CN102166403B

CN102166403B - Multilayer core golf ball

Info

Publication number: CN102166403B
Application number: CN201010625197.XA
Authority: CN
Inventors: 迈克尔·J·沙利文; 布莱恩·科米厄; 道格拉斯·S·戈古恩
Original assignee: Acushnet Co
Current assignee: Acushnet Co
Priority date: 2009-12-02
Filing date: 2010-12-02
Publication date: 2015-02-18
Anticipated expiration: 2030-12-02
Also published as: CN102166403A

Abstract

The invention relates to a multilayer core golf ball, comprising a multilayer core and a casing layer. The multilayer core comprises a soft and thermosetting rubber center, a hard thermoplastic middle core layer and a thin thermosetting rubber outer core layer. The maximal hardness of the core is a point or an area that is 01.mm to 8.0mm measured from the radial direction of an outer surface of the core to the inner surface. The maximal core hardness is preferably 10% higher than the outer surface hardness of the core.

Description

Multilayer core golf ball

Cross reference related application

The application is submit on March 20th, 2009 12/407, the part continuation application of 856,12/407,856 be on January 10th, 2008 submit to application number be 11/972, the part continuation application of the U.S. Patent application of 240, here by introducing the full content including above-mentioned application in.

Technical field

The present invention relates in general to golf, and more particularly, relates to the golf with multilayer core, and described multilayer core comprises the outer sandwich layer of soft thermoset rubber center, hard thermoplasticity intermediate core layer and thin thermoset rubber.

Background technology

The golf with multilayer core is known.Such as, United States Patent (USP) 6,852,044 discloses the golf with multilayer core, and described multilayer core has the inner core that is relatively soft, low ball hardness (compression) surrounded by the outer core of relative stiffness.United States Patent (USP) 5,772,531 disclose a kind of solid golf ball, and it comprises: have by the solid core of internal layer, intermediate layer and the outer three-decker formed, and for the shell of coated solid core.Publication number be 2006/0128904 U.S. Patent application also disclose the golf of multilayer core.Other examples of multilayer core can be, such as, and United States Patent (USP) 5,743,816,6,071,201,6,336,872,6,379,269,6,394,912,6,406,383,6,431,998,6,569,036,6,605,009,6,626,770,6,815,521,6,855,074,6,913,548,6,981,926,6,988,962,7,074,137,7,153,467 and 7,255, obtain in 656.

The invention provides a kind of Golf ball structure of new multilayer core, wherein, this core comprises the outer sandwich layer of soft thermoset rubber center, hard thermoplasticity intermediate core layer and thin thermoset rubber.Here the new construction disclosed has unique core hardness gradient, and wherein maximum core hardness is greater than the maximum core hardness of conventional core and/or maximum core hardness and is positioned at specified distance from the outmost surface of core.

Summary of the invention

In one embodiment, the present invention relates to the golf comprising core and shell.This core is made up of the outer sandwich layer of diene rubber center, thermoplasticity intermediate core layer and diene rubber.This center has the diameter of 1.000 inches to 1.580 inches, the central hardness of 40 Shore C hardness to 70 Shore C hardness, the case hardness of 50 Shore C hardness to 85 Shore C hardness.Intermediate core layer has the thickness of 0.005 inch to 0.100 inch, and 60 Shore D hardness or larger outer surface hardness.Outer sandwich layer has the thickness of 0.010 inch to 0.100 inch, and 80 Shore C hardness or larger outer surface hardness.The outer surface hardness of outer sandwich layer is greater than the case hardness at center.The highest hardness of this core is positioned at 0.25mm to the 5.00mm distance radially-inwardly measured from the outer surface of this core.The outer surface hardness high 10% or larger of the outer sandwich layer of this maximized surface hardness ratio.Shell has the thickness of 0.010 inch to 0.050 inch, and the composition being less than 60 Shore D hardness by material hardness is formed.

In another embodiment, the present invention relates to the golf comprising core and shell.Described core is made up of the outer sandwich layer of diene rubber center, thermoplasticity intermediate core layer and diene rubber.Described center has the diameter of 1.400 inches to 1.550 inches, the central hardness of 45 Shore C hardness to 60 Shore C hardness, and the case hardness of 55 Shore C hardness to 85 Shore C hardness.Described intermediate core layer has the thickness of 0.020 inch to 0.070 inch, and 65 Shore D hardness or larger outer surface hardness.Described outer sandwich layer has the thickness of 0.020 inch to 0.050 inch, and 85 Shore C hardness or larger outer surface hardness.The outer surface hardness of outer sandwich layer is greater than the case hardness at center.The highest hardness of core is positioned at 0.50mm to the 5.00mm distance radially-inwardly measured from the outer surface of core.The outer surface hardness high 10% or larger of the outer sandwich layer of maximized surface hardness ratio.Shell has the thickness of 0.010 inch to 0.050 inch, and the composition being less than 60 Shore D hardness by material 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 the golf 30 according to one embodiment of the present invention, and it comprises inner core 32, intermediate core 34, outer core 36 and shell 38.Although what show in Fig. 1 is simple layer, any one or more in inner core 32, intermediate core 34, outer core 36 and shell 38 can be made up of one deck, two-layer or multilayer.

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

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

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

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

Multilayer core of the present invention comprises inner core, intermediate core and outer core.The overall diameter (also referring to the external diameter of outer sandwich layer here) of this multilayer core is 1.000 or 1.300 or 1.400 or 1.500 or 1.580 or 1.600 or 1.610 or 1.620 inches and the upper limit is in the scope of 1.600 or 1.610 or 1.620 or 1.630 or 1.640 or 1.650 or 1.660 inches at lower limit, wherein the upper limit is greater than lower limit (such as, when being instantly limited to 1.610 inches, the upper limit is 1.620,1.630,1.640,1.650 or 1.660 inches).In specific embodiment, 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 inches or 1.620 inches.

Inner core is made up of center, or is made up of center and additional inner sandwich layer, or 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 larger, or 1.000 inches or larger, or 1.250 inches or larger, or 1.300 inches or larger, or 1.350 inches or larger, or 1.390 inches or larger, or 1.400 inches or larger, or 1.425 inches or larger, or 1.450 inches or larger, or this overall diameter 0.250 or 0.500 or 0.750 or 1.000 or 1.250 or 1.300 or 1.325 or 1.350 or 1.390 or 1.400 or 1.440 or 1.450 inch and the upper limit is in the scope of 1.450 or 1.460 or 1.475 or 1.490 or 1.500 or 1.520 or 1.550 or 1.580 or 1.600 inches within the range having a lower limit of.

The central hardness of inner core 20 or 25 or 30 or 35 or 40 or 45 or 50 or 55 or 57 Shore C hardness and the upper limit is in the scope of 57 or 60 or 65 or 70 or 75 or 90 Shore C hardness within the range having a lower limit of.The outer surface hardness of inner core 20 or 50 or 55 or 70 or 75 or 78 Shore C hardness and the upper limit is in the scope of 75 or 78 or 80 or 85 or 90 or 95 Shore C hardness within the range having a lower limit of, wherein the upper limit is greater than lower limit (such as, when being instantly limited to 75, the upper limit is 78,80,85,90 or 95).Inner core has negative hardness gradient, zero hardness gradient, or is up to the positive hardness gradient of 45 Shore C hardness, or from the positive hardness gradient of 10 Shore C hardness to 45 Shore C hardness.In specific embodiment, the center that inner core is formed by zero gradient formula forms, and as such as United States Patent (USP) 7,537,530 and 7,537, disclosed in 529, their whole disclosures is included in by reference here.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 or 20 or 30 or 35 or 40 or 50 or 60 and the upper limit is that in the scope of 40 or 50 or 60 or 70 or 80 or 90, wherein the upper limit is greater than lower limit (such as, when being instantly limited to 50, its upper limit is 60,70,80 or 90).

Each inner sandwich layer is preferably formed by rubber composition.In specific embodiment, the center that inner core is formed by rubber composition forms.In another specific embodiment, inner core is made up of center and additional inner sandwich layer, and both are formed by identical or different rubber compositions.In another specific embodiment, inner core is made up of center, the first additional inner sandwich layer and the second additional inner sandwich layer, and each wherein in them is formed by identical or different rubber compositions.

Suitable rubbers composition for the formation of inner sandwich layer comprises base rubber, initator, coagent, and optionally comprise zinc oxide, zinc stearate or stearic acid, antioxidant, and one or more in softening accelerator (softand fast agent).Suitable base rubber comprises natural and synthetic rubber, includes but not limited to, polybutadiene, polyisoprene, ethylene propylene rubber (" EPR "), SBR styrene butadiene rubbers, styrene block copolymer rubber is (as SI, SIS, SB, SBS, SIBS etc., wherein " S " is styrene, and " I " is isoprene, and " B " is butadiene), butyl rubber, halogenated butyl rubber, polystyrene elastomers, polyethylene elastomer, polyurethane elastomer, SPUA, the elastomer of metallocene catalyst and plastic body, isobutene and the copolymer to ring-alkylated styrenes, isobutene and the halogenated copolymers to ring-alkylated styrenes, the copolymer of butadiene and acrylonitrile, polychlorobutadiene, alkyl acrylate rubbers, chlorination isoprene rubber, Chlorination of Acrylonitrile isoprene rubber, and their combination of two or more (combination of other thermosets of such as polybutadiene and small amount, this thermosets is selected from cis-polyisoprene, using trans-polyisoprene, natural gum, polychlorobutadiene, polynorbornene, poly-octene, polypenthylene, butyl rubber, EPR, EPDM, styrene-butadiene and similar thermosets).Preferred diene rubber, particularly polybutadiene (comprises and has 1 of at least 40% cis-structure, 4-polybutadiene), styrene-butadiene, and polybutadiene and other elastomeric mixtures, the amount of the polybutadiene wherein existed is at least 40% of the total polymer weight of mixture.Particularly preferred polybutadiene comprises neodymium catalysis high-cis polybutadiene, and cobalt, nickel or lithium catalysis polybutadiene.The suitable example of commercially available polybutadiene includes, but not limited to Buna CB neodymium catalysis cis-rich polybutadiene rubber, as Buna CB 23, and cobalt catalysis cis-rich polybutadiene rubber, as can be from company trade obtains with 221; The SE BR-1220 that can obtain from The Dow Chemical Company business; Can from Polimeri business obtains bR 40 and BR 60; Can obtain from UBE Industries, Inc. business rubber; The BR 01 that can obtain from Japan Synthetic Rubber Co., Ltd. business; With the Neodene neodymium catalysis cis-rich polybutadiene rubber that can obtain from Karbochem business, as Neodene BR40.

Suitable initator comprises organic peroxide, can produce the high-energy radiation source of free radical and their combination.The high-energy radiation source that can produce free radical includes but not limited to, electron beam, ultraviolet radiation, gamma radiation, X-ray radiation, infrared radiation, heat and their combination.Suitable 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) cyclohexane; Di-t-butyl peroxide; Di t-amyl peroxide; Tert-butyl peroxide; T-butylcumylperoxide; 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexin-3; Two (2-tert-butyl-peroxy isopropyl) benzene; Dilauroyl peroxide; Dibenzoyl peroxide; T-butyl hydroperoxide; Lauryl peroxide; Benzoyl peroxide; And their combination.Can include but not limited to by the example of suitable peroxide that obtains of business, can obtain from Akzo Nobel business bC cumyl peroxide, and can from RT Vanderbilt Company, Inc. business obtains peroxide, as aNS benzoyl peroxide, 2311,1-bis-(tert-butyl hydroperoxide) 3,3,5-trimethyl-cyclohexane and two (tert-butyl peroxide) n-butyl pentanoate of 230-XL 4,4-.

Peroxide initiator reagent is present in rubber composition to measure as follows usually: the amount of every 100 parts of base rubber at least 0.05 weight portions, or every 100 parts by weight of base rubber 0.05 weight portions 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 the amount in the scope of every 100 parts by weight of base rubber 2.5 weight portions or 3 weight portions or 5 weight portions or 6 weight portions or 10 weight portions or 15 weight portions within the range having a lower limit of.

Coagent uses to increase solid state usually together with peroxide.Suitable coagent includes but not limited to, the slaine of unsaturated carboxylic acid, unsaturated ethylene alkenyl compound and polyfunctional monomer (as trimethylol-propane trimethacrylate), phenylene BMI and their combination.The object lesson of suitable slaine includes but not limited to, one or more slaines of acrylic acid, diacrylate, methacrylic acid and dimethacrylate, wherein metal is selected from magnesium, calcium, zinc, aluminium, lithium, nickel and sodium.In specific embodiment, coagent is selected from the zinc salt of acrylic acid, diacrylate, methacrylic acid and dimethacrylate and their mixture.In another specific embodiment, coagent is dizinc acrylate resin.When coagent be dizinc acrylate resin and/or zinc dimethacrylate time, this coagent typically with every 100 parts by weight of base rubber 1 or 5 or 10 or 15 or 19 or 20 weight portions within the range having a lower limit of and the upper limit be every 100 parts by weight of base rubber 24 or 25 or 30 or 35 or 40 or 45 or 50 or 60 weight portions scope in amount be contained in rubber composition.When using the lower coagent of one or more activity as monomethacrylate zinc and various liquid propene hydrochlorate and methacrylate, the consumption of active lower coagent can be identical with the amount of zinc dimethacrylate coagent or higher with dizinc acrylate resin.Can be obtained the ball hardness of needs by adjustment cross-linking amount, cross-linking amount can such as be realized by the type and amount that change coagent.

Rubber composition optionally comprises curing agent.Suitable curing agent includes but not limited to, sulphur, 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, dithiocar-bamate, thiuramsulfides, guanidine, thiocarbamide, xanthates, dithiophosphates, aldamine, dibenzothiazyl disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, and their combination.

Rubber composition optionally comprises one or more antioxidants.Antioxidant is the compound that can suppress or prevent rubber oxidative degradation.Some antioxidants are also as free radical scavenger; Therefore, when rubber composition comprises antioxidant, the consumption of initator can be equally high or higher with amount disclosed herein.Suitable antioxidant comprises, such as, and EEDQ antioxidant, amine antioxidants and phenol antioxidant.

Rubber composition also can comprise one or more fillers to adjust density and/or the proportion of core.The filler of example comprises deposition aqueous silicon dioxide, clay, talcum, asbestos, glass fibre, aramid fiber, mica, calcium metasilicate, zinc sulfate, barium sulfate, zinc sulphide, lithopone, silicate, carborundum, diatomite, polyvinyl chloride, carbonate (such as, calcium carbonate, zinc carbonate, brium carbonate and magnesium carbonate), metal (such as, titanium, tungsten, aluminium, bismuth, nickel, molybdenum, iron, plumbous, copper, boron, cobalt, beryllium, zinc and tin), metal alloy (such as, steel, brass, bronze, boron carbide whisker and tungsten carbide whisker), metal oxide (such as, zinc oxide, tin oxide, iron oxide, calcium oxide, aluminium oxide, titanium dioxide, magnesia and zirconia), particulate carbonaceous material (such as, graphite, carbon black, flocking, bitumen, cellulose fluff and leather fiber), microballoon (such as, glass and pottery), flying dust, abrasive material (such as, pulverize and the core material reclaimed) again, Nano filling, and two or more combination above-mentioned.The amount of the microparticle material existed in rubber composition typically every 100 parts by weight of base rubber 5 weight portions or 10 weight portions and the upper limit is in the scope of every 100 parts by weight of base rubber 30 weight portions or 50 weight portions or 100 weight portions within the range having a lower limit of.Filler material can be double-functional packing, as zinc oxide (its can as filler/plumper) and titanium dioxide (its can as filler/brightener material).

Rubber composition can also comprise one or more additives being selected from processing aid, processing oil, plasticizer, colouring agent, fluorescer, chemical blowing and foaming agent, defoamer, stabilizing agent, softening agent, anti-impact modifier, free radical scavenger, accelerator, antiscorching agent etc.The amount of the additive existed in rubber composition typically every 100 parts by weight of base rubber 0 weight portions and the upper limit is in the scope of every 100 parts by weight of base rubber 20 weight portions or 50 weight portions or 100 weight portions or 150 weight portions within the range having a lower limit of.

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

Suitable softening accelerator includes but not limited to, organic sulfur and metallic organosulfur compound; Organosulfur compound, comprises list, two and polysulfide, mercaptan and sulfhydryl compound; Inorganic sulphide compounds; The blend of organosulfur compound and inorganic sulphide compounds; The compound of VIA race; The not replacement of sulfur-bearing or metal and unsubstituted aromatics organic compound; Aromatic organometallic compound; Quinhydrones; Benzoquinones; Quinhydrone; Catechol; Resorcinol; And their combination.

Here, " organosulfur compound " refers to any compound containing carbon, hydrogen and sulphur, and wherein sulphur is bonded directly at least 1 carbon.Here, term " sulphur compound " refers to such compound, and it is elementary sulfur, polymerised sulphur (polymeric sulfur) or their combination.Should understand further, term " elementary sulfur " refers to S ₈circulus, and " polymerised sulphur " is the structure of at least one the additional sulphur comprised relative to elementary sulfur.

Suitable is especially the organosulfur compound with following general formula as what soften accelerator:

Wherein, R ₁-R ₅can be C ₁-C ₈alkyl; Halogen; Mercapto (-SH), Carboxylation base; Sulfonation base; And hydrogen; With random order; And also can be phenyl-pentafluoride thiophenol; 2-fluoro thiophenol; 3-fluoro thiophenol; 4-fluoro thiophenol; 2,3-fluoro thiophenol; 2,4-fluoro thiophenol; 3,4-fluoro thiophenol; 3,5-fluoro thiophenol; 2,3,4-fluoro thiophenol; 3,4,5-fluoro thiophenol; 2,3,4,5-phenyl tetrafluoride thiophenol; 2,3,5,6-phenyl tetrafluoride thiophenol; 4-chlorine phenyl tetrafluoride thiophenol; Reptazin; 2-chlorothio-phenol; 3-chlorothio-phenol; 4-chlorothio-phenol; 2,3-chlorothio-phenol; 2,4-chlorothio-phenol; 3,4-chlorothio-phenol; 3,5-chlorothio-phenol; 2,3,4-chlorothio-phenol; 3,4,5-chlorothio-phenol; 2,3,4,5-tetrachlorobenzene thiophenol; 2,3,5,6-tetrachlorobenzene thiophenol; Phenyl-pentabromide thiophenol; 2-bromo thiophenol; 3-bromo thiophenol; 4-bromo thiophenol; 2,3-bromo thiophenol; 2,4-bromo thiophenol; 3,4-bromo thiophenol; 3,5-bromo thiophenol; 2,3,4-bromo thiophenol; 3,4,5-bromo thiophenol; 2,3,4,5-tetrabromo-benzene thiophenol; 2,3,5,6-tetrabromo-benzene thiophenol; Pentaiodobenzene thiophenol; 2-iodobenzene thiophenol; 3-iodobenzene thiophenol; 4-iodobenzene thiophenol; 2,3-iodobenzene thiophenol; 2,4-iodobenzene thiophenol; 3,4-iodobenzene thiophenol; 3,5-iodobenzene thiophenol; 2,3,4-iodobenzene thiophenol; 3,4,5-iodobenzene thiophenol; 2,3,4,5-tetraiodo-benzene thiophenol; 2,3,5,6-tetraiodo-benzene thiophenol; Their zinc salt; Their non-metal salt, such as, the ammonium salt of reptazin; Reptazin magnesium; Reptazin cobalt; And their combination.Preferably, benzene halide thiol compounds is reptazin, and it can commercially in a pure form or trade name a95 (containing the sulphur compound based on the carrier of clay, reptazin heap(ed) capacity is 45%) obtains. a95 can obtain from the Struktol Company of America business of Ohio Stow.PCTP can obtain from the eChinachem business in San Francisco of California in a pure form, and obtains from the eChinachem business in San Francisco of California in a salt form.Suitable organosulfur compound is disclosed in such as United States Patent (USP) 6,635,716,6,919,393,7,005,479 and 7,148 further, in 279, is included in by their full content by reference here.

Suitable containing metal organosulfur compound is including but not limited to the cadmium of, diethyldithiocar bamic acid, diamyl dithiocarbamate, dimethyl dithiocarbamic acid and their combination, copper, lead and tellurium analog.Other example at United States Patent (USP) 7,005, open in 479, by reference its full content is included in here.

Suitable disulfide includes but not limited to 4,4 '-Diphenyl disulfide ether; 4,4 '-xylyl disulfide; 2,2 '-benzamido Diphenyl disulfide ether; Two (2-aminophenyl) disulfide; Two (4-aminophenyl) disulfide; Two (3-aminophenyl) disulfide; 2,2 '-bis-(the amino naphthyl of 4-) disulfide; 2,2 '-bis-(the amino naphthyl of 3-) disulfide; 2,2 '-bis-(the amino naphthyl of 4-) disulfide; 2,2 '-bis-(the amino naphthyl of 5-) disulfide; 2,2 '-bis-(the amino naphthyl of 6-) disulfide; 2,2 '-bis-(the amino naphthyl of 7-) disulfide; 2,2 '-bis-(the amino naphthyl of 8-) disulfide; 1,1 '-bis-(the amino naphthyl of 2-) disulfide; 1,1 '-bis-(the amino naphthyl of 3-) disulfide; 1,1 '-bis-(the amino naphthyl of 3-) disulfide; 1,1 '-bis-(the amino naphthyl of 4-) disulfide; 1,1 '-bis-(the amino naphthyl of 5-) disulfide; 1,1 '-bis-(the amino naphthyl of 6-) disulfide; 1,1 '-bis-(the amino naphthyl of 7-) disulfide; 1,1 '-bis-(the amino naphthyl of 8-) disulfide; 1,2 '-diaminostilbene, 2 '-two sulfo-dinaphthyl; 2,3 '-diaminostilbene, 2 '-two sulfo-dinaphthyl; Two (4-chlorphenyl) disulfide; Two (2-chlorphenyl) disulfide; Two (3-chlorphenyl) disulfide; Two (4-bromophenyl) disulfide; Two (2-bromophenyl) disulfide; Two (3-bromophenyl) disulfide; Two (4-fluorophenyl) disulfide; Two (4-iodophenyl) disulfide; Two (2,5-dichlorophenyl) disulfide; Two (3,5-dichlorophenyl) disulfide; Two (2,4-dichlorophenyl) disulfide; Two (2,6-dichlorophenyl) disulfide; Two (2,5-dibromo phenyl) disulfide; Two (3,5-dibromo phenyl) disulfide; Two (the chloro-5-bromophenyl of 2-) disulfide; Two (2,4,6-trichlorophenyl) disulfide; Two (2,3,4,5,6-five chlorophenyl) disulfide; Two (4-cyano-phenyl) disulfide; Two (2-cyano-phenyl) disulfide; Two (4-nitrobenzophenone) disulfide; Two (2-nitrobenzophenone) disulfide; 2,2 '-dithiobenzoic acid ethyl ester; 2,2 '-dithiobenzoic acid methyl esters; 2,2 '-dithiobenzoic acid; 4,4 '-dithiobenzoic acid ethyl ester; Two (4-acetylphenyl) disulfide; Two (2-acetylphenyl) disulfide; Two (4-Fonnylphenyl) disulfide; Two (4-carbamyl phenyl) disulfide; 1,1 '-dinaphthyl disulfide; 2,2 '-dinaphthyl disulfide; 1,2 '-dinaphthyl disulfide; 2,2 '-bis-(1-chlorine dinaphthyl) disulfide; 2,2 '-bis-(1-bromonaphthalene base) disulfide; 1,1 '-bis-(2-chloronaphthyl, methylnaphthyl) disulfide; 2,2 '-bis-(1-cyanonaphthyl) disulfide; 2,2 '-bis-(1-acetyl group naphthyl) disulfide etc.; And their combination.

Suitable inorganic sulphide compounds includes but not limited to, titanium sulfide, manganese sulfide, and the sulfide analog of iron, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, tin and bismuth.

The compound of suitable VIA race includes but not limited to, elementary sulfur and polymerised sulphur, those as obtained from the Elastochem of Ohio Chardon, Inc. business; Sulfur catalyst compound, comprise PB (RM-S)-80 elementary sulfur and PB (CRST)-65 polymerised sulphur, both all can obtain from Elastochem, Inc.; Tellurium catalyst, as and selenium catalyst, as both all can from RT Vanderbilt Company, and Inc. business obtains.

Suitable not sulfur-bearing or the replacement of metal and do not replace aromatics organic component and include but not limited to, 4,4 '-dibenzenyl, azobenzene and their combination.The size preferable range of aromatic organic radicals is at C ₆to C ₂₀, and more preferably C ₆to C ₁₀.

Suitable replacement and do not replace aromatic organometallic compound and include but not limited to that there is formula (R ₁) _x-R ₃-M-R ₄-(R ₂) _ythose, wherein R ₁and R ₂be respectively hydrogen or substituted or unsubstituted C _1-20straight chain, branching or cyclic alkyl, alkoxyl or alkylthio group, or be monocycle, many rings, the C of condensed ring ₆to C ₂₄aryl; X and y is the integer of 0 to 5 respectively; R ₃and R ₄be selected from respectively monocycle, many rings, the C of condensed ring ₆to C ₂₄aryl; M comprises azo group or metal component.Preferably, R ₃and R ₄be selected from C respectively ₆to C ₁₀aryl, be more preferably selected from phenyl, benzyl, naphthyl, phenylamino and benzothiazolyl.Preferably, R ₁and R ₂be selected from replacement and unsubstituted C respectively _1-10straight chain, branching with cyclic alkyl, alkoxyl and alkylthio group, and C ₆to C ₁₀aryl.Work as R ₁, R ₂, R ₃and R ₄when being substituted, replace can comprise following substituent one or more: hydroxyl and slaine thereof; Sulfydryl and slaine thereof; Halogen; Amino, nitro, cyano group and acylamino-; Carboxyl comprises ester, acid and slaine thereof; Silicyl; Acrylic and slaine thereof; Sulfonyl and sulfonamide; And phosphate and phosphorous acid base.When M is metal component, it can be the metallic element of any suitable.Usually this metal is transition metal, and is preferably tellurium or selenium.

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

Wherein, R ₁, R ₂, R ₃and R ₄separately be selected from: hydrogen, halogen group (F, CI, Br, I), alkyl, carboxyl (-COOH) and slaine (such as ,-COO thereof ^-m ⁺) and ester (-COOR), acetate (-CH ₂and ester (-CH COOH) ₂cOOR), formoxyl (-CHO), acyl group (-COR), acetyl group (-COCH ₃), carbonyl halide (-COX), sulfonic group (-SO ₃and ester (-SO H) ₃r), halosulfonyl groups (-SO ₂x), sulfinic acid base (-SO ₂h), alkyl sulphinyl (-SOR), carbamoyl (-CONH ₂), halogenated alkyl, cyano group (-CN), alkoxyl (-OR), hydroxyl (-OH) and slaine (such as ,-O thereof ^-m ⁺), amino (-NH ₂), nitro (-NO ₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as phenoxy group etc.), aryl alkyl [such as, cumenyl (-C (CH ₃) ₂phenyl); Benzyl (-CH ₂phenyl)], nitroso (-NO), acetylamino (-NHCOCH ₃), vinyl (-CH=CH ₂).Particularly preferred quinhydrones comprises the compound and hydrate thereof that are represented by above formula, wherein R ₁, R ₂, R ₃and R ₄separately be selected from: slaine (the e.g. ,-COO of carboxyl ^-m ⁺), acetate (-CH ₂and ester (-CH COOH) ₂cOOR), slaine (the such as ,-O of hydroxyl (-OH), hydroxyl ^-m ⁺), amino (-NH ₂), nitro (-NO ₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as, phenoxy group etc.), aryl alkyl [such as, cumenyl (-C (CH ₃) ₂phenyl), benzyl (-CH ₂phenyl)], nitroso (-NO), acetylamino (-NHCOCH ₃), vinyl (-CH=CH ₂).The example of quinhydrones suitable especially includes but not limited to, quinhydrones; Four chlorohydroquinones; 2-chlorohydroquinone; 2-bromohydroquinone; 2,5-dichloro hydroquinone; 2,5-bis-bromohydroquinone; Four bromohydroquinones; 2-methylnaphthohydroquinone; TBHQ; The two amyl hydroquinone of 2,5-; With 2-(2-chlorphenyl) quinhydrones hydrate.Particularly preferably quinhydrones and four chlorohydroquinones are more particularly preferably 2-(2-chlorphenyl) quinhydrones hydrates.Suitable quinhydrones is open in the U.S. Patent application of 2007/0213440 at such as publication number further, is included in by its full content by reference here.

Suitable benzoquinones comprises the compound and hydration compound thereof that following molecular formula represents.

Wherein, R ₁, R ₂, R ₃and R ₄separately be selected from: hydrogen, halogen group (F, CI, Br, I), alkyl, carboxyl (-COOH) and slaine (such as ,-COO thereof ^-m ⁺) and ester (-COOR), acetate (-CH ₂and ester (-CH COOH) ₂cOOR), formoxyl (-CHO), acyl group (-COR), acetyl group (-COCH ₃), carbonyl halide (-COX), sulfonic group (-8O ₃and ester (-SO H) ₃r), halosulfonyl groups (-SO ₂x), sulfinic acid base (-SO ₂h), alkyl sulphinyl (-SOR), carbamoyl (-CONH ₂), halogenated alkyl, cyano group (-CN), alkoxyl (-OR), hydroxyl (-OH) and slaine (such as ,-O thereof ^-m ⁺), amino (-NH ₂), nitro (-NO ₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as phenoxy group etc.), aryl alkyl [such as, cumenyl (-C (CH ₃) ₂phenyl); Benzyl (-CH ₂phenyl)], nitroso (-NO), acetylamino (-NHCOCH ₃), vinyl (-CH=CH ₂).Particularly preferred benzoquinones comprises the compound and hydrate thereof that are represented by above formula, wherein R ₁, R ₂, R ₃and R ₄separately be selected from: slaine (the such as ,-COO of carboxyl ^-m ⁺), acetate (-CH ₂and ester (-CH COOH) ₂cOOR), slaine (the such as ,-O of hydroxyl (-OH), hydroxyl ^-m ⁺), amino (-NH ₂), nitro (-NO ₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as, phenoxy group etc.), aryl alkyl [such as, cumenyl (-C (CH ₃) ₂phenyl), benzyl (-CH ₂phenyl)], nitroso (-NO), acetylamino (-NHCOCH ₃), vinyl (-CH=CH ₂).More particularly preferably methyl-p-benzoquinone and chloranil.Suitable benzoquinones is open in the U.S. Patent application of 2007/0213442 at such as publication number further, is included in by its full content by reference here.

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

Wherein, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇and R ₈separately be selected from: hydrogen, halogen group (F, CI, Br, I), alkyl, carboxyl (-COOH) and slaine (such as ,-COO thereof ^-m ⁺) and ester (-COOR), acetate (-CH ₂and ester (-CH COOH) ₂cOOR), formoxyl (-CHO), acyl group (-COR), acetyl group (-COCH ₃), carbonyl halide (-COX), sulfonic group (-SO ₃and ester (-SO H) ₃r), halosulfonyl groups (-SO ₂x), sulfinic acid base (-SO ₂h), alkyl sulphinyl (-SOR), carbamoyl (-CONH ₂), halogenated alkyl, cyano group (-CN), alkoxyl (-OR), hydroxyl (-OH) and slaine (such as ,-O thereof ^-m ⁺), amino (-NH ₂), nitro (-NO ₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as phenoxy group etc.), aromatic alkyl [such as, cumenyl (-C (CH ₃) ₂phenyl); Benzyl (-CH ₂phenyl)], nitroso (-NO), acetylamino (-NHCOCH ₃), vinyl (-CH=CH ₂).Particularly preferred quinhydrone comprises the compound and hydrate thereof that are represented by above formula, wherein R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇and R ₈separately be selected from: slaine (the such as ,-COO of carboxyl ^-m ⁺), acetate (-CH ₂and ester (-CH COOH) ₂cOOR), slaine (the such as ,-O of hydroxyl (-OH), hydroxyl ^-m ⁺), amino (-NH ₂), nitro (-NO ₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as, phenoxy group etc.), aryl alkyl [such as, cumenyl (-C (CH ₃) ₂phenyl), benzyl (-CH ₂phenyl)], nitroso (-NO), acetylamino (-NHCOCH ₃), vinyl (-CH=CH ₂).Particularly preferred quinhydrone also comprises the wherein R represented by above formula ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇and R ₈for the compound of hydrogen.Suitable quinhydrone is open in the U.S. Patent application of 2007/0213441 at such as publication number further, is included in by its full content by reference here.

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

Wherein, R ₁, R ₂, R ₃and R ₄separately be selected from: hydrogen, halogen group (F, CI, Br, I), alkyl, carboxyl (-COOH) and slaine (such as ,-COO thereof ^-m ⁺) and ester (-COOR), acetate (-CH ₂and ester (-CH COOH) ₂cOOR), formoxyl (-CHO), acyl group (-COR), acetyl group (-COCH ₃), carbonyl halide (-COX), sulfonic group (-SO ₃and ester (-SO H) ₃r), halosulfonyl groups (-SO ₂x), sulfinyl group (-SO ₂h), alkyl sulphinyl (-SOR), carbamoyl (-CONH ₂), halogenated alkyl, cyano group (-CN), alkoxyl (-OR), hydroxyl (-OH) and slaine (such as ,-O thereof ^-m ⁺), amino (-NH ₂), nitro (-NO ₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as phenoxy group, etc.), aromatic alkyl [such as, cumenyl (-C (CH ₃) ₂phenyl); Benzyl (-CH ₂phenyl)], nitroso (-NO), acetylamino (-NHCOCH ₃), vinyl (-CH=CH ₂).Suitable catechol is open in the U.S. Patent application of 2007/0213144 at such as publication number further, is included in by its full content by reference here.

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

Wherein, R ₁, R ₂, R ₃and R ₄separately be selected from: hydrogen, halogen group (F, CI, Br, I), alkyl, carboxyl (-COOH) and slaine (such as ,-COO thereof ^-m ⁺) and ester (-COOR), acetate (-CH ₂and ester (-CH COOH) ₂cOOR), formoxyl (-CHO), acyl group (-COR), acetyl group (-COCH ₃), carbonyl halide (-COX), sulfonic group (-SO ₃and ester (-SO H) ₃r), halosulfonyl groups (-SO ₂x), sulfinic acid base (-SO ₂h), alkyl sulphinyl (-SOR), carbamoyl (-CONH ₂), halogenated alkyl, cyano group (-CN), alkoxyl (-OR), hydroxyl (-OH) and slaine (such as ,-O thereof ^-m ⁺), amino (-NH ₂), nitro (-NO ₂), aryl (such as, phenyl, tolyl etc.), aryloxy group (such as phenoxy group etc.), aromatic alkyl [such as, cumenyl (-C (CH ₃) ₂phenyl); Benzyl (-CH ₂phenyl)], nitroso (-NO), acetylamino (-NHCOCH ₃), vinyl (-CH=CH ₂).Particularly preferably 2-nitro-resorcinol.Suitable resorcinol is open in the U.S. Patent application of 2007/0213144 at such as publication number further, is included in by its full content by reference here.

When rubber composition comprises one or more quinhydrones, benzoquinones, quinhydrone, catechol, when resorcinol or their combination, be present in the quinhydrones in described composition, benzoquinones, quinhydrone, catechol and/or resorcinol total amount typically are 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 for 0.1 weight portion of every 100 parts of base rubber within the range having a lower limit of or 0.15 weight portion or 0.25 weight portion or 0.3 weight portion or 0.375 weight portion and the upper limit is the amount in 0.5 weight portion of every 100 parts of base rubber or the scope of 1 weight portion or 1.5 weight portions or 2 weight portions or 3 weight portions.

In specific embodiment, softening accelerator is selected from reptazin zinc, reptazin, xylyl disulfide, Diphenyl disulfide ether, dixylyl disulfide, 2-nitro-resorcinol and their combination.

The proper types of base rubber, initator, coagent, filler and additive and amount are more completely at such as United States Patent (USP) 6,566,483,6,695,718,6,939,907,7,041,721 and 7,138, describe in 460, by reference its full content is included in here.Diene rubber compsns suitable is especially open in the U.S. Patent application of 2007/0093318 at such as publication number further, is included in by its full content by reference here.

Inner core is encapsulated by intermediate core, intermediate core is individual layer, bilayer or multilayer, and preferred gross thickness 0.005 or 0.010 or 0.020 or 0.025 or 0.035 or 0.040 or 0.045 inch and the upper limit is in the scope of 0.045 or 0.050 or 0.060 or 0.070 or 0.080 or 0.090 or 0.100 inch within the range having a lower limit of.

The outer surface hardness of intermediate core is 40 Shore C hardness or larger, or 70 Shore C hardness or larger, or 80 Shore C hardness or larger, or 85 Shore C hardness or larger, or 89 Shore C hardness or larger, or 90 Shore C hardness or larger, or 93 Shore C hardness or larger, or 95 Shore C hardness or larger, or 60 Shore D hardness or larger, or 63 Shore D hardness or larger, or 65 Shore D hardness or larger, or the hardness number of outer surface 40 or 45 or 50 or 80 or 85 or 89 Shore C hardness and the upper limit is in the scope of 80 or 85 or 90 or 93 or 95 Shore C hardness within the range having a lower limit of, wherein the upper limit is greater 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 and is 20 or 30 or 35 or 40 or 45 or 50 or 55 or 57 or 58 or 60 or 63 or 65 or 66 or 70 and the upper limit is the Shore D outer surface hardness of 60 or 65 or 66 or 70 or 72 or 75 or 80 or 85 or 90, wherein the upper limit is greater than lower limit (such as, when being instantly limited to 65, the upper limit is 66,70,72,75,80,85 or 90).In specific embodiment, intermediate core is single layer, and it has uniform hardness in whole layer.

Each intermediate core layer is formed by thermoplastic polymer composition.Suitable thermoplastic polymer composition for the formation of inner sandwich layer includes but not limited to, part and the ionomer neutralized completely and their blend, comprise HNP with part neutralize ionomeric blend (as at publication number be 2006/0128904 U.S. Patent application in disclosed in), HNP and extra thermoplasticity and thermosets are (as acid copolymer, engineered thermoplastic materials, based on the HNP of fatty acid/salt, polybutadiene, polyurethane, polyureas, polyester, the polymeric material of thermoplastic elastomer (TPE) and other routines) blend, and particularly at such as United States Patent (USP) 6, 653, 382, 6, 756, 436, 6, 777, 472, 6, 894, 098, 6, 919, 393 and 6, 953, ionomer compositions disclosed in 820.Suitable HNP composition is also included within such as United States Patent (USP) 6,653,382,6,756,436,6,777,472,6,894,098,6,919,393 and 6,953, disclosed in 820 those.Here by reference the full content of above-mentioned all documents is included in.The acid content (before neutralization) of preferred ionomer compositions is at 1wt% to 30wt%, or 5wt% to 20wt%.

What be also suitable for forming intermediate core layer is the graft copolymer of ionomer and polyamide, and the polymer of following non-ionomeric (comprises its homopolymers and copolymer, and they with at least one grafting or the functional group of copolymerization (as maleic anhydride, amine, epoxy radicals, isocyanate group, hydroxyl, sulfonic group, phosphonate group etc.) compatible derivative): polyester, particularly use compatible group as those of sulfonic group or phosphonate group modification, comprise poly-(PETP) of modification, poly-(butylene terephthalate) of modification, poly-(the terephthalic acid (TPA) 1 of modification, 2-propylene diester), poly-(the terephthalic acid (TPA) 1 of modification, 3-propylene diester), poly-(the aphthenic acids second diester) of modification, and at United States Patent (USP) 6, 353, 050, 6, 274, 298 and 6, 001, disclosed in 930 those, and their blend of two or more, polyamide, polyamide-ether and polyamide-ester, and at United States Patent (USP) 6,187,864,6,001,930 and 5,981, disclosed in 654 those, and their blend of two or more, thermosetting and thermoplastic polyurethane, polyureas, polyurethane-polyurea blend, and their two kinds or more kinds of blends, fluoropolymer, as United States Patent (USP) 5,691,066,6,747,110 and 7,009, disclosed in 002, and their two kinds or more kinds of blends, non-from poly-acid polymer, as E/Y-and E/X/Y-type copolymer, wherein E is alkene (such as, ethene), and Y is carboxylic acid, as acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid or itaconic acid, X is the vinyl esters of softening comonomer as aliphatic carboxylic acid, and wherein said acid has 2-10 carbon, and the carbon number of alkyl is the alkyl ether of 1-10, and alkyl alkylacrylate, the carbon number as alkyl 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 and 5,703, disclosed in 166 those, and their two kinds or more kinds of blends, polystyrene, 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, particularly use the polypropylene of grafting and the polyethylene of grafting of functional group's (maleic anhydride as sulfonic acid) modification, and their two kinds or more kinds of blends, the polyvinyl chloride of polyvinyl chloride and grafting, and their two kinds or more kinds of blends, polyvinyl acetate, preferably has the vinyl acetate being less than about 9% weight, and their two kinds or more kinds of blends, Merlon, the blend of PC/Abs, the blend of Merlon/polyurethane, the blend of polycarbonate/polyester, and their two kinds or more kinds of blends, polyvinyl alcohol, and their two kinds or more kinds of blends, polyethers, as poly (arylene ether), polyphenylene ether, the block copolymer of alkenyl arene and vinyl-arene and polyesteramide (amic ester), with their two kinds or more kinds of blends, polyimides, polyether-ketone, polyamidoimide, and their two kinds or more kinds of blends, polycarbonate/polyester copolymer and blend, and two or more combination any of above-mentioned polymer.What other were suitable is at United States Patent (USP) 5,919,100,6,872,774 and 7,074, and thermoplastic compounds disclosed in 137.Here by reference the full content of above-mentioned document is included in.

Can include but not limited to by the example of suitable thermoplastic that obtains of business: thermoplastic polyether block's acid amides, can obtain from Arkema Inc. business; ionomer resin, thermoplastic polyester elastomer, and with trade name hPF1000 and HPF 2000 sell from poly-material, they can obtain from E.I.du Pont de Nemours and Company business; ionomer, can obtain from ExxonMobil Chemical Company business; iO ionomeric ethylene acrylic copolymer, can obtain from The Dow Chemical Company business; ionomer resin, can obtain from A.Schulman Inc. business; based on the thermoplastic elastomer (TPE) of polyurethane, can obtain from BASF business; And polycarbonate/polyester blend, can obtain from SABIC Innovative Plastics business.

The other materials being suitable for being formed intermediate core layer comprises United States Patent (USP) 7,300, core composition disclosed in 364, here by reference to the full content introducing its disclosure.Such as, suitable material comprises the HNP neutralized with organic aliphatic acid and salt, metal cation or both combinations.Except with organic aliphatic acid and salt neutralization HNP, core compound also can comprise at least one swelling index at least about 40 elastomeric material.Preferred swelling index is at least about 50.Production resilience golf and be therefore applicable to that polymer of the present invention includes but not limited to can be from cB23, CB22 that Corporation business obtains, the BR60 that can obtain from Enichem business, and the 1207G that can obtain from Goodyear Corp. business.In addition, the typical Mooney viscosity of the rubber in golf prepared in accordance with the present invention as polybutadiene is about 40 to about 80, more preferably about 45 to about 65, and most preferably about 45 to about 55.Mooney viscosity is typically measured according to ASTM-D1646.

The thermoplastic compounds being suitable for being formed shell disclosed herein is also suitable for forming intermediate core layer.

In specific embodiment, intermediate core comprises the layer formed by two or more ionomeric blends.In particular aspects preferably, the blend of the 50wt%/50wt% of the ethylene/methacrylic acid that intermediate core layer is neutralized by two kinds of different parts is formed.In another particular aspects of present embodiment, intermediate core layer is formed by the composition comprising the first high acid levels ionomer and the second high acid levels ionomer blend, wherein the first high acid levels ionomer optionally neutralizes (such as with the cation different from the second high acid levels ionomer 8150 Hes the blend of the 50wt%/50wt% of 9120, can obtain from E.I.du Pont de Nemours and Company business), and wherein said composition optionally comprises one or more melt flow modifier (melt flow modifiers), as ionomer, Ethylene-acid copolymers or ester terpolymer.

In another specific embodiment, intermediate core comprises the layer formed by the blend of the polymer of the non-ionomeric of one or more ionomers and maleic anhydride graft.In particular aspects preferably, the polymer of non-ionomeric is metallocene catalyzed polymers.In another particular aspects preferably, intermediate core layer is formed by the poly blend of metallocene catalyst of the ethylene/methacrylic acid partly neutralized and maleic anhydride graft.

In another specific embodiment, intermediate core comprises at least one layer, and it is formed by being selected from following composition: part and the ionomer neutralized completely, polyester, polyamide, polyurethane, polyureas, polyurethane/polyurea blend, fluoropolymer and their two kinds or more kinds of blends.Special desirably United States Patent (USP) 6,872, " the non-non-ionomeric composition from poly-hardening polymer and at least one E/Y copolymer or E/X/Y terpolymer is comprised " disclosed in 774, with United States Patent (USP) 7,074, the rigid core of hard disclosed in 137 material, includes the full content that it discloses here by reference in.

In another specific embodiment, intermediate core comprises by the layer being selected from following composition and being formed: part and the ionomer neutralized completely, and their two kinds or more kinds of blends, optionally with the non-ionomeric polyblend of maleic anhydride graft; Polyester elastomer; Polyamide elastomer, and their two or more combination.

Intermediate core layer composition can flow with minimizing or when preventing molded (overmolding) with thermosetting diene compositions-treated or fusion.Optional process also can be included in molding forward direction raw material and add peroxide, or carries out molding post processing with such as crosslinker solution, electron beam, gamma radiation, isocyanates or amine aqueous solution process etc.When thermoset layer can to make at this layer of crosslinked temperature thereon about 5 to 30 minutes of molding time, this temperature typically is 280 °F to 360 °F this process and can prevents intermediate layer from melting and flowing, or seam (equator) place " leakage " goes out in a mold.

Suitable thermoplasticity intermediate core layer composition is further at such as United States Patent (USP) 5,919,100,6,872,774 and 7,074, open in 137, includes the full content that it discloses here by reference in.

The outer core of intermediate core is encapsulated, outer core is individual layer, bilayer or multilayer, and preferred gross thickness 0.005 or 0.010 or 0.020 or 0.025 or 0.030 or 0.035 inch and the upper limit is in the scope of 0.035 or 0.040 or 0.045 or 0.050 or 0.060 or 0.070 or 0.075 or 0.080 or 0.100 or 0.150 inch within the range having a lower limit of.In specific embodiment, the gross thickness of outer core is 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 larger, or 45 Shore C hardness or larger, or 50 Shore C hardness or larger, or 60 Shore C hardness or larger, or 70 Shore C hardness or larger, or 75 Shore C hardness or larger, or 80 Shore C hardness or larger, or 85 Shore C hardness or larger, or 90 Shore C hardness or larger, or the hardness number of outer surface 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 or 90 Shore C hardness and the upper limit is in the scope of 60 or 70 or 75 or 80 or 82 or 85 or 90 or 92 or 93 or 95 Shore C hardness within the range having a lower limit of, wherein the upper limit is greater than lower limit (such as, when being instantly limited to 70, the upper limit is 75, 80, 82, 85, 90, 92, 93 or 95).Outer sandwich layer preferably have 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 be 60 or 62 or 64 or 65 or 66 or 70 scope in Shore D outer surface hardness.In specific embodiment, the outer surface hardness of outer core is greater than the outer surface hardness of inner core.In particular aspects preferably, the outer surface hardness of outer core differs 5 Shore C stiffness units or larger with the outer surface hardness of inner core, or 10 Shore C stiffness units or larger, or 15 Shore C stiffness units or larger, or 20 Shore C stiffness units or larger.In another specific embodiment, outer core is single layer, its case hardness 20 or 25 or 30 or 35 or 40 or 50 Shore C hardness and the upper limit is in the scope of 60 or 70 or 80 Shore C hardness within the range having a lower limit of, and by being selected from United States Patent (USP) 7,537,530 and 7,537, disclosed in 529, those rubber composition is formed, and the full content disclosed by reference is here included in.

Each outer sandwich layer is preferably formed by rubber composition.Suitable rubber composition comprise aforementioned disclose for the formation of inner sandwich layer those.Each outer sandwich layer can be the rubber composition identical or different from the composition being used for being formed inner sandwich layer.Inner sandwich layer or outer sandwich layer can comprise the curing agent of 1 to 100phr further.Preferably, if there is curing agent, curing agent is present in outer core compound, instead of in inner sandwich layer composition.Suitable curing agent includes but not limited to ionomer, acid copolymer and terpolymer, polyamide and polyester.Curing agent is further at such as United States Patent (USP) 6,120,390 and 6,284, and open in 840, the full content disclosed by reference is here included in.Using trans-polyisoprene can also be added (such as, TP-301 using trans-polyisoprene, can from Kuraray Co., Ltd. business obtains) or trans butadiene rubber to increase the rigidity of sandwich layer and/or to improve cold forming character, this by molding easier in golf ball manufacturing process outward sandwich layer half shell improve machinability.When being contained in core compound, curing agent preferably exists with the amount of 5-10pph.

Multilayer core of the present invention preferably has unique core hardness gradient, and wherein maximum core hardness is positioned at the specified distance from the outmost surface of core.In specific embodiment, maximum core hardness is positioned at the following distance radially-inwardly measured from the outer surface of this core, this distance within the range having a lower limit of 0.10 or 0.15 or 0.20 or 0.25 or 0.50mm and the upper limit be 2.50 or 5.00 or 6.00 or 6.50 or 7.00 or 8.00mm scope in.In another specific embodiment, maximum core hardness higher than the outer surface hardness 5% or larger of outer sandwich layer, or 10% or larger, or 15% or larger, or 20% or larger.

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 be 1.18 or 1.25 or 1.30 or 1.40 or 1.50 or 5.00g/cc scope 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 individual layer, and the proportion of outer sandwich layer is identical with the proportion of intermediate core layer, substantially the same or be greater than the proportion of intermediate core layer.In particular aspects preferably, the proportion of outer sandwich layer is greater than the proportion of inner sandwich layer, and outer sandwich layer is formed by densified thin layer composition.Densified thin layer composition comprises such as by United States Patent (USP) 6,494, disclosed in 795 those, the full content disclosed by reference is here included in.Be suitable for also having by United States Patent (USP) 6,149,535 and 6 as densified thin layer composition equally, 152, thermoplastic disclosed in 834, the full content disclosed by reference is here included in.In specific embodiment, outer core is the densified thin layer of individual layer, preferably its proportion is 1.2 or larger, or 1.5 or larger, or 1.8 or larger, or two or more, and its thickness 0.001 or 0.005 or 0.010 or 0.020 inch and the upper limit is in the scope of 0.020 or 0.030 or 0.035 or 0.045 or 0.050 or 0.060 inch within the range having a lower limit of.This densified thin layer preferably as coatings such as liquid solution, dispersion, paint, paste, gel, fused mass, if any the natural or non-natural rubber latex of load or filling, polyurethane, polyureas, epoxy resin, polyester, any reactivity or non-reacted coating or cast material; Then solidify, dry or be evaporated to equilibrium solid level.Densified thin layer also can by compression or injection moulding, RIM, casting, spraying, dipping, powder coated or on inner core any means of deposition materials formed.Densified thin layer also can have for load the thermoplastic polymer increasing the filler of proportion, fiber, thin slice or particle, it can be coated with as shallow layer, and meet aforementioned preferred specific gravity balance.A particular instance of densified thin layer, it is obtained by soft polybutadiene and tungsten powder compression moulding, 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 comprises the material that any reaction forms solid, as epoxy resin, styrenated polyester, polyurethane or polyureas, liquid polybutadiene, silicone rubber, silicate gel, agar gel etc.Casting, RIM, dipping and spraying are the methods of the reactive densified thin layer of preferred coating.Non-reactive material comprises melting or can the polymer of liquid form, any combination of the powder be dissolved or dispersed in solvent flashing.Densified thin layer is more completely open in the U.S. Patent application of 2005/0059510 at publication number, and the full content disclosed by reference is here included in.

The parameter that the distribution of weight that can change the core disclosed here is expected to realize some, as the speed of rotation, ball hardness and initial velocity.

In specific embodiment, the invention provides core assembly, it is made up of inner core and intermediate core, and wherein, owing to using very soft inner core and adamantine intermediate core layer, core assembly has the low-down speed of rotation.Therefore, in particular aspects preferably, the moment of inertia (" MOI ") of the core assembly be made up of inner core and intermediate core is 86gcm ²or larger, or 87gcm ²or larger, or 88gcm ²or it is larger.Measure in the MOI-005-104 the moment of inertia instrument that MOI manufactures at the Inertia Dynamics by Connecticut State Collinsville.This instrument connects PC, by COMM port communication and by MOI instrument software 1.2 version drive.

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

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

Multilayer core is encapsulated by shell, shell can be individual layer, the shell of bilayer or multilayer, preferred gross thickness 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 in the scope of 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 within the range having a lower limit of, wherein the upper limit is greater 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 0.010 or 0.015 or 0.020 or 0.025 or 0.027 or 0.029 or 0.030 inch and the upper limit is in the scope of 0.030 or 0.033 or 0.034 or 0.035 or 0.040 or 0.050 inch within the range having a lower limit of, and outer surface hardness 20 or 30 or 35 or 40 or 45 or 50 or 52 or 55 or 58 Shore D hardness and the upper limit is in the scope of 55 or 58 or 60 or 65 or 70 Shore D hardness within the range having a lower limit of, wherein the upper limit is greater than lower limit (such as, when being instantly limited to 58 Shore D hardness, the upper limit is 60 or 65 or 70 Shore D hardness), or outer surface hardness is 65 Shore D hardness or lower, or 60 Shore D hardness or lower, or be less than 60 Shore D hardness.

Shell is preferably simple layer, it is formed by the composition with certain material hardness, described hardness 30 or 35 or 40 or 45 or 50 or 52 or 55 or 58 Shore D hardness and the upper limit is in the scope of 55 or 58 or 60 or 65 Shore D hardness within the range having a lower limit of, wherein the upper limit is greater than lower limit (such as, when being instantly limited to 58 Shore D hardness, the upper limit is 60 or 65 Shore D hardness).Shell composition preferably have according to ASTMD6272-98 code B measure within the range having a lower limit of 5,000 or 12,000psi and the upper limit be 24,000 or 50,000psi scope in flexural modulus.

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

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 and HPF 2000, can obtain from E.I.du Pont de Nemours and Company business; ionomer, can obtain from ExxonMobil Chemical Company business; iO ionomeric ethylene acrylic copolymer, can obtain from The Dow Chemical Company business; And ionomer resin, can obtain from A.Schulman Inc. business); Polyethylene, comprises such as low density polyethylene (LDPE), LLDPE and high density polyethylene (HDPE); Polypropylene; Rubber toughened olefin polymer; Acid copolymer, 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 the graft copolymer of ionomer and polyamide, comprise, such as, thermoplastic polyether block's acid amides, can obtain from Arkema Inc business; Crosslinked using trans-polyisoprene and their blend; Based on the thermoplastic elastomer (TPE) of polyester, as can obtain from E.I.du Pont de Nemours and Company business; Based on the thermoplastic elastomer (TPE) of polyurethane, as can obtain from BASF business; Synthesis or natural vulcanized rubber; And their combination.

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

Polyurethane shell composition of the present invention comprises those that formed by the product of at least one polyisocyanates and at least one curing agent.Curing agent can comprise such as, one or more diamines, one or more polyalcohols or their combination.At least one polyisocyanates can be combined with one or more polyalcohols and form prepolymer, and then this prepolymer is combined with at least one curing agent.Thus, when describing polyalcohol here, they are suitable for being used in one or both components of polyurethane material, namely as a part for prepolymer, with in curing agent.Curing agent comprises polyol curatives, and it is preferably selected from: ethylene glycol; Diglycol; Polyethylene glycol; Propane diols; Polypropylene glycol; Low-molecular-weight polytetramethylene ether diol; Two (2-hydroxyl-oxethyl) benzene of 1,3-; Two [2-(2-hydroxyl-oxethyl) ethyoxyl] benzene of 1,3-; Two { 2-[2-(2-hydroxyl-oxethyl) ethyoxyl] ethyoxyl } benzene of 1,3-; BDO; 1,5-PD; 1,6-hexylene glycol; Resorcinol-two (beta-hydroxy ethyoxyl) ether; Quinhydrones-two (beta-hydroxy ethyl) ether; Trimethylolpropane; And their combination.

The polyurethane shell composition that the present invention is suitable for also comprises those that formed by the product of at least one isocyanates and at least one curing agent, or those formation by the product of at least one isocyanates, at least one polyalcohol and at least one curing agent.Preferred isocyanates comprises and is selected from following those: 4,4 '-methyl diphenylene diisocyanate, poly-4, the liquid 4 of 4 '-methyl diphenylene diisocyanate, carbodiimide modified, 4 '-methyl diphenylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanate, to phenylene vulcabond, toluene di-isocyanate(TDI), IPDI, to methylxylene diisocyanate, a methylxylene diisocyanate, adjacent methylxylene diisocyanate and their combination.Preferred polyalcohol comprises and is selected from following those: PPG, hydroxy-end capped polybutadiene, PEPA, polycaprolactone polyol, polycarbonate polyol and their combination.Preferred curing agent comprises polyamine curing agent, polyol curatives and their combination.Particularly preferably polyamine curing agent.Preferred polyamine curing agent comprises, such as, and 3,5-dimethyl sulphur-based-2,4-toluenediamine or its isomers; 3,5-diethyltoluene-2,4-diamines or its isomers; 4,4 '-bis-(Zhong Ding is amino)-diphenyl methane; Isosorbide-5-Nitrae-bis-(Zhong Ding is amino) benzene, 4,4 '-methylene-bis-(2-chloroaniline); 4,4 '-methylene-bis-(chloro-2, the 6-diethylanilines of 3-); Two p-aminobenzoic acid 1,3-PD esters; Polytetramethylene ether-two P aminobenzoates; N, N '-dialkyl group MDA; P, p '-methylene dianiline (MDA); Phenylenediamine; 4,4 '-methylene-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-diethyl aniline); And their combination.

The present invention is not limited to use specific polyisocyanates in shell composition.Suitable polyisocyanates includes but not limited to, 4, and the liquid MDI, 4 of 4 '-methyl diphenylene diisocyanate (" MDI "), polymeric MDI, carbodiimide modified, 4 '-dicyclohexyl methyl hydride diisocyanate (" H ₁₂mDI "), to phenylene vulcabond (" PPDI "), toluene di-isocyanate(TDI) (" TDI "), 3; 3 '-dimethyl-4,4 '-diphenylene vulcabond (" TODI "), IPDI (" IPDI "), cyclohexane diisocyanate (" HDI "), naphthalene diisocyanate (" NDI "); XDI (" XDI "); To tetramethylxylene diisocyanate (p-TMXDI "); Between tetramethylxylene diisocyanate (" m-TMXDI "); Ethylidene diisocyanate; Propylidene-1,2-vulcabond; Tetramethylene-Isosorbide-5-Nitrae-vulcabond; Cyclohexyl diisocyanate; 1,6-hexamethylene diisocyanate (" HDI "); Dodecane-1,12-vulcabond; Cyclobutane-1,3-vulcabond; Cyclohexane-1,3-vulcabond; Cyclohexane-Isosorbide-5-Nitrae-vulcabond; 1-isocyanate group-3,3,5-trimethyl-5-isocyanatometyl cyclohexylamine; Methyl cyclohexane support vulcabond; The triisocyanate of HDI; Triisocyanate, aphthacene vulcabond, naphthalene diisocyanate, the anthracene vulcabond of 2,4,4-trimethyl-1,6-hexane diisocyanate (" TMDI "); And their combination.Those skilled in the art know polyisocyanates and have more than one NCO, such as, and two, three and four NCOs.Preferably, polyisocyanates is selected from MDI, PPDI, TDI and their combination.More preferably, polyisocyanates comprises MDI.Be to be understood that, as used herein, term " MDI " comprises 4, the liquid MDI of 4 '-methyl diphenylene diisocyanate, polymeric MDI, carbodiimide modified and their combination, in addition, the vulcabond of use can be " low free monomer ", and one of ordinary skill in the art can understand, it has " dissociating " monomeric diisocyanate base of reduced levels compared to conventional vulcabond, and namely composition of the present invention typically has the free monomer group being less than about 0.1%.The example of the vulcabond of " low free monomer " includes 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 being less than 14%.Preferably, at least one polyisocyanates has the NCO being no more than 8.5%, is more preferably 2.5% to 8.0%, is even more preferably 4.0% to 7.2%, and most preferably 5.0% to 6.5%.

The invention is not restricted to use specific polyalcohol in shell composition.In one embodiment, the molecular weight of polyalcohol is about 200 to about 6000.Exemplary polyalcohol includes but not limited to, PPG, hydroxy-end capped polybutadiene (comprising part/complete all hydrogenated derivative), PEPA, polycaprolactone polyol and polycarbonate polyol.Particularly preferably polytetramethylene ether diol (" PTMEG "), polyethylene glycol propane diols, polyoxypropylene diols and their combination.Hydrocarbon chain can have saturated or unsaturated bond, and replaces or unsubstituting aromatic yl and cyclic group.Preferably, polyalcohol of the present invention comprises PTMEG.Suitable PEPA includes but not limited to, polyethylene glycol adipate, poly adipate succinic acid ester, poly-adipate glycol propylene glycol ester, phthalic acid-1,6-hexylene glycol ester and their combination.Hydrocarbon chain can have saturated or unsaturated bond, or substituted or unsubstituted aryl and cyclic group.Suitable polycaprolactone polyol includes but not limited to, 1, the PCL that the PCL that the PCL that the PCL that the PCL that 6-hexylene glycol causes, diethylene glycol (DEG) cause, trimethylolpropane cause, neopentyl glycol cause, BDO cause and their combination.Hydrocarbon chain can have saturated or unsaturated bond, or replaces or unsubstituting aromatic yl and cyclic group.Suitable Merlon includes but not limited to, polyphthalate carbonate.Hydrocarbon chain can have saturated or unsaturated bond, or replaces or unsubstituting aromatic yl and cyclic group.

Polyamine fixative is also suitable for being used in the curing agent of urethane composition, and has had been found that the anti-cutting that can promote gained ball, shear resistant and impact resistance.Preferred polyamine fixative includes but not limited to, 3,5-dimethyl sulphur-based-2,4-toluenediamine and isomers thereof; 3,5-diethyltoluene-2,4-diamines and isomers thereof, as 3,5-diethyltoluene-2,6-diamines; 4,4 '-bis-(Zhong Ding is amino)-diphenyl methane; Isosorbide-5-Nitrae-bis-(Zhong Ding is amino) benzene, 4,4 '-methylene-bis-(2-chloroaniline); 4,4 '-methylene-bis-(chloro-2, the 6-diethylanilines of 3-); Polytetramethylene ether-two P aminobenzoates; N, N '-dialkyl group MDA; P, p '-methylene dianiline (MDA) (" MDA "); M-phenylene diamine (MPD) (" MPDA "); 4,4 '-methylene-bis-(2-chloroaniline) (" 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-diethyl aniline); Two p-aminobenzoic acid 1,3-PD esters; And their combination.Preferably, curing agent of the present invention comprises 3,5-dimethyl sulphur-based-2,4-toluenediamine and isomers thereof, as ETHACURE300.Suitable polyamine fixative comprises primary amine and secondary amine, and it preferably has the weight average molecular weight of scope in about 64 to about 2000.

One of at least can join in urethane composition in glycol, triol, tetrol or hydroxy-end capped fixative.Suitable glycol, triol and four alcohol groups comprise ethylene glycol; Diethylene glycol (DEG); Polyethylene glycol; Propane diols; Polypropylene glycol; Low-molecular-weight polytetramethylene ether diol; Two (2-hydroxyl-oxethyl) benzene of 1,3-; Two [2-(2-hydroxyl-oxethyl) ethyoxyl] benzene of 1,3-; Two { 2-[2-(2-hydroxyl-oxethyl) ethyoxyl] ethyoxyl } benzene of 1,3-; BDO; 1,5-PD; 1,6-hexylene glycol; Resorcinol-two (4-hydroxyethyl) ether; Quinhydrones-two (4-hydroxyethyl) ether; And their combination.Preferably hydroxy-end capped fixative comprises ethylene glycol; Diethylene glycol (DEG); BDO; 1,5-PD; 1,6-hexylene glycol, trimethylolpropane and their combination.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 understand like this.

Hydroxy-end capped group that is that can comprise one or more saturated, undersaturated, aromatics with amine fixative and ring-type.In addition, hydroxy-end cappedly one or more halogen group can be comprised with amine fixative.Urethane composition can be formed by the blend of curing agent or mixture.But if needed, urethane composition can be formed by single curing agent.

Any method that those of ordinary skill in the art know may be used to polyisocyanates of the present invention, polyalcohol and curing agent are combined.A kind of common method, is called as one step process in this area, comprises and mix polyisocyanates, polyalcohol and curing agent simultaneously.The method obtains the mixture of heterogeneous body (more random), and makes the control of producer to the molecular structure of resulting composition lower.Preferred mixed method is called as prepolymer process.In the method, before adding curing agent, mixing polyisocyanates and polyalcohol separately.This method provide the mixture compared with homogeneous, obtain more consistent polymer composition.

Suitable polyurethane is further at such as United States Patent (USP) 5,334,673,6,506,851,6,756,436,6,867,279,6,960,630 and 7,105, and open in 623, the full content disclosed by reference is here included in.Suitable polyureas is open in the U.S. Patent application of 60/401,047 at such as United States Patent (USP) 5,484,870 and 6,835,794 and application number further, and the full content disclosed by reference is here included in.Suitable polyurethane-polyurea shell material comprises polyurethane/polyurea blend and comprises the copolymer of carbamate and urea segment, if publication number is disclosed in the U.S. Patent application of 2007/0117923, the full content disclosed by reference is here included in.

The composition comprising ionomer or two or more ionomeric blends is also particularly suitable for forming shell.Preferred ionomer shell composition comprises:

A () comprises " high acid levels ionomer (high acid ionomer) " (namely having the acid content being greater than 16wt%), as composition;

B (such as, () comprise the polymer of the non-ionomeric of high acid levels ionomer and maleic anhydride graft functionalized polymeric) composition.The blend of the polymer of particularly preferred high acid levels ionomer and maleic anhydride graft is the Surlyn of 84wt%/16wt% with blend.The blend of the polymer of high acid levels ionomer and maleic anhydride graft is further at such as United States Patent (USP) 6,992,135 and 6,677, and open in 401, the full content disclosed by reference is here included in;

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

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

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

F () comprises the composition of blend, it comprises melt flow modifiers alternatively;

G () comprises the composition of the first high acid levels ionomer and the ionomeric blend of the second high acid levels, wherein the first high acid levels ionomer cation different from the second high acid levels ionomer neutralizes (such as 50/50 with blend), comprise one or more melt flow modifiers alternatively as ionomer, Ethylene-acid copolymers or the terpolymer with ester; And

H () comprises the ionomeric composition of ethylene acid/ester of the first high acid levels ionomer and the ionomeric blend of the second high acid levels and 0-10wt%, wherein the first high acid levels ionomer cation different from the second high acid levels ionomer neutralizes, and ethylene acid/ester ionomer neutralizes with from the first high acid levels ionomer or the identical cation of the second high acid levels ionomer or neutralizes (such as 40-50wt%'s with the different cation of the first and second high acid levels ionomers 40-50wt%'s with 0-10wt%'s blend).

with be the E/MAA copolymer of different brackets, wherein acid groups sodium ion part neutralizes. with be the E/MAA copolymer of different brackets, wherein acid groups zinc ion part neutralizes. be E/MAA copolymer, wherein acid groups lithium ion part neutralizes. be the magnesium ionomer of very low modulus, there is medium acid content. be E/MAA copolymer resin, it is nominally and obtains with the methacrylic acid of 15wt%. ionomer, polymer and copolymer all can obtain from E.I.du Pont de Nemours and Company business.

Ionomer shell composition can with nonionic thermoplastic resin, specifically, this is the character in order to control product.The example of suitable non-ionic thermal plastic resin includes but not limited to, polyurethane, polyether ester, polyamide ether, polyethers urea, thermoplastic polyether block's acid amides are (such as block copolymer, can obtain from Arkema Inc. business), SBS, styrene (Ethylene/Butylene)-styrene block copolymer, polyamide, polyester, polyolefin (such as, polyethylene, polypropylene, ethylene-propylene copolymer, polyethylene-(methyl) acrylate, polyethylene-(methyl) acrylic acid, there is the functionalized polymeric of maleic anhydride graft functionalized polymeric, can obtain from E.I.duPont de Nemours and Company business, the polymer of epoxy functional, elastomer (such as, ethylene propylene diene monomer rubber, the polyolefin of metallocene catalyst) and the abrasive flour of thermo-setting elastomer.

Ionomer golf spherical shell composition can comprise flow ability modifying agent, e.g., but is not limited to, acid copolymer resin, especially acid copolymer resin can obtain from E.I.du Pontde Nemours and Company business.

Suitable ionomer shell material is further at such as United States Patent (USP) 6,653,382,6,756,436,6,894,098,6,919,393 and 6,953, and open in 820, the full content disclosed by reference is here included in.

Shell composition can comprise one or more of fillers, the filler for rubber composition of the present invention provided as above-mentioned (such as, titanium dioxide, barium sulfate etc.), and/or additive, as colouring agent, fluorescer, brightening agent, antioxidant, dispersant, UV absorbent, light stabilizer, plasticizer, surfactant, compatilizer, blowing agent, reinforcing agent, releasing agent etc.

In specific embodiment, shell is the simple layer formed by full aliphatic polyurea.In another specific embodiment, shell is the simple layer that polyurea composition disclosed in the U.S. Patent application of 2009/0011868 is formed by being preferably selected from publication number, and the full content disclosed by reference is here included in.

Suitable shell material and structure also comprise, but being not limited to, is U.S. Patent application, the United States Patent (USP) 5,919 of 2005/0164810 at publication number, 100,6,117,025,6,767,940 and 6,960,630 and publication number for disclosed in the PCT application of WO00/23519 and WO00/29129 those, the full content disclosed by reference is here included in.

Aqueous vapor barrier layer is set between core and shell alternatively.Aqueous vapor barrier layer is further at such as United States Patent (USP) 6,632,147,6,838,028,6,932,720,7,004,854 and 7,182,702 and publication number be open in the U.S. Patent application of 2003/0069082,2003/0069085,2003/0130062,2004/0147344,2004/0185963,2006/0068938,2006/0128505 and 2007/0129172, the full content disclosed by reference is here included in.

Golf ball layer except innermost layer and outermost one or more layers be optionally the layer of non-uniform thickness.In order to object of the present disclosure, " layer of non-uniform thickness " refers to such layer, and it has projection, net, rib etc. and is positioned at the varied in thickness this layer making this layer.The layer of non-uniform thickness preferably have following in one or more: multiple projections placed on it, multiple longitudinal net, multiple horizontal net or multiple circle-shaped net.In the specific embodiment of one, the layer of non-uniform thickness comprises the multiple projections being placed in its outer surface and/or inner surface.Projection can be integrally manufactured with this layer, or can manufacture separately and be then attached on this layer.Projection can have any shape or section, include but not limited to, trapezoidal, sinusoidal, dome-shaped, stairstepping, cylindrical, conical, frustroconical, rectangle, the pyramid with polygon bottom surface, truncated pyramid shape or polyhedron shape.The suitable shape of inner side and outer side projection and section are also included in United States Patent (USP) 6,293, disclosed in 877 those, the full content disclosed by reference is here included in.In another specific embodiment, the layer of non-uniform thickness comprises the circular net in multiple inner side and/or the outside arranged thereon.In the particular aspects of present embodiment, the existence of net adds the rigidity of nonuniform thick layer.Net can be longitudinal net, horizontal net or circle-shaped net.

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

The layer of non-uniform thickness is open in the U.S. Patent application of 2008/0248898 at such as United States Patent (USP) 6,773,364 and publication number further, and the full content disclosed by reference is here included in.

Except above-mentioned disclosed material, 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, polyesteramide, polyetheramides, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polyarylate, polyacrylate, polyphenylene oxide, impact modification polyphenylene oxide, high-impact polystyrene, diallyl phthalate polymer, metallocene catalyzed polymers, styrene-acrylonitrile (SAN), olefin-modified SAN, acrylonitrile-styrene-acrylonitrile, phenylethylene-maleic anhydride (S/MA) polymer, styrol copolymer, functionalized styrene copolymer, functionalized styrene terpolymer, styrene copolymer, cellulosic polymer, liquid crystal polymer (LCP), Ethylene-Propylene-Diene rubber (EPDM), vinyl-vinyl acetate copolymer (EVA), ethylene propylene rubber (EPR), ethylene vinyl acetate, polyureas and polysiloxanes.Suitable polyamide as additional materials in composition disclosed herein also comprises the resin obtained in the following manner: (1) (a) dicarboxylic acids is as oxalic acid, adipic acid, decanedioic acid, terephthalic acid (TPA), M-phthalic acid or 1,4 cyclohexane dicarboxylic acids and (b) diamine are as the polycondensation of ethylenediamine, butanediamine, pentanediamine, hexamethylene diamine or decamethylene diamine, Isosorbide-5-Nitrae-cyclohexyl diamine or m-xylene diamine; (2) cyclic lactames is as the ring-opening polymerisation of epsilon-caprolactams or omega-lauric lactam; (3) amino carboxylic acid is as the polycondensation of 6-aminocaprolc acid, 9 aminononanoic acid, 11-aminoundecanoic acid or 12-aminolauric acid; Or (4) copolymerization of cyclic lactames and dicarboxylic acids and diamine.The object lesson of suitable polyamide comprises nylon 6, nylon66 fiber, NYLON610, nylon 11, nylon 12, the nylon of copolymerization, nylon MXD 6 and nylon 46.

Other preferred materials being suitable for additional materials in golf composition disclosed in being used as here comprise Skypel polyester elastomer, can obtain from the SKChemicals business of Korea S; diblock and triblock copolymer, can obtain from the Kuraray Corporation business of Japanese Kurashiki; And diblock and triblock copolymer, can obtain from the KratonPolymers LLC business in Houston city, Texas.

Ionomer is also suitable for composition disclosed herein blended very much.Ionomer resin that is that suitable ionomer comprises alpha-olefin/copolymers of unsaturated carboxylic acids type or terpolymer type.Copolymers ionomers is by with in metal ion and alpha-olefin and have the α of 3-8 carbon atom, and at least part of carboxyl in the copolymer of beta-unsaturated carboxylic acid obtains.Terpolymer type ionomer is by with in metal ion and alpha-olefin, have the α of 3-8 carbon atom, and beta-unsaturated carboxylic acid and have the α of 2-22 carbon atom, at least part of carboxyl in the terpolymer of beta-unsaturated carboxylic acid ester obtains.The suitable example for copolymer type and the ionomeric alpha-olefin of terpolymer type comprises ethene, propylene, 1-butylene and 1-hexene.The suitable example for copolymer type and the ionomeric unsaturated carboxylic acid of terpolymer type comprises acrylic acid, methacrylic acid, ethylacrylic acid, α-chloro-acrylicacid, butenoic acid, maleic acid, fumaric acid and itaconic acid.Copolymer type and terpolymer type ionomer comprise the ionomer with different acid contents and sour degree of neutralization, and they are neutralized by unit price described herein or bivalent cation.Be suitable for can the business ionomer that obtain comprise blended with composition disclosed herein ionomer resin, can obtain from E.I.du Pont deNemours and Company business, and ionomer, can obtain from ExxonMobilChemical Company business.

Silicone material is also highly suitable for composition disclosed herein blended.Suitable silicone material comprises the monomer, oligomer, prepolymer and the polymer that add or do not add reinforcer.One type of suitable silicone material can combine the thiazolinyl that at least 1 has at least 2 carbon atoms in their molecule.The example of these thiazolinyls includes but not limited to, vinyl, pi-allyl, cyclobutenyl, pentenyl, hexenyl and decene base.Alkenyl-functional groups can be positioned at any position of silicone structure, comprises an end position or two end positions of this structure.The organic group of remaining in this component (such as, non-thiazolinyl) and silicon bonding is independently selected from the alkyl of not fatty race unsaturated part or halo alkyl.These nonrestrictive example comprises: alkyl, as methyl, ethyl, propyl group, butyl, amyl group and hexyl; Cycloalkyl, as cyclohexyl and suberyl; Aryl, as phenyl, tolyl and xylyl; Aralkyl, as benzyl and phenethyl; And haloalkyl, as 3,3,3-tri-fluorinated propyl and chloromethyl.The another kind of type of suitable silicone material has the alkyl of the unsaturated part of not fatty race.Object lesson comprises: the dimethyl siloxane-methyl hexenyl silicone copolymers of trimethylsiloxy group end-blocking; The dimethyl siloxane-methyl hexenyl silicone copolymers of dimethyhexenes base siloxy end-blocking; The dimethyl siloxane-methyl vinyl siloxane copolymer of trimethylsiloxy group end-blocking; Methyl phenyl siloxane-dimethyl siloxane-methyl the vinyl siloxane copolymer of trimethylsiloxy group end-blocking; The dimethyl polysiloxane of dimethylvinylsiloxy siloxy end-blocking; The dimethyl siloxane-methyl vinyl siloxane copolymer of dimethylvinylsiloxy siloxy end-blocking; The methyl phenyl silicone of dimethyl ethenyl siloxy end-blocking; Methyl phenyl siloxane-dimethyl siloxane-methyl the vinyl siloxane copolymer of dimethyl ethenyl siloxy end-blocking; And above-mentioned listed copolymer, wherein at least one group is dimethyl hydroxyl siloxy.Be suitable for can the business example of silicone that obtain comprise blended with composition disclosed herein silicone rubber, can obtain from the Dow Corning Corporation business of state of Michigan Midland; silicone rubber, can obtain from the General Electric Company business of New York Waterford; And silicone, can obtain from the Wacker Chemie AG business of Germany.

The copolymer of other types also can join in golf composition disclosed herein.Such as, the suitable copolymer comprising epoxy monomer comprises SBS, and wherein polybutadiene block comprises epoxy radicals, and SIS, and wherein polyisoprene blocks comprises epoxy radicals.ESBS A1005, ESBS A1010, ESBS A1020, ESBS AT018 and ESBS AT019 epoxidized styrene-butadiene-styrene block copolymer can be comprised by the example of epoxy-functional copolymer that obtains of business, can obtain from the Daicel ChemicalIndustries Inc. business of Japan.

For the formation of each golf ball layer of the present invention from poly-composition can with nonionic thermoplastic resin, specifically, this is to control properties of product.The example of suitable non-ionic thermal plastic resin includes but not limited to, polyurethane, polyether ester, polyamide ether, polyethers-urea, thermoplastic polyether block's acid amides (can obtain from Arkema Inc. business), SBS, styrene (Ethylene/Butylene) styrene block copolymer, polyamide, polyester, polyolefin are (such as, polyethylene, polypropylene, ethylene-propylene copolymer), the abrasive flour of ethene-(methyl) acrylate, ethene-(methyl) acrylic acid, the functionalized polymeric with maleic anhydride graft and epoxidation etc., elastomer (such as, the polyethylene of EPDM, metallocene catalyst) and thermo-setting elastomer.

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

The invention is not restricted to the technique of any specific formation golf ball layer.Should be appreciated that described each layer can be formed by any suitable technology, comprise injection moulding, compression moulding, casting and reaction injection molding(RIM).Especially, thermosetting thin layer can be formed by the method for the formation sulfuration of any conventional or other cross-linked rubber thin layers, includes but not limited to the casting of compression molding, rubber injection mold, liquid rubber and lamination.

When adopting injection moulding, said composition easily can be supplied to pellet or the granular form in the trunnion of injection machine typically, and, said composition is 150 °F to 600 °F in temperature in injection machine, is preferably in 200 °F to the thermotank under 500 °F by screw melting and transmission.The composition of fusing is finally injected in closed die cavity, and this die cavity can cool at ambient temperature or at elevated temperatures, but typically, and mold cools down is to the temperature of 50 °F to 70 °F.Stop 1 second to 300 seconds in the mould closed, preferably after 20 seconds to 120 seconds, core and/or core are added that one or more additional wick or shell take out from mould, makes it cool in the temperature of environment temperature or reduction, or be placed in the dry ice etc. of cooling fluid as water, frozen water, solvent.

When adopting compression molding to form core, first said composition forms prefabricated component or blank material, and it typically is cylindrical or roughly spherical, and its weight slightly overweights the desired wt of the core be molded as.Before this step, composition can first be extruded or otherwise melt and force it by die head (die), is then cut into cylindrical preform.Then this prefabricated component is placed in compression mould chamber, and compresses to the mold temperature of 400 °F to 400 °F, preferably 250 °F to 400 °F, more preferably 300 °F at 150 °F.When compression molding is outer, first formed the casing half of layer material by injection moulding.Then by golf assembly Bao Mi in two and half shells, be then placed on compression mould chamber and compress.

Reaction injection molding(RIM) technique is further at such as United States Patent (USP) 6,083,119,7,208,562,7,281,997,7,282,169,7,338,391 and publication number be open in the U.S. Patent application of 2006/0247073, the full content disclosed by reference is here included in.

Here thermoplastic layer can to produce the mode process of the hardness gradient of plus or minus.Employ in the golf ball layer of the present invention of thermoset rubber wherein, the technique producing gradient and/or the rubber compounding producing gradient can be adopted.The gradient processes and the application number more completely submitted in such as on March 14th, 2008 of filling a prescription that produce gradient are 12/048,665, the application number submitted on July 27th, 2007 is 11/829,461, the application number submitted on July 3rd, 2007 is 11/772,903, the application number submitted on August 1st, 2007 is 11/832,163, the application number submitted on August 1st, 2007 is 11/832, open in the U.S. Patent application of 197, the full content disclosed by reference is here included in.

Golf of the present invention typically has more than 0.700, is more preferably more than 0.750, more preferably the COR of more than 0.780.Here COR used, determines according to known code, and wherein golf or golf assembly (e.g., golf ball core) penetrate from air bubble with two given speed, and calculate under speed 125ft/s.Trajectory shadow shield is fast to measure ball between the air bubble and steel plate of fixed range.When ball flies to steel plate, it excites each shadow shield, measures the time at each shadow shield place.This provide the incident traveling time be inversely proportional to the incidence rate of ball.Pellet impact steel plate also rebounds by shadow shield, again measures and advances the required time between each shadow shield.This providing with the exit velocities of ball is the outgoing traveling time of inverse ratio.Then COR, COR=V is calculated as outgoing traveling time and the ratio of incident traveling time _{go out}/ V _enter=T _enter/ T _{go out}.

The hardness that golf of the present invention has usually is 40 or larger, or within the range having a lower limit of 40 or 50 or 60 or 65 or 80 or 85 or 90 and the upper limit is in the scope of 80 or 85 or 90 or 100 or 110 or 115 or 120, wherein the upper limit is greater 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 affect spin rate and the feel that ball leaves rod (driver).As the Compressionby Any Other Name of JeffDalton, Science and Golf IV, Proceedings of the World ScientificCongress of Golf (Eric Thain ed., Routledge, disclosed in 2002) in (" J.Dalton "), several diverse ways may be used for measuring hardness, comprise Atti ball hardness, Riehle ball hardness, the load under different dead load and skew (offset)/deflection is measured and effective modulus.For the purposes of the present invention, " ball hardness " refers to Atti ball hardness and uses Atti ball hardness testing device to measure according to known method, and wherein, piston is used for ball to press to spring.The stroke of piston is fixing and the deflection of measuring spring.The measurement of spring deflection not from spring contact to ball; But start when skew is roughly the spring deflection of first 1.25mm (0.05 inch).The low-down core of rigidity can not make spring bend more than 1.25mm, thus obtains the ball hardness measurement of 0.Atti ball qualimeter is designed for that to measure diameter be the object of 1.680 inches; Thus, padded for the core of less object as the golf total height to 1.680 inches must be obtained accurate reading.According to formula given in J.Dalton, Atti ball hardness can be converted to Riehle (core), Riehle (ball), 100kg deflection, 130-10kg deflection or effective modulus.

Golf of the present invention typically has 60% or larger, preferably 65% or larger, and more preferably 75% or larger pit coverage rate.

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

Golf of the present invention preferably has 70-95gcm ², preferred 75-93gcm ², and more preferably 76-90gcm ²the moment of inertia (" MOI ").For the embodiment of low MOI, the MOI of golf is preferably 85gcm ²or lower, or 83gcm ²or it is lower.For the embodiment of high MOI, the MOI of golf is preferably 86gcm ²or larger, or 87gcm ²or it is larger.Measure in the moment of inertia instrument of the model MOI-005-104 that MOI manufactures at the Inertia Dynamics of Connecticut State Collinsville.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 mean value of the repetitive measurement of relatively each hemisphere, notes avoiding measuring at the separator bar of core or blemish such as hole or prominence.Hardness measurement is according to " identation hardnesses of Durometer measurements rubber and plastics " of ASTMID-2240.Owing to being curved surface, should be noted that and guarantee before carrying out case hardness reading, golf or golf assembly are placed under penetrator between two parties.All hardness measurement can be used for the digital durometer through calibration of 0.1 stiffness units by reading, and read hardness reading when 1 second after being configured to obtain full-scale reading.Digital durometer must be connected on the pedestal of automatic station (automatic stand), and also must be parallel to this pedestal bottom it.Weight on hardometer and impact speed meet ASTM D-2240.

The central hardness of core obtains according to following code.Lightly core is pressed into internal diameter to be about slightly less than in the hemisphere clamper of the diameter of core, makes core just be clamped in the hemispherical portion of clamper, make the geometric center plane of this core expose simultaneously.Utilize friction to be fixed in clamper by core, it can not move in cutting and polishing step thus, but friction can not be too large in order to avoid the shape of distortion core itself.Fixed core makes the separator bar of core be roughly parallel to the top of clamper.Before fixing, measurement becomes the diameter of the core of 90 degree with this direction.Also measure the top of bottom to core of clamper, think that calculating in the future provides reference point.Use band saw or other suitable cutting elements to carry out rough cut in the geometric center of the exposure a little more than core, guarantee that this step SMIS does not move in clamper.The remainder of the core still in clamper is fixed on the substrate of surface grinding machine." slightly " surface finish exposed is become the surface of smooth planar, expose the geometric center of core, this can confirm from clamp base to the height of core exposed surface by measuring, and guarantees that accurate half ± 0.004 inch of the core original height as above recorded is removed.Core is stayed in clamper, find the center of core with central straight angle square, and carefully mark, measure its hardness at centre mark place according to ASTM D-2240.Then, other hardness measurements apart from any distance place, center of core are carried out in the following manner: from centre mark radially outward setting-out, and along this line in any distance, typically with the increment measurement hardness apart from center 2mm.Apart from center specified distance hardness should along respectively separately the radial arms of 180 ° or separately 90 ° of location measure at least 2 times, preferably 4 times, be then averaged.All all still carrying out when not upsetting its orientation in clamper at core through the hardness measurement carried out in the plane of geometric center, make test surfaces be parallel to the bottom of clamper consistently, and be therefore also parallel to the bottom of hardometer proper alignment.

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

In order to object of the present disclosure, the hardness gradient at center is defined by the hardness measurement of the central point at central outer surface and core." to bear " and " just " refers to deduct by the hardness number of the outer surface of golf assembly the result of the inner most hardness number of this assembly.Such as, if the outer surface of solid central lower than the hardness number at center (namely surface ratio center is soft), then hardness gradient is " bearing " gradient.During the hardness gradient of measuring center, first central hardness determined according to the code of the central hardness of above-mentioned acquisition core.Once marked the center of core and determine its hardness, the hardness measurement apart from any distance place, center of core is carried out in the following manner: from mark center radially outward setting-out, and typically with the increment measurement of 2mm and the distance marking distance center.All all still carrying out when not upsetting its orientation in clamper at core through the hardness measurement carried out in the plane of geometric center, make test surfaces be parallel to the bottom of clamper consistently.On core, the difference of hardness in any precalculated position is calculated as the hardness that average surface hardness deducts suitable reference point, thus the core that surface is softer than its center will have negative hardness gradient, described suitable reference point in single, the solid core such as in core center.

Hardness gradient is more completely at such as United States Patent (USP) 7,429,221, the application number of submission was 11/939 with on November 14th, 2007,632, on November 14th, 2007 submit to application number be on November 14th, 11/939,634,2007 submit to application number be on November 14th, 11/939,635 and 2007 submit to application number be 11/939, open in the U.S. Patent application of 637, the full content disclosed by reference is here included in.

Be to be understood that " material hardness " and " hardness directly measured on golf " has essential distinction.In order to object of the present disclosure, the hardness of material is measured according to ASTM D2240, and generally includes the hardness measuring flat " sheet " or " compressing tablet " that this material is formed.Directly typically produce different hardness numbers in the upper hardness measured of golf (or other spherical surfaces).This species diversity of hardness number, because of some questions, includes, but not limited to the material composition of spherical structure (such as, the type of core, the quantity etc. of core and/or shell), ball (or spheroid) diameter and adjacent layer.Also should be appreciated that two kinds of measuring technique nonlinear correlations, therefore, a kind of hardness number can not connect with another hardness number simply.

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

Here all patents quoted, publication, test procedure and other bibliography, comprise priority text, intactly include the application in the degree that content disclosed by it is not inconsistent with the present invention all by reference, and described in include in all judicial districts be allowed to and all carry out such including in.

Although describe exemplary embodiment of the invention in detail, should be understood that to those skilled in the art, do not departing under purport of the present invention and scope, other modification are obvious and easily obtain.Therefore, be not intended to make appended right be only limitted to example given here and description, on the contrary, claim can be interpreted as the feature comprising the patentability innovation that all the present invention have, and comprises all features that one skilled in the art of the present invention are considered as equivalent feature.

Claims

1. golf, comprising:

By the following core formed:

Center, it is formed by the first diene rubber compsns, and diameter is 1.000 inches to 1.580 inches, and central hardness is 40 Shore C hardness to 70 Shore C hardness, case hardness SH _centerbe 50 Shore C hardness to 85 Shore C hardness;

Intermediate core layer, it is formed by thermoplastic compounds, and thickness is 0.005 inch to 0.100 inch, and outer surface hardness is 60 Shore D hardness or larger; With

Outer sandwich layer, it is formed by the second diene rubber compsns, and thickness is 0.010 inch to 0.100 inch, and outer surface hardness SH _outwardbe 80 Shore C hardness or larger;

Wherein SH _outwardbe greater than SH _center;

The wherein highest hardness SH of this core _peakbe positioned at 0.25mm to the 5.00mm distance radially-inwardly measured from the outer surface of core; Further,

Wherein SH _peakhigher than SH _outward10% or more; With

Thickness is the shell that 0.010 inch of composition being less than 60 Shore D hardness to 0.050 inch and by material hardness is formed.

2. the golf of claim 1, wherein SH _peakhigher than SH _outward20% or more.

3. the golf of claim 1, wherein SH _peakbe positioned at 0.50mm to the 5.00mm distance radially-inwardly measured from the outer surface of core.

4. the golf of claim 1, wherein SH _peakbe positioned at 0.50mm to the 2.50mm distance radially-inwardly measured from the outer surface of core.

5. the golf of claim 1, wherein SH _peakhigher than SH _outward20% or more; And wherein SH _peakbe positioned at 0.50mm to the 5.00mm distance radially-inwardly measured from the outer surface of core.

6. the golf of claim 1, wherein SH _outwardwith SH _centerdiffer 5 Shore C stiffness units or more.

7. the golf of claim 1, wherein SH _outwardwith SH _centerdiffer 10 Shore C stiffness units or more.

8. the golf of claim 1, wherein, described center has positive hardness gradient, and wherein the central hardness at center and the difference of case hardness are 10 to 45 Shore C hardness.

9. the golf of claim 1, wherein, the diameter at described center is 1.300 inches to 1.490 inches, and the thickness of described intermediate core layer is 0.020 inch to 0.070 inch, and the thickness of described outer sandwich layer is 0.030 inch to 0.040 inch.

10. the golf of claim 1, the case hardness of wherein said intermediate core layer is 65 Shore D hardness or larger.

The golf of 11. claims 1, the case hardness of wherein said intermediate core layer is 70 Shore D hardness or larger.

The golf of 12. claims 1, wherein SH _outwardbe 85 Shore C hardness or larger.

The golf of 13. claims 1, the thermoplastic compounds of wherein said intermediate core layer is selected from the ionomer of part neutralization and the ionomer of all neutralizations and they two or more blend.

14. golf, comprising:

By the following core formed:

Center, it is formed by the first diene rubber compsns, and diameter is 1.400 inches to 1.550 inches, and central hardness is 45 Shore C hardness to 70 Shore C hardness, and case hardness SH _centerbe 55 Shore C hardness to 85 Shore C hardness;

Intermediate core layer, it is formed by thermoplastic compounds, and thickness is 0.020 inch to 0.070 inch, and outer surface hardness is 65 Shore D hardness or larger; With

Outer sandwich layer, it is formed by the second diene rubber compsns, and thickness is 0.020 inch to 0.050 inch, and outer surface hardness SH _outwardbe 85 Shore C hardness or larger;

Wherein SH _outwardbe greater than SH _center;

The wherein highest hardness SH that has of this core _peakbe positioned at 0.50mm to the 5.00mm distance radially-inwardly measured from the outer surface of core; Further, wherein SH _peakhigher than SH _outward10% or more; With

Thickness is the shell that 0.010 inch of composition being less than 60 Shore D hardness to 0.050 inch and by material hardness is formed, and wherein shell composition is selected from polyurethane, polyureas and polyurethane-polyurea blend.

The golf of 15. claims 14, wherein SH _peakhigher than SH _outward20% or more.

The golf of 16. claims 14, wherein SH _peakbe positioned at 0.50mm to the 2.50mm distance radially-inwardly measured from the outer surface of core.

The golf of 17. claims 14, wherein SH _peakhigher than SH _outward20% or more; Wherein SH _peakbe positioned at 0.50mm to the 2.50mm distance radially-inwardly measured from the outer surface of core.

The golf of 18. claims 14, wherein SH _outwardwith SH _centerdifference be 5 Shore C stiffness units or more.

The golf of 19. claims 14, wherein SH _outwardwith SH _centerdifference be 10 Shore C stiffness units or more.

The golf of 20. claims 14, wherein, described center has positive hardness gradient, and the central hardness at wherein said center differs 10 to 45 Shore C hardness with case hardness.