably 20 seconds to 120 seconds, core and/or core are added that one or more additional wick or shell are from mould In tool take out so that it is in the temperature of ambient temperature or reduction cool down, or be placed in cooling fluid such as water, In dry ice in frozen water, solvent etc..

When using compression molding to form core, said composition is initially formed prefabricated component or blank material, its Typically cylindrical or substantially spherical, its weight slightly overweights the desired wt of the core being molded as.At this Before step, compositions can first be extruded or otherwise melts and be forced through die head (dic), cylindrical preform then it is cut into.Then this prefabricated component is placed in compression mould chamber, And 150 °F to 400 °F, preferably 250 °F to 400 °F, the mould temperature of more preferably 300 °F to 400 °F The lower compression of degree.When compression molding outer layer, first pass through the casing half of injection cambium layer material.Then will Golf assembly Bao Mi, in two half-shell, is then placed on compression mould chamber and compresses.

Reaction injection molding(RIM) technique further such as United States Patent (USP) 6,083,119,7,208,562,7,281,997, 7,282,169,7,338,391 and Publication No. 2006/0247073 U.S. Patent application disclosed in, this In include in by quoting the full content disclosed.

Here thermoplastic layer can process in the way of producing the hardness gradient of plus or minus.Use wherein In the golf ball layer of the present invention of thermoset rubber, technique and/or the generation producing gradient can be used The rubber compounding of gradient.The technique of generation gradient and formula are more completely on March 14th, such as 2008 Application No. 11/829,461 that Application No. on the July 27th, 12/048,665,2007 submitted to submits to, The application number of the Application No. submission on August 1st, 11/772,903,2007 that on July 3rd, 2007 submits to It it is the U.S. Patent application of the Application No. 11/832,197 that on August 1st, 11/832,163,2007 submits to Disclosed in, include in incorporated herein by the full content disclosed.

The golf of the present invention typically has more than 0.700, more preferably more than 0.750, more excellent Select the COR of more than 0.780.Used herein of COR, determine according to known code, wherein Gao Er Husband's ball or golf assembly (e.g., golf ball core) penetrate from air bubble with two given speed, and Calculate under speed 125ft/s.Trajectory dark slide between the air bubble and steel plate of fixed range with measure Ball speed.When ball flies to steel plate, it excites each dark slide, measures the time at each dark slide. This provides the incident traveling time that the incidence rate with ball is inversely proportional to.Pellet impact steel plate also rebounds by hiding Tabula rasa, again measures and advances the required time between each dark slide.This provides the exit velocities with ball Outgoing traveling time in inverse ratio.Then the ratio as outgoing traveling time with incident traveling time calculates COR, COR=V_{Go out}/V_Enter=T_Enter/T_{Go out}。

The ball hardness that the golf of the present invention is generally of is 40 or bigger, or within the range having a lower limit of 40 or 50 or 60 65 or 80 85 or 90 and the upper limit be 80 or 85 or 90 or 100 or 110 or 115 Or in the range of 120, wherein the upper limit more than lower limit (such as, when being instantly limited to 85, the upper limit is 90,100, 110,115 or 120).In golf ball design, ball hardness is key factor.Such as, the hardness of core can Leave spin rate and the feel of rod (driver) affecting ball.Compression such as Jeff Dalton By A ny Other Name, Science and Golf IV, Proceedings of the World Scientific Disclosed in Congress of Golf (Eric Thain ed., Routledge, 2002) (" J.Dalton "), if A dry different method may be used for measuring hardness, and including Atti ball hardness, Riehle ball hardness, not Measure and effective modulus with the load/deflection under dead load and skew (offset).For the present invention Purpose, " ball hardness " refer to Atti ball hardness and use Atti ball hardness testing device according to known method Measuring, wherein, piston is used for pressing the ball against spring.The stroke of piston is fixing and measures spring Deflection.The measurement of spring deflection is not from the beginning of spring contact to ball；But in skew substantially Start during the spring deflection of first 1.25mm (0.05 inch).The low-down core of rigidity will not make spring Flexure is more than 1.25mm, thus obtains the ball hardness measurement of 0.Atti ball qualimeter is design For measuring the object of a diameter of 1.680 inches；It is, therefore, necessary to by less object such as golf The padded total height to 1.680 inches of core obtain accurate reading.Can be according to institute in J.Dalton The formula be given Atti ball hardness is converted to Riehle (core), Riehle (ball), 100kg deflection, 130-10kg deflection or effective modulus.

The golf of the present invention typically has 60% or bigger, preferably 65% or bigger, and more preferably The pit coverage rate of 75% or bigger.

The golf of the present invention can have the overall diameter of arbitrary dimension.Golf of the present invention preferred Diameter 1.680 inches and model that the upper limit is 1.740 or 1.760 or 1.780 or 1.800 inches within the range having a lower limit of In enclosing.

The golf of the present invention preferably has 70-95g cm², preferably 75-93g cm², and more preferably 76-90g·cm²The moment of inertia (" MOI ").For the embodiment of low MOI, the MOI of golf is preferred For 85g cm²Or lower, or 83g cm²Or it is lower.For the embodiment of high MOI, golf MOI be preferably 86g cm²Or bigger, or 87g cm²Or it is bigger.MOI is in the Connecticut State The moment of inertia instrument of model MOI-005-104 that the Inertia Dynamics of Collinsville manufactures is surveyed Amount.This instrument connects PC, by COMM port communication and by MOI instrument software 1.2 version Drive.

The case hardness of golf ball layer obtains from the meansigma methods of the repetitive measurement of the most each hemisphere, notes keeping away Exempt to measure in separator bar or the surface defect such as hole or prominence of core.Hardness measurement is according to ASTM " Durometer measurements rubber and the identation hardness of plastics " of D-2240.Owing to being curved surface, it should Noting guaranteeing before carrying out case hardness reading, golf or golf assembly are centrally placed in firmly Under degree meter pressure head.Can reading to the calibrated digital durometer of 0.1 stiffness units for all of Hardness measurement, and when being configured to obtain after full-scale reading 1 second, read hardness reading.Digital durometer must Must be connected on the sensor of automatic station (automatic stand), and bottom it, also must be parallel to this impression Device.Weight and impact speed on durometer meet ASTM D-2240.

The central hardness of core obtains according to following code.Lightly core is pressed into internal diameter and is about slightly less than the straight of core In the hemisphere clamper in footpath so that core is clamped in the hemispherical portion of clamper just, makes the several of this core simultaneously What central plane exposes.Utilizing friction to be fixed in clamper by core, thus it is in cutting and polishing step In will not move, but friction can not be too big in order to avoid the shape of distortion core itself.Fixed core makes dividing of core The top of clamper it is roughly parallel to every line.Before fixing, measurement becomes the core of 90 degree with the direction Diameter.Also measure the top to core, the bottom of clamper, think that calculating in the future provides reference point.Use Band saw or other suitable cutting elements carry out rough cut in the geometric center of the exposure of slightly above core, really Protect this step SMIS not move in clamper.The remainder of the still core in clamper is fixed on table On the substrate of face polisher." slightly " surface exposed is polished into the surface of smooth planar, exposes the several of core What center, this can confirm from clamp base to the height of core exposed surface by measuring, it is ensured that as On accurate half ± 0.004 inch of core original height that records be removed.Core is stayed in clamper, use Central straight angle square finds the center of core, and careful labelling, according to ASTM D-2240 at centre mark Measure its hardness.Then, other hardness measurements at the center any distance of core are entered in the following manner OK: from centre mark radially outward setting-out, and along this line in any distance, typically with away from center 2mm Increment measurement hardness.Hardness away from center specified distance should be fixed along separating 180 ° or separately 90 ° respectively The radial arms of position is measured at least 2 times, preferably 4 times, is then averaged.All through geometric center Plane on the hardness measurement that carries out all carry out when its orientation still and do not upset in clamper by core, make Test surfaces is parallel to the bottom of clamper consistently, and therefore suitably align also parallel with durometer Bottom.

A hardness point should be only measured in any specific geometric position.

For purposes of this disclosure, the hardness gradient at center is by the central point at central outer surface and core Hardness measurement defines." bear " and " just " refers to that the hardness number of the outer surface with golf assembly deducts The result of the inner most hardness number of this assembly.Such as, if the outer surface of solid central is than the hardness at center Be worth low (i.e. surface ratio center is soft), then hardness gradient is " bearing " gradient.During the hardness gradient of measuring center, First central authorities' hardness determine according to the code of the central hardness of above-mentioned acquisition core.Once marked the center of core And determining its hardness, the hardness measurement at the center any distance of core is carried out in the following manner: from Mark center radially outward setting-out, and typically with increment measurement and the labelling distance away from center of 2mm. All in the hardness measurement carried out in the plane of geometric center all at core still in clamper and do not have Carry out when upsetting its orientation so that test surfaces is parallel to the bottom of clamper consistently.On core any pre- The difference of hardness that location is put is calculated as average surface hardness and deducts the hardness of suitable reference point, thus surface is soft Core in its center will have negative hardness gradient, and described suitable reference point comes in single, solid core Say such as in core center.

Hardness gradient more completely in such as United States Patent (USP) 7,429,221, and carry on November 14th, 2007 Application No. 11/939,634 that Application No. on the November 14th, 11/939,632,2007 handed over submits to, The Application No. 11/939,635 of submission on November 14th, 2007 and on November 14th, 2007 submit to Application No. 11/939, disclosed in the U.S. Patent application of 637, whole incorporated herein by disclosed Content is included in.

It is to be understood that " material hardness " and " hardness directly measured on golf " is to have essential distinction 's.For purposes of this disclosure, the hardness of material is measured according to ASTM D2240, and generally includes survey Measure flat " sheet " or the hardness of " tabletting " that this material is formed.Directly at golf (or other spherical surfaces) The hardness of upper measurement typically produces different hardness numbers.This species diversity of hardness number because of some questions, Include, but not limited to spherical structure (such as, the type of core, core and/or the quantity etc. of shell), ball (or ball Body) the material composition of diameter and adjacent layer.It will also be understood that two kinds are measured technology nonlinear correlation, Therefore, a kind of hardness number can not connect with another hardness number simply.

When here providing numerical lower limits and numerical upper limits, cover and can use any of these numerical value Combination.

All patents referred to herein, publication, test procedure and other lists of references, including preferential Power text, all intactly includes in the degree that its disclosure is not inconsistent with the present invention by quoting Application, and described in include in and be allowed in all judicial districts all carrying out such including in.

Although having described exemplary embodiment of the invention in detail, it should be appreciated that common for this area For technical staff, under without departing from spirit and scope of the present invention, other modification are substantially and easily to obtain ?.Therefore, it is not intended that scope of the appended claims is only limitted to example given here and description, On the contrary, claim can be construed to include the feature that the patentability that all present invention have is innovated, including One skilled in the art of the present invention are considered as all features of equivalent feature.

Claims (17)

1. golf, it comprises:

Inner core, it comprises the center formed by the first thermoset composition, and wherein, this inner core has The diameter of 1.000 inches to 1.580 inches, the central authorities of 40 Shore C hardness to 70 Shore C hardness Hardness and the case hardness of 50 Shore C hardness to 95 Shore C hardness, described inner core comprises attached Add inner sandwich layer；

Intermediate core layer, its thickness with 0.010 inch to 0.070 inch, 65 Shore D hardness are extremely The outer surface hardness of 95 Shore D hardness, and by selected from metal composites, composite and The compositions of inorganic/organic blend compositions is formed, and wherein said metal composites includes aluminum, Huang Copper, chromium, copper, ferrum, lead, magnesium, molybdenum, nickel, nickel-silver, niobium, silver, steel, tantalum, stannum, titanium, Titanium/nickel alloy, tungsten, vanadium and zinc, described composite includes matrix material and embeds matrix Filament material in material, described inorganic/organic blend compositions includes glass ionomer, resin Modified glass ionomer, fatty acid modified glass ionomer, ceramers, inorganic organic material, Silicon ionomer, dental cement or restorative compositions, polymerizable cement, ionomer cement, Burning polymer composites, ionomer cement, fluoroaluminosilicate glass, fluoroaluminosilicate Glass powder, polyalkenes acid esters cement, flexible composite and their blend；

Outer sandwich layer, it is formed by the second thermoset composition, and has 0.010 inch to 0.075 English Very little thickness and the outer surface hardness of 45 Shore C hardness to 90 Shore C hardness；With

Shell, it has the thickness of 0.010 inch to 0.050 inch, and is 30 by material hardness Shore D hardness is formed to the compositions of 65 Shore D hardness.

2. the golf of claim 1, wherein said inner core a diameter of 1.400 inches to 1.490 Inch.

3. the golf of claim 1, the outer surface hardness of wherein said intermediate core layer is 75 Shore D hardness is to 95 Shore D hardness.

4. the golf of claim 1, wherein said additional inner sandwich layer is by thermoset composition shape Become.

5. the golf of claim 1, wherein said additional inner sandwich layer is by thermoplastic compounds shape Become.

6. the golf of claim 1, wherein said golf also comprise be arranged on described in Thermoplastic core layer between core and described intermediate core layer.

7. the golf of claim 1, wherein said golf also comprise be arranged on described in Between thermoplastic core layer between sandwich layer and outer core layer.

8. the golf of claim 1, wherein said golf also comprise be arranged on described in The first thermoplastic core layer between core and described intermediate core layer and be arranged on described intermediate core layer and described The second thermoplastic core layer between outer sandwich layer.

9. golf, it comprises:

Inner core, it comprises the center formed by the first thermoplastic compounds, and wherein, described inner core has The diameter of 1.000 inches to 1.580 inches, the central authorities of 40 Shore C hardness to 70 Shore C hardness Hardness and the case hardness of 50 Shore C hardness to 95 Shore C hardness, described inner core comprises attached Add inner sandwich layer；

Intermediate core layer, its thickness with 0.010 inch to 0.070 inch and 65 Shore D hardness To the case hardness of 95 Shore D hardness, and by selected from metal composites, composite and The compositions of inorganic/organic blend compositions is formed, and wherein said metal composites includes aluminum, Huang Copper, chromium, copper, ferrum, lead, magnesium, molybdenum, nickel, nickel-silver, niobium, silver, steel, tantalum, stannum, titanium, Titanium/nickel alloy, tungsten, vanadium and zinc, described composite includes matrix material and embeds matrix Filament material in material, described inorganic/organic blend compositions includes glass ionomer, resin Modified glass ionomer, fatty acid modified glass ionomer, ceramers, inorganic organic material, Silicon ionomer, dental cement or restorative compositions, polymerizable cement, ionomer cement, Burning polymer composites, ionomer cement, fluoroaluminosilicate glass, fluoroaluminosilicate Glass powder, polyalkenes acid esters cement, flexible composite and their blend；

Outer sandwich layer, it is formed by the second thermoplastic compounds, and has 0.010 inch to 0.075 English Very little thickness, the case hardness of 45 Shore C hardness to 90 Shore C hardness；With

Shell, it has the thickness of 0.010 inch to 0.050 inch, and is 30 by material hardness Shore D hardness is formed to the compositions of 65 Shore D hardness.

10. the golf of claim 9, wherein said inner core a diameter of 1.400 inches extremely 1.490 inch.

The golf of 11. claim 9, the outer surface hardness of wherein said intermediate core layer is 75 Shore D hardness is to 95 Shore D hardness.

The golf of 12. claim 9, wherein said additional inner sandwich layer is by thermoset composition shape Become.

The golf of 13. claim 9, wherein said additional inner sandwich layer is by thermoplastic compounds shape Become.

The golf of 14. claim 9, wherein said golf also comprise be arranged on described in Thermosetting core layer between core and described intermediate core layer.

The golf of 15. claim 9, wherein said golf also comprise be arranged on described in Between thermosetting core layer between sandwich layer and outer core layer.

The golf of 16. claim 9, wherein said golf also comprise be arranged on described in The first thermosetting core layer between core and described intermediate core layer and be arranged on described intermediate core layer and described The second thermosetting core layer between outer sandwich layer.

17. golf, it comprises:

Core, it consists of:

Inner sandwich layer, it is formed by the first thermoplastic compounds, and has 1.000 inches to 1.580 Diameter, the central hardness of 40 Shore C hardness to 70 Shore C hardness and 50 Xiao of inch Family name's C hardness to the case hardness of 95 Shore C hardness,

Intermediate core layer, its thickness with 0.010 inch to 0.070 inch and 65 Shore D Hardness is to the case hardness of 95 Shore D hardness, and by selected from metal composites, composite The compositions of compositions and inorganic/organic blend compositions is formed, wherein said metallic combination Thing include aluminum, pyrite, chromium, copper, ferrum, lead, magnesium, molybdenum, nickel, nickel-silver, niobium, silver, Steel, tantalum, stannum, titanium, titanium/nickel alloy, tungsten, vanadium and zinc, described composite bag Include matrix material and the filament material embedded in matrix material, described inorganic/organic blend group Compound include glass ionomer, resin modified glass ionomer, fatty acid modified glass ionomer, Ceramers, inorganic organic material, silicon ionomer, dental cement or restorative combination Thing, polymerizable cement, ionomer cement, burning polymer composites, from poly- Thing cement, fluoroaluminosilicate glass, fluoroaluminosilicate glass powder, polyalkenes acid esters cementation Agent, flexible composite and their blend,

First outer sandwich layer, it forms by the second thermoplastic compounds, and

Second outer sandwich layer, it is formed by thermoset composition, and has 0.010 inch to 0.075 The thickness of inch and the case hardness of 45 Shore C hardness to 90 Shore C hardness；With

Shell, it has the thickness of 0.010 inch to 0.050 inch, and is 30 by material hardness Shore D hardness is formed to the compositions of 65 Shore D hardness.