CN102166403A - Multilayer core golf ball - Google Patents

Multilayer core golf ball Download PDF

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CN102166403A
CN102166403A CN201010625197XA CN201010625197A CN102166403A CN 102166403 A CN102166403 A CN 102166403A CN 201010625197X A CN201010625197X A CN 201010625197XA CN 201010625197 A CN201010625197 A CN 201010625197A CN 102166403 A CN102166403 A CN 102166403A
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hardness
core
shore
golf
inch
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CN102166403B (en
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迈克尔·J·沙利文
布莱恩·科米厄
道格拉斯·S·戈古恩
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Acushnet Co
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Acushnet Co
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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
The cross reference related application
The application is 12/407 of submission on March 20th, 2009,856 part continuation application, 12/407,856 is that the application number of submitting on January 10th, 2008 is 11/972, the full content of above-mentioned application is included in the part continuation application of 240 U.S. Patent application here in by introducing.
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 soft thermoset rubber center, hard thermoplasticity intermediate core layer and the thin outer sandwich layer of thermoset rubber.
Background technology
Golf with multilayer core is known.For example, United States Patent (USP) 6,852,044 has disclosed the golf with multilayer core, and described multilayer core has the inner core soft relatively, low ball hardness (compression) by the outer core encirclement of relative stiffness.United States Patent (USP) 5,772,531 have disclosed a kind of solid golf ball, and it comprises: have solid core by internal layer, intermediate layer and the outer three-decker of forming, and the shell that is used to coat solid core.Publication number is the golf that 2006/0128904 U.S. Patent application has also disclosed the multilayer core.Other examples of multilayer core can, for example, 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, obtain in 074,137,7,153,467 and 7,255,656.
The invention provides a kind of golf structure of new multilayer core, wherein, this core comprises soft thermoset rubber center, hard thermoplasticity intermediate core layer and the thin outer sandwich layer of thermoset rubber.Here the new construction of Pi Luing has unique core hardness gradient, and wherein maximum core hardness is positioned at from the specified distance of the outmost surface of core greater than the maximum core hardness and/or the maximum core hardness of conventional core.
Summary of the invention
In one embodiment, the present invention relates to comprise the golf of 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 1.000 inches to 1.580 inches diameter, 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 0.005 inch to 0.100 inch thickness and 60 Shore D hardness or bigger outer surface hardness.Outer sandwich layer has 0.010 inch to 0.100 inch thickness and 80 Shore C hardness or bigger 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 of radially inwardly measuring from the outer surface of this core.This maximum case hardness is than the outer surface hardness high 10% of outer sandwich layer or bigger.Shell has 0.010 inch to 0.050 inch thickness, and is formed by the composition of material hardness less than 60 Shore D hardness.
In another embodiment, the present invention relates to comprise the golf of 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 1.400 inches to 1.550 inches diameter, 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 0.020 inch to 0.070 inch thickness and 65 Shore D hardness or bigger outer surface hardness.Described outer sandwich layer has 0.020 inch to 0.050 inch thickness and 85 Shore C hardness or bigger 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 of radially inwardly measuring from the outer surface of core.Maximum case hardness is than the outer surface hardness high 10% of outer sandwich layer or bigger.Shell has 0.010 inch to 0.050 inch thickness, and is formed by the composition of material hardness less than 60 Shore D hardness.
Description of drawings
Fig. 1 is the profile according to the golf of one embodiment of the present invention.
The specific embodiment
The golf that has the multilayer core and seal the shell of this core is disclosed.Fig. 1 has shown 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 among Fig. 1 is simple layer, any one in inner core 32, intermediate core 34, outer core 36 and the shell 38 or a plurality of can the composition by one deck, two-layer or multilayer.
In specific embodiment, each in inner core 32, intermediate core 34, outer core 36 and the shell 38 all is a simple layer.
In another specific embodiment, inner core 32 is made up of two-layer, and in intermediate core 34, outer core 36 and the shell 38 each all is a 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 another embodiment, intermediate core 34 is made up of two-layer, and in inner core 32, outer core 36 and the shell 38 each all is a simple layer.
Multilayer core of the present invention comprises inner core, intermediate core and outer core.The overall diameter of this multilayer core (external diameter that also refers to outer sandwich layer here) is that 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 are in 1.600 or 1.610 or 1.620 or 1.630 or 1.640 or 1.650 or 1.660 inches the scope at lower limit, wherein the upper limit greater than lower limit (for example, when being limited to 1.610 inches instantly, on be limited to 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 the center, perhaps is made up of center and additional inner sandwich layer, perhaps 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 bigger, perhaps 1.000 inches or bigger, perhaps 1.250 inches or bigger, perhaps 1.300 inches or bigger, perhaps 1.350 inches or bigger, perhaps 1.390 inches or bigger, perhaps 1.400 inches or bigger, perhaps 1.425 inches or bigger, perhaps 1.450 inches or bigger, perhaps 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 are in 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 the scope to this overall diameter within the range having a lower limit of.
The central hardness of inner core within the range having a lower limit of 20 or 25 or 30 or 35 or 40 or 45 or 50 or 55 or 57 Shore C hardness and on be limited in the scope of 57 or 60 or 65 or 70 or 75 or 90 Shore C hardness.The outer surface hardness of inner core within the range having a lower limit of 20 or 50 or 55 or 70 or 75 or 78 Shore C hardness and on be limited in the scope of 75 or 78 or 80 or 85 or 90 or 95 Shore C hardness, wherein the upper limit greater than lower limit (for example, instantly be limited at 75 o'clock, on be limited to 78,80,85,90 or 95).Inner core has negative hardness gradient, and zero hardness gradient perhaps is up to the positive hardness gradient of 45 Shore C hardness, perhaps from the positive hardness gradient of 10 Shore C hardness to 45 Shore C hardness.In specific embodiment, inner core is made up of the center that the zero gradient prescription forms, and as disclosed in the United States Patent (USP) 7,537,530 and 7,537,529 for example, by reference their whole disclosures is included in 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, perhaps ball hardness within the range having a lower limit of 10 20 or 30 35 or 40 50 or 60 and on be limited in 40 or 50 or 60 or 70 or 80 or 90 the scope, wherein the upper limit is greater than lower limit (for example, instantly be limited at 50 o'clock, be limited to 60,70,80 or 90 on it).
Each inner sandwich layer is preferably formed by rubber composition.In specific embodiment, inner core is made up of the center that 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 wherein each in them is formed by identical or different rubber compositions.
The suitable rubber composition that is used to form inner sandwich layer comprises basic rubber, initator, and coagent, and randomly comprise in zinc oxide, zinc stearate or stearic acid, antioxidant and the softening accelerator (softand fast agent) one or more.Suitable basic rubber comprises natural and synthetic rubber, include 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, " I " is isoprene, " B " is butadiene), butyl rubber, halogenated butyl rubber, the polystyrene elastomer, the polyethylene elastomer body, polyurethane elastomer, SPUA, the elastomer of metallocene catalyst and plastic body, isobutene and to the copolymer of ring-alkylated styrenes, isobutene and to the halogenated copolymers of ring-alkylated styrenes, the copolymer of butadiene and acrylonitrile, polychlorobutadiene, alkyl acrylate rubber, the chlorination isoprene rubber, acrylonitrile chlorination isoprene rubber, and they two or more combination (for example combination of polybutadiene and more a spot of other thermosets, 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, polybutadiene (comprise and have 1 of at least 40% cis-structure, the 4-polybutadiene) particularly, styrene-butadiene, and polybutadiene and other elastomeric mixtures, wherein the amount of the polybutadiene of Cun Zaiing be at least mixture total polymer weight 40%.Particularly preferred polybutadiene comprises the polybutadiene of neodymium catalysis high-cis polybutadiene and cobalt, nickel or lithium catalysis.The suitable examples of commercially available polybutadiene includes, but not limited to Buna CB neodymium catalysis cis-rich polybutadiene rubber, as Buna CB 23 and
Figure BSA00000436993200041
Cobalt catalysis cis-rich polybutadiene rubber, as can from The commercial acquisition of company
Figure BSA00000436993200043
With 221; Can be from the commercial SE BR-1220 that obtains of The Dow Chemical Company; Can be from Polimeri
Figure BSA00000436993200044
Commercial acquisition
Figure BSA00000436993200045
BR 40 and BR 60; Can be from UBE Industries, the commercial acquisition of Inc. Rubber; Can be from Japan Synthetic Rubber Co., the commercial BR 01 that obtains of Ltd.; With can be from the commercial Neodene neodymium catalysis cis-rich polybutadiene rubber that obtains of Karbochem, as Neodene BR40.
The high-energy radiation source that suitable initator comprises organic peroxide, can produce 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-radiation, infrared radiation, heat, and their combination.Suitable organic peroxide includes but not limited to cumyl peroxide; 4,4-two (tert-butyl hydroperoxide) n-butyl pentanoate; 1,1-two (tert-butyl hydroperoxide)-3,3,5-trimethyl-cyclohexane; 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) cyclohexane; Di-t-butyl peroxide; Peroxidating two tertiary pentyls; Tert-butyl peroxide; The tert-butyl peroxide isopropylbenzene; 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexin-3; Two (the 2-tert-butyl group-peroxidating isopropyl) benzene; Dilauroyl peroxide; Dibenzoyl peroxide; T-butyl hydroperoxide; The peroxidating lauryl; Benzoyl peroxide; And their combination.The example of the suitable peroxide that can commercially obtain includes but not limited to, can obtain from Akzo Nobel commerce BC cumyl peroxide and can be from RT Vanderbilt Company, Inc. is commercial to be obtained
Figure BSA00000436993200052
Peroxide, as
Figure BSA00000436993200053
The ANS benzoyl peroxide,
Figure BSA00000436993200054
2311,1-two (tert-butyl hydroperoxide) 3,3, the 5-trimethyl-cyclohexane and
Figure BSA00000436993200055
230-XL 4, two (tert-butyl peroxide) n-butyl pentanoates of 4-.
Peroxide initiator reagent is present in the rubber composition with following amount usually: the amount of per 100 parts of basic rubber at least 0.05 weight portions, perhaps per within the range having a lower limit of 100 weight portions basis rubber 0.05 weight portion 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 on be limited to amount in the scope of per 100 weight portions basis 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.
Coagent uses to increase solid state with peroxide usually.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, and 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 a dizinc acrylate resin.When coagent is dizinc acrylate resin and/or zinc dimethacrylate, this coagent typically with per 100 weight portions basis rubber 1 or 5 or 10 or 15 or 19 or 20 weight portions within the range having a lower limit of and on the amount that is limited in the scope of per 100 weight portions basis rubber 24 or 25 or 30 or 35 or 40 or 45 or 50 or 60 weight portions be contained in the rubber composition.When using the lower coagent of one or more activity such as monomethyl zinc acrylate resin and various liquid propene hydrochlorate and methacrylate, the consumption of the coagent that activity is lower can be identical or higher with the amount of dizinc acrylate resin and zinc dimethacrylate coagent.Can be by adjusting the ball hardness that crosslinked amount obtains needs, crosslinked amount can for example realize by type and the amount that changes coagent.
Rubber composition randomly comprises curing agent.Suitable curing agent includes but not limited to, sulphur, N-oxygen diethylidene-2-[4-morpholinodithio sulfenamide, N, the N-di-o-tolylguanidine, the dimethyl dithiocarbamate bismuth, N-cyclohexyl-2-[4-morpholinodithio sulfenamide, N, the 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 randomly 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 comprised antioxidant, the consumption of initator can be the same with amount disclosed herein high or higher.Suitable antioxidant comprises, for example, and EEDQ antioxidant, amine antioxidants and phenol antioxidant.
Rubber composition also can comprise one or more fillers to adjust the density and/or the proportion of core.The filler of example comprises the 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 (for example, calcium carbonate, zinc carbonate, brium carbonate and magnesium carbonate), metal (for example, titanium, tungsten, aluminium, bismuth, nickel, molybdenum, iron, plumbous, copper, boron, cobalt, beryllium, zinc and tin), metal alloy (for example, steel, brass, bronze, boron carbide whisker and tungsten carbide whisker), metal oxide (for example, zinc oxide, tin oxide, iron oxide, calcium oxide, aluminium oxide, titanium dioxide, magnesia and zirconia), particulate carbonaceous material (for example, graphite, carbon black, flocking, bitumen, cellulose fluff and leather fiber), microballoon (for example, glass and pottery), flying dust, abrasive material (for example again, the core material of pulverizing and reclaiming), Nano filling, and above-mentioned two or more combination.Typically per within the range having a lower limit of 100 weight portions of the amount of the microparticle material that exists in rubber composition basis rubber 5 weight portions or 10 weight portions and on be limited in the scope of per 100 weight portions basis rubber 30 weight portions or 50 weight portions or 100 weight portions.Filler material can be double-functional packing, as zinc oxide (it can be used as filler/plumper) and titanium dioxide (it can be used as filler/brightener material).
Rubber composition can also comprise one or more additives that are 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.Typically per within the range having a lower limit of 100 weight portions of the amount of the additive that exists in rubber composition basis rubber 0 weight portion and on be limited in the scope of per 100 weight portions basis rubber 20 weight portions or 50 weight portions or 100 weight portions or 150 weight portions.
Rubber composition randomly 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 on the amount that is limited in 1.00phr or 2.00phr or 3.00phr or the 5.00phr scope exist.In another embodiment, softening accelerator with 2.00phr or 2.35phr within the range having a lower limit of and on the amount that is limited in 3.00phr or 4.00phr or the 5.00phr scope exist.In another optional high concentration embodiment, softening accelerator with 5.00phr or 6.00phr or 7.00phr within the range having a lower limit of and on the amount that is limited in the scope of 8.00phr or 9.00phr or 10.00phr exist.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; The inorganic sulphide compounds; The blend of organosulfur compound and inorganic sulphide compounds; The compound of VIA family; The not replacement of sulfur-bearing or metal and unsubstituted aromatics organic compound; The aromatics organo-metallic compound; Quinhydrones; Benzoquinones; Quinhydrone; Catechol; Resorcinol; And their combination.
Here, " organosulfur compound " is meant any compound that contains carbon, hydrogen and sulphur, and wherein sulphur is bonded directly at least 1 carbon.Here, term " sulphur compound " is meant such compound, and it is elementary sulfur, polymerised sulphur (polymeric sulfur) or their combination.Should be understood that further that term " elementary sulfur " is meant S 8Circulus, and " polymerised sulphur " is the structure that comprises with respect at least one additional sulphur of elementary sulfur.
Suitable especially is the organosulfur compound with following general formula as what soften accelerator:
Figure BSA00000436993200071
Wherein, R 1-R 5Can be C 1-C 8Alkyl; Halogen; Mercapto (SH), carboxylic acid base; The sulfonation base; And hydrogen; With random order; And also can be the phenyl-pentafluoride thiophenol; The 2-fluoro thiophenol; The 3-fluoro thiophenol; The 4-fluoro thiophenol; 2, the 3-fluoro thiophenol; 2, the 4-fluoro thiophenol; 3, the 4-fluoro thiophenol; 3, the 5-fluoro thiophenol; 2,3, the 4-fluoro thiophenol; 3,4, the 5-fluoro thiophenol; 2,3,4,5-phenyl tetrafluoride thiophenol; 2,3,5,6-phenyl tetrafluoride thiophenol; 4-chlorine phenyl tetrafluoride thiophenol; Reptazin; The 2-chlorothio-phenol; The 3-chlorothio-phenol; The 4-chlorothio-phenol; 2, the 3-chlorothio-phenol; 2, the 4-chlorothio-phenol; 3, the 4-chlorothio-phenol; 3, the 5-chlorothio-phenol; 2,3, the 4-chlorothio-phenol; 3,4, the 5-chlorothio-phenol; 2,3,4,5-tetrachlorobenzene thiophenol; 2,3,5,6-tetrachlorobenzene thiophenol; The phenyl-pentabromide thiophenol; The 2-bromo thiophenol; The 3-bromo thiophenol; The 4-bromo thiophenol; 2, the 3-bromo thiophenol; 2, the 4-bromo thiophenol; 3, the 4-bromo thiophenol; 3, the 5-bromo thiophenol; 2,3, the 4-bromo thiophenol; 3,4, the 5-bromo thiophenol; 2,3,4,5-tetrabromo-benzene thiophenol; 2,3,5,6-tetrabromo-benzene thiophenol; The 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, for example, the ammonium salt of reptazin; Reptazin magnesium; The reptazin cobalt; And their combination.Preferably, the benzene halide thiol compounds is a reptazin, and it can be from commercial with pure form or trade name
Figure BSA00000436993200081
A95 (contain the sulphur compound based on the carrier of clay, the reptazin heap(ed) capacity is 45%) obtains. A95 can obtain from the Struktol Company of America of Ohio Stow is commercial.PCTP can obtain from the eChinachem in San Francisco of California is commercial with pure form, and obtains from the eChinachem in San Francisco of California is commercial with the form of salt.Suitable organosulfur compound for example further is disclosed in the United States Patent (USP) 6,635,716,6,919,393,7,005,479 and 7,148,279, by reference their full content is included in here.
Suitable containing metal organosulfur compound 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 is at United States Patent (USP) 7,005, and is open in 479, by reference its full content included in here.
Suitable disulfide includes but not limited to 4,4 '-the diphenyl disulfide; 4,4 '-the xylyl disulfide; 2,2 '-benzamido diphenyl disulfide; Two (2-aminophenyl) disulfide; Two (4-aminophenyl) disulfide; Two (3-aminophenyl) disulfide; 2,2 '-two (the amino naphthyl of 4-) disulfide; 2,2 '-two (the amino naphthyl of 3-) disulfide; 2,2 '-two (the amino naphthyl of 4-) disulfide; 2,2 '-two (the amino naphthyl of 5-) disulfide; 2,2 '-two (the amino naphthyl of 6-) disulfide; 2,2 '-two (the amino naphthyl of 7-) disulfide; 2,2 '-two (the amino naphthyl of 8-) disulfide; 1,1 '-two (the amino naphthyl of 2-) disulfide; 1,1 '-two (the amino naphthyl of 3-) disulfide; 1,1 '-two (the amino naphthyl of 3-) disulfide; 1,1 '-two (the amino naphthyl of 4-) disulfide; 1,1 '-two (the amino naphthyl of 5-) disulfide; 1,1 '-two (the amino naphthyl of 6-) disulfide; 1,1 '-two (the amino naphthyl of 7-) disulfide; 1,1 '-two (the amino naphthyl of 8-) disulfide; 1,2 '-diaminostilbene, 2 '-two sulfo-dinaphthyls; 2,3 '-diaminostilbene, 2 '-two sulfo-dinaphthyls; 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, the 5-dichlorophenyl) disulfide; Two (3, the 5-dichlorophenyl) disulfide; Two (2, the 4-dichlorophenyl) disulfide; Two (2, the 6-dichlorophenyl) disulfide; Two (2, the 5-dibromo phenyl) disulfide; Two (3, the 5-dibromo phenyl) disulfide; Two (2-chloro-5-bromophenyl) disulfide; Two (2,4, the 6-trichlorophenyl) disulfide; Two (2,3,4,5, the 6-five chlorophenyl) disulfide; Two (4-cyano-phenyl) disulfide; Two (2-cyano-phenyl) disulfide; Two (4-nitrobenzophenone) disulfide; Two (2-nitrobenzophenone) disulfide; 2,2 '-the dithiobenzoic acid ethyl ester; 2,2 '-the dithiobenzoic acid methyl esters; 2,2 '-dithiobenzoic acid; 4,4 '-the dithiobenzoic acid ethyl ester; Two (4-acetylphenyl) disulfide; Two (2-acetylphenyl) disulfide; Two (4-formoxyl phenyl) disulfide; Two (4-carbamyl phenyl) disulfide; 1,1 '-the dinaphthyl disulfide; 2,2 '-the dinaphthyl disulfide; 1,2 '-the dinaphthyl disulfide; 2,2 '-two (1-chlorine dinaphthyl) disulfide; 2,2 '-two (1-bromonaphthalene base) disulfide; 1,1 '-two (2-chloronaphthyl, methylnaphthyl) disulfide; 2,2 '-two (1-cyano group naphthyl) disulfide; 2,2 '-two (1-acetyl group naphthyl) disulfide etc.; And their combination.
Suitable inorganic sulphide compounds includes but not limited to the sulfide analog of titanium sulfide, manganese sulfide and iron, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, tin and bismuth.
The compound of suitable VIA family includes but not limited to, elementary sulfur and polymerised sulphur, and as can be from the Elastochem of Ohio Chardon, commercial those that obtain of Inc.; The sulfur catalyst compound comprises PB (RM-S)-80 elementary sulfur and PB (CRST)-65 polymerised sulphur, and both all can be from Elastochem, and Inc. obtains; The tellurium catalyst, as
Figure BSA00000436993200091
And the selenium catalyst, as
Figure BSA00000436993200092
Both all can be from RT Vanderbilt Company, and Inc. is commercial to be obtained.
The suitable not sulfur-bearing or the replacement of metal and do not replace the aromatics organic component and include but not limited to, 4,4 '-dibenzenyl, azobenzene and their combination.The big or small preferable range of aromatics organic group is at C 6To C 20, and more preferably C 6To C 10
Suitable replacement and do not replace the aromatics organo-metallic compound and include but not limited to have formula (R 1) x-R 3-M-R 4-(R 2) yThose, R wherein 1And R 2Be respectively hydrogen or replacement or unsubstituted C 1-20Straight chain, branching or cyclic alkyl, alkoxyl or alkylthio group, perhaps be monocycle, C many rings, condensed ring 6To C 24Aryl; X and y are respectively 0 to 5 integers; R 3And R 4Be selected from monocycle, C many rings, condensed ring respectively 6To C 24Aryl; M comprises azo group or metal component.Preferably, R 3And R 4Be selected from C respectively 6To C 10Aryl, more preferably be selected from phenyl, benzyl, naphthyl, phenylamino and benzothiazolyl.Preferably, R 1And R 2Be selected from respectively and replace and unsubstituted C 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, replacement 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 was metal component, it can be the metallic element of any suitable.Usually this metal is a transition metal, and is preferably tellurium or selenium.
Suitable quinhydrones includes but not limited to compound that following formula is represented and hydrate thereof.
Figure BSA00000436993200101
Wherein, R 1, R 2, R 3And R 4Be independently selected from respectively: hydrogen, halogen group (F, CI, Br, I), alkyl, carboxyl (COOH) and slaine (for example ,-COO -M +) and ester (COOR), acetate (CH 2COOH) and ester (CH 2COOR), formoxyl (CHO), acyl group (COR), acetyl group (COCH 3), carbonyl halide (COX), sulfonic group (SO 3H) and ester (SO 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 (for example ,-O -M +), amino (NH 2), nitro (NO 2), aryl (for example, phenyl, tolyl etc.), aryloxy group (for example phenoxy group etc.), aryl alkyl [for example, cumenyl (C (CH 3) 2Phenyl); Benzyl (CH 2Phenyl)] nitroso (NO), acetylamino (NHCOCH, 3), vinyl (CH=CH 2).Particularly preferred quinhydrones comprises compound and the hydrate of being represented by following formula thereof, wherein R 1, R 2, R 3And R 4Be independently selected from respectively: the slaine of carboxyl (as ,-COO -M +), acetate (CH 2COOH) and ester (CH 2COOR), hydroxyl (OH), the slaine of hydroxyl (for example ,-O -M +), amino (NH 2), nitro (NO 2), aryl (for example, phenyl, tolyl etc.), aryloxy group (for example, phenoxy group etc.), aryl alkyl [for example, cumenyl (C (CH 3) 2Phenyl), benzyl (CH 2Phenyl)] nitroso (NO), acetylamino (NHCOCH, 3), vinyl (CH=CH 2).The example of Shi Yi quinhydrones includes but not limited to especially, quinhydrones; The tetrachloro quinhydrones; The 2-chlorohydroquinone; The 2-bromohydroquinone; 2, the 5-dichloro hydroquinone; 2,5-two bromohydroquinones; The tetrabromo quinhydrones; The 2-methylnaphthohydroquinone; The 2-tertiary butylated hydroquinone; 2, the two amyl hydroquinone of 5-; And 2-(2-chlorphenyl) quinhydrones hydrate.Preferred especially quinhydrones and tetrachloro quinhydrones more particularly preferably are 2-(2-chlorphenyl) quinhydrones hydrates.Suitable quinhydrones is open in 2007/0213440 the U.S. Patent application at for example publication number further, by reference its full content is included in here.
Suitable benzoquinones comprises compound and the hydrated thing thereof that following molecular formula is represented.
Figure BSA00000436993200111
Wherein, R 1, R 2, R 3And R 4Be independently selected from respectively: hydrogen, halogen group (F, CI, Br, I), alkyl, carboxyl (COOH) and slaine (for example ,-COO -M +) and ester (COOR), acetate (CH 2COOH) and ester (CH 2COOR), formoxyl (CHO), acyl group (COR), acetyl group (COCH 3), carbonyl halide (COX), sulfonic group (8O 3H) and ester (SO 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 (for example ,-O -M +), amino (NH 2), nitro (NO 2), aryl (for example, phenyl, tolyl etc.), aryloxy group (for example phenoxy group etc.), aryl alkyl [for example, cumenyl (C (CH 3) 2Phenyl); Benzyl (CH 2Phenyl)] nitroso (NO), acetylamino (NHCOCH, 3), vinyl (CH=CH 2).Particularly preferred benzoquinones comprises compound and the hydrate of being represented by following formula thereof, wherein R 1, R 2, R 3And R 4Be independently selected from respectively: the slaine of carboxyl (for example ,-COO -M +), acetate (CH 2COOH) and ester (CH 2COOR), hydroxyl (OH), the slaine of hydroxyl (for example ,-O -M +), amino (NH 2), nitro (NO 2), aryl (for example, phenyl, tolyl etc.), aryloxy group (for example, phenoxy group etc.), aryl alkyl [for example, cumenyl (C (CH 3) 2Phenyl), benzyl (CH 2Phenyl)] nitroso (NO), acetylamino (NHCOCH, 3), vinyl (CH=CH 2).Special more preferable methyl 1,4-benzoquinone and chloranil.Suitable benzoquinones is open in 2007/0213442 the U.S. Patent application at for example publication number further, by reference its full content is included in here.
Suitable quinhydrone includes but not limited to compound and the hydrate thereof that following molecular formula is represented.
Figure BSA00000436993200112
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7And R 8Be independently selected from respectively: hydrogen, halogen group (F, CI, Br, I), alkyl, carboxyl (COOH) and slaine (for example ,-COO -M +) and ester (COOR), acetate (CH 2COOH) and ester (CH 2COOR), formoxyl (CHO), acyl group (COR), acetyl group (COCH 3), carbonyl halide (COX), sulfonic group (SO 3H) and ester (SO 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 (for example ,-O -M +), amino (NH 2), nitro (NO 2), aryl (for example, phenyl, tolyl etc.), aryloxy group (for example phenoxy group etc.), aromatic alkyl [for example, cumenyl (C (CH 3) 2Phenyl); Benzyl (CH 2Phenyl)] nitroso (NO), acetylamino (NHCOCH, 3), vinyl (CH=CH 2).Particularly preferred quinhydrone comprises compound and the hydrate of being represented by following formula thereof, wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7And R 8Be independently selected from respectively: the slaine of carboxyl (for example ,-COO -M +), acetate (CH 2COOH) and ester (CH 2COOR), hydroxyl (OH), the slaine of hydroxyl (for example ,-O -M +), amino (NH 2), nitro (NO 2), aryl (for example, phenyl, tolyl etc.), aryloxy group (for example, phenoxy group etc.), aryl alkyl [for example, 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 that is represented by following formula 1, R 2, R 3, R 4, R 5, R 6, R 7And R 8Compound for hydrogen.Suitable quinhydrone is open in 2007/0213441 the U.S. Patent application at for example publication number further, by reference its full content is included in here.
Suitable catechol comprises compound and the hydrate thereof that following molecular formula is represented:
Figure BSA00000436993200121
Wherein, R 1, R 2, R 3And R 4Be independently selected from respectively: hydrogen, halogen group (F, CI, Br, I), alkyl, carboxyl (COOH) and slaine (for example ,-COO -M +) and ester (COOR), acetate (CH 2COOH) and ester (CH 2COOR), formoxyl (CHO), acyl group (COR), acetyl group (COCH 3), carbonyl halide (COX), sulfonic group (SO 3H) and ester (SO 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 (for example ,-O -M +), amino (NH 2), nitro (NO 2), aryl (for example, phenyl, tolyl etc.), aryloxy group (for example phenoxy group, or the like), aromatic alkyl [for example, cumenyl (C (CH 3) 2Phenyl); Benzyl (CH 2Phenyl)] nitroso (NO), acetylamino (NHCOCH, 3), vinyl (CH=CH 2).Suitable catechol is open in 2007/0213144 the U.S. Patent application at for example publication number further, by reference its full content is included in here.
Suitable resorcinol comprises compound and the hydrate thereof that following molecular formula is represented:
Figure BSA00000436993200131
Wherein, R 1, R 2, R 3And R 4Be independently selected from respectively: hydrogen, halogen group (F, CI, Br, I), alkyl, carboxyl (COOH) and slaine (for example ,-COO -M +) and ester (COOR), acetate (CH 2COOH) and ester (CH 2COOR), formoxyl (CHO), acyl group (COR), acetyl group (COCH 3), carbonyl halide (COX), sulfonic group (SO 3H) and ester (SO 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 (for example ,-O -M +), amino (NH 2), nitro (NO 2), aryl (for example, phenyl, tolyl etc.), aryloxy group (for example phenoxy group etc.), aromatic alkyl [for example, cumenyl (C (CH 3) 2Phenyl); Benzyl (CH 2Phenyl)] nitroso (NO), acetylamino (NHCOCH, 3), vinyl (CH=CH 2).Preferred especially 2-nitro-resorcinol.Suitable resorcinol is open in 2007/0213144 the U.S. Patent application at for example publication number further, by reference its full content is included in here.
When rubber composition comprises one or more quinhydrones, benzoquinones, quinhydrone, catechol, when resorcinol or their combination, be present in the quinhydrones in the described composition, benzoquinones, quinhydrone, catechol and/or resorcinol total amount typically are per 100 parts of basic rubber at least 0.1 weight portions or at least 0.15 weight portion or at least 0.2 weight portion, perhaps for 0.1 weight portion of per 100 parts of basic 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 on be limited to amount in the scope of 0.5 weight portion of per 100 parts of basic rubber or 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, dixylyl disulfide, 2-nitro-resorcinol, reaches their combination.
The suitable type of basis rubber, initator, coagent, filler and additive and amount are more completely at for example United States Patent (USP) 6,566,483,6,695,718,6,939,907,7,041, describe in 721 and 7,138,460, by reference its full content is included in here.Shi Yi diene rubber composition is open in 2007/0093318 the U.S. Patent application at for example publication number further especially, by reference its full content is included in here.
Inner core is sealed by intermediate core, intermediate core is individual layer, bilayer or multilayer, and preferred gross thickness within the range having a lower limit of 0.005 or 0.010 or 0.020 or 0.025 or 0.035 or 0.040 or 0.045 inch and on be limited in 0.045 or 0.050 or 0.060 or 0.070 or 0.080 or 0.090 or 0.100 inch the scope.
The outer surface hardness of intermediate core is 40 Shore C hardness or bigger, perhaps 70 Shore C hardness or bigger, perhaps 80 Shore C hardness or bigger, perhaps 85 Shore C hardness or bigger, perhaps 89 Shore C hardness or bigger, perhaps 90 Shore C hardness or bigger, perhaps 93 Shore C hardness or bigger, perhaps 95 Shore C hardness or bigger, perhaps 60 Shore D hardness or bigger, perhaps 63 Shore D hardness or bigger, perhaps 65 Shore D hardness or bigger, perhaps the hardness number of outer surface within the range having a lower limit of 40 or 45 or 50 or 80 or 85 or 89 Shore C hardness and on be limited in the scope of 80 or 85 or 90 or 93 or 95 Shore C hardness, wherein the upper limit is greater than lower limit (for example, instantly be limited at 85 o'clock, on be limited to 90,93 or 95).Intermediate core preferably have be limited to down 20 30 or 35 40 or 45 50 or 55 57 or 58 60 or 63 65 or 66 or 70 and on be limited to 60 or 65 or 66 or 70 or 72 or 75 or 80 or 85 or 90 Shore D outer surface hardness, wherein the upper limit greater than lower limit (for example, instantly be limited at 65 o'clock, on be limited to 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.The suitable thermoplastic polymer composition that is used to form inner sandwich layer includes but not limited to, the ionomer of part and neutralization fully and their blend comprise the ionomeric blend (as being disclosed in 2006/0128904 the U.S. Patent application at publication number) of HNP and part neutralization, and HNP and extra thermoplasticity and thermosets are (as acid copolymer, the engineered thermoplastic material, based on the HNP of fatty acid/salt, polybutadiene, polyurethane, polyureas, polyester, thermoplastic elastomer (TPE) and other conventional polymeric materials) blend, and particularly at for example United States Patent (USP) 6,653,382,6,756,436,6,777,472,6,894,098,6,919, disclosed ionomer compositions in 393 and 6,953,820.Suitable HNP composition for example is also included within those disclosed in the United States Patent (USP) 6,653,382,6,756,436,6,777,472,6,894,098,6,919,393 and 6,953,820.Here by reference the full content of above-mentioned all documents is included in.The acid content (before the neutralization) of preferred ionomer compositions is at 1wt% to 30wt%, perhaps 5wt% to 20wt%.
What also suit the formation intermediate core layer is the graft copolymer of ionomer and polyamide; And following non-ionomeric polymer (comprises its homopolymers and copolymer, and they with functional group at least a grafting or copolymerization (as maleic anhydride, amine, epoxy radicals, isocyanate group, hydroxyl, sulfonic group, phosphonate group etc.) compatible derivative): polyester, particularly use those of compatible group such as sulfonic group or phosphonate group modification, poly-(PETP) that comprises modification, poly-(butylene terephthalate) of modification, poly-(the terephthalic acid (TPA) 1 of modification, the 2-propylene diester), poly-(terephthalic acid (TPA) 1, the 3-propylene diester) of modification, poly-(the aphthenic acids second diester) of modification, and at United States Patent (USP) 6,353,050,6,274,298 and 6, those disclosed in 001,930, and their two or more blend; Polyamide, polyamide-ether and polyamide-ester, and at United States Patent (USP) 6,187, those disclosed in 864,6,001,930 and 5,981,654, and their two or more blend; Thermosetting and thermoplastic polyurethane, polyureas, polyurethane-polyurea blend, and their two kinds or more kinds of blends; Fluoropolymer, disclosed in 066,6,747,110 and 7,009,002 as United States Patent (USP) 5,691, 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 (for example, ethene), and Y is a carboxylic acid, as acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid or itaconic acid, X is the vinyl esters of softening comonomer such 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, be the alkyl methacrylate of 1-10 as the carbon number of alkyl; And their two kinds or more kinds of blends; The metallocene catalyst polymer, as by United States Patent (USP) 6,274, those disclosed in 669,5,919,862,5,981,654 and 5,703,166, and their two kinds or more kinds of blends; Polystyrene, as poly-(styrene-copolymerization maleic anhydride), acrylonitrile-butadiene-styrene (ABS), poly-(styrene-sulphonic acid ester), polyethylene styrene, and their two kinds or more kinds of blends; Polypropylene and polyethylene are particularly used the polypropylene of grafting of functional group's (as maleic anhydride of sulfonic acid) modification and the polyethylene of grafting, 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 that is less than about 9% weight, and their two kinds or more kinds of blends; Merlon, the blend of PC, 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 any two or more combination of above-mentioned polymer.What other were suitable is at United States Patent (USP) 5,919, disclosed thermoplastic compounds in 100,6,872,774 and 7,074,137.Here by reference the full content of above-mentioned document is included in.
The example of the suitable thermoplastic that can commercially obtain includes but not limited to: Thermoplastic polyether block acid amides can obtain from Arkema Inc. is commercial;
Figure BSA00000436993200152
Ionomer resin,
Figure BSA00000436993200153
Thermoplastic polyester elastomer and with trade name
Figure BSA00000436993200154
HPF1000 and HPF 2000 sell from poly-material, they can be from the commercial acquisition of E.I.du Pont de Nemours and Company;
Figure BSA00000436993200161
Ionomer can obtain from ExxonMobil Chemical Company is commercial;
Figure BSA00000436993200162
IO ionomeric ethylene acrylic copolymer can obtain from The Dow Chemical Company is commercial;
Figure BSA00000436993200163
Ionomer resin can obtain from A.Schulman Inc. is commercial;
Figure BSA00000436993200164
Based on the thermoplastic elastomer (TPE) of polyurethane, can obtain from BASF is commercial; And
Figure BSA00000436993200165
The polycarbonate/polyester blend can obtain from SABIC Innovative Plastics is commercial.
The suitable other materials that forms intermediate core layer comprises United States Patent (USP) 7,300, and disclosed core composition in 364 is here by with reference to the full content of introducing its disclosure.For example, Shi Yi material comprises the HNP with organic aliphatic acid and salt, metal cation or both combinations neutralization.Except the HNP with the neutralization of organic aliphatic acid and salt thereof, core compound can comprise that also at least a swelling index is at least about 40 elastomeric material.Preferred swelling index is at least about 50.Production resilience golf and therefore be applicable to polymer of the present invention include but not limited to can from Commercial CB23, the CB22 that obtains of Corporation can be from the commercial BR60 that obtains of Enichem, and can be from the commercial 1207G that obtains of Goodyear Corp..In addition, the rubber in the golf prepared in accordance with the present invention such as the typical Mooney viscosity of polybutadiene are 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 that is suitable for forming shell disclosed herein also is suitable for forming intermediate core layer.
In specific embodiment, intermediate core comprises the layer that is formed by two or more ionomeric blends.In the particular aspects of this embodiment, intermediate core layer is formed by the blend of the 50wt%/50wt% of the ethylene/methacrylic acid of two kinds of different part neutralizations.In another particular aspects of present embodiment, intermediate core layer is formed by the composition that comprises the first high acid content ionomer and the second high acid content ionomer blend, wherein the first high acid content ionomer (is for example randomly used the cation neutralization different with the second high acid content ionomer
Figure BSA00000436993200167
8150 Hes
Figure BSA00000436993200168
The blend of 50wt%/50wt% of 9120, can obtain from E.I.du Pont de Nemours and Company is commercial), and wherein said composition randomly comprises one or more melt flow modifier (melt flow modifiers), as ionomer, ethene-acid copolymer or ester terpolymer.
In another specific embodiment, intermediate core comprises the layer that the blend by the non-ionomeric polymer of one or more ionomers and maleic anhydride graft forms.In the particular aspects of this embodiment, non-ionomeric polymer is the metallocene catalyst polymer.In another particular aspects of this embodiment, intermediate core layer is formed by the ethylene/methacrylic acid of part neutralization and the poly blend of metallocene catalyst of maleic anhydride graft.
In another specific embodiment, intermediate core comprises at least one layer, and it forms by being selected from following composition: ionomer, polyester, polyamide, polyurethane, polyureas, polyurethane/polyurea blend, fluoropolymer and their two kinds or more kinds of blends of part and neutralization fully.Suitable especially is United States Patent (USP) 6,872, disclosed in 774 " comprising non-non-ionomer compositions " from poly-hardening polymer and at least a E/Y copolymer or E/X/Y terpolymer, with United States Patent (USP) 7,074, disclosed hard rigid core material in 137 is included the full content of its disclosure here by reference in.
In another specific embodiment, intermediate core comprises by being selected from the layer that following composition forms: the part and the ionomer of neutralization fully, and their two kinds or more kinds of blends, randomly with the non-ionomer polymer blend of maleic anhydride graft; Polyester elastomer; Polyamide elastomer, and their two or more combination.
The intermediate core layer composition can be with thermosetting diene compositions-treated or fusion to reduce or to flow when preventing molded (overmolding).Optional processing also can be included in the molding forward direction raw material and add peroxide, or carries out the molding post processing with for example crosslinker solution, electron beam, gamma radiation, isocyanates or amine aqueous solution processing etc.When thermoset layer can make under the crosslinked temperature of this layer thereon molding in the time of about 5 to 30 minutes, this temperature typically is 280 to 360 this processing and can prevents the intermediate layer fusing and flow, or locates " leakage " at the mould centre joint (equator) and go out.
Suitable thermoplasticity intermediate core layer composition further for example disclosing in the United States Patent (USP) 5,919,100,6,872,774 and 7,074,137, is included the full content of its disclosure here in by reference.
Intermediate core is sealed with outer core, outer core is individual layer, bilayer or multilayer, and preferred gross thickness within the range having a lower limit of 0.005 or 0.010 or 0.020 or 0.025 or 0.030 or 0.035 inch and on be limited in 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 the scope.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 bigger, perhaps 45 Shore C hardness or bigger, perhaps 50 Shore C hardness or bigger, perhaps 60 Shore C hardness or bigger, perhaps 70 Shore C hardness or bigger, perhaps 75 Shore C hardness or bigger, perhaps 80 Shore C hardness or bigger, perhaps 85 Shore C hardness or bigger, perhaps 90 Shore C hardness or bigger, perhaps the hardness number of outer surface within the range having a lower limit of 20 or 25 or 30 or 35 or 40 or 45 or 50 or 55 or 60 or 70 or 80 or 82 or 85 or 90 Shore C hardness and on be limited 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, wherein the upper limit greater than lower limit (for example, instantly be limited at 70 o'clock, on be limited to 75,80,82,85,90,92,93 or 95).Outer sandwich layer preferably have within the range having a lower limit of 40 45 or 50 53 or 55 57 or 58 and on be limited to Shore D outer surface hardness in 60 or 62 or 64 or 65 or 66 or 70 the scope.In specific embodiment, the outer surface hardness of outer core is greater than the outer surface hardness of inner core.In the particular aspects of this embodiment, the outer surface hardness of outer core and the outer surface hardness of inner core differ 5 Shore C stiffness units or bigger, or 10 Shore C stiffness units or bigger, or 15 Shore C stiffness units or bigger, or 20 Shore C stiffness units or bigger.In another specific embodiment, outer core is single layer, its case hardness within the range having a lower limit of 20 or 25 or 30 or 35 or 40 or 50 Shore C hardness and on be limited in the scope of 60 or 70 or 80 Shore C hardness, and by being selected from United States Patent (USP) 7,537,530 and 7,537, the rubber composition of those disclosed forms in 529, by reference the full content of its disclosure is included in here.
Each outer sandwich layer is preferably formed by rubber composition.Suitable rubber composition comprises aforementioned those that inner sandwich layer discloses that are used to form.Each outer sandwich layer can be and the identical or different rubber composition of composition that is used for forming inner sandwich layer.Inner sandwich layer or outer sandwich layer can further comprise 1 to 100phr curing agent.Preferably, if there is curing agent, curing agent is present in the outer core compound, rather than in the inner sandwich layer composition.Suitable curing agent includes but not limited to ionomer, acid copolymer and terpolymer, polyamide and polyester.Curing agent further for example disclosing in the United States Patent (USP) 6,120,390 and 6,284,840, is included the full content of its disclosure in here by reference.(for example can also add using trans-polyisoprene, the TP-301 using trans-polyisoprene, can be from Kuraray Co., Ltd. commercial the acquisition) or trans butadiene rubber with the rigidity that increases sandwich layer and/or improve cold forming character, this can improve machinability by sandwich layer half shell outside the easier molding in the golf manufacture process.In the time of in 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 of radially inwardly measuring from the outer surface of this core, this distance within the range having a lower limit of 0.10 0.15 or 0.20 0.25 or 0.50mm and on be limited to 2.50 5.00 or 6.00 6.50 or 7.00 or the scope of 8.00mm in.In another specific embodiment, maximum core hardness is higher than the outer surface hardness 5% of outer sandwich layer or bigger, or 10% or bigger, or 15% or bigger, or 20% or bigger.
The proportion of each sandwich layer within the range having a lower limit of 0.50 0.90 or 0.95 0.99 or 1.00 1.05 or 1.10g/cc and on be limited to 1.18 1.25 or 1.30 1.40 or 1.50 or the scope of 5.00g/cc in, perhaps 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 the proportion of outer sandwich layer and intermediate core layer is identical, substantially the same or greater than the proportion of intermediate core layer.In the particular aspects of this embodiment, the proportion of outer sandwich layer is greater than the proportion of inner sandwich layer, and outer sandwich layer is formed by the dense thin layer composition.The dense thin layer composition for example comprises by United States Patent (USP) 6,494, and those disclosed in 795 is included the full content of its disclosure in here by reference.Same suitable as the also having by United States Patent (USP) 6,149 of dense thin layer composition, disclosed thermoplastic in 535 and 6,152,834 is included the full content of its disclosure in here by reference.In specific embodiment, outer core is the fine and close thin layer of individual layer, preferred its proportion is 1.2 or bigger, or 1.5 or bigger, or 1.8 or bigger, or 2 or bigger, with and thickness within the range having a lower limit of 0.001 or 0.005 or 0.010 or 0.020 inch and on be limited in 0.020 or 0.030 or 0.035 or 0.045 or 0.050 or 0.060 inch the scope.This densification thin layer is preferably as coatings such as liquid solution, dispersion, lacquer, paste, gel, fused mass, if any the natural of load or filling or non-natural rubber latex, polyurethane, polyureas, epoxy resin, polyester, any reactivity or non-reacted coating or cast material; Solidify then, dry or be evaporated to the balance solid level.Fine and close thin layer also can be by compression or injection moulding, RIM, casting, spraying, dipping, powder coated or any means formation of deposition materials on inner core.Fine and close thin layer also can have the thermoplastic polymer of the filler, fiber, thin slice or the particle that increase proportion for load, makes it can be used as the shallow layer coating, and satisfies aforementioned preferred specific gravity balance.A particular instance of fine and close thin layer, it is made with compression moulding by soft polybutadiene and tungsten powder, and its thickness is 0.021 inch to 0.025 inch, and proportion is 1.31, and Shore C hardness is about 72.For the reactive fluid system, suitable material comprises that any reaction forms the material of 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 fine and close thin layer of preferred coating.But non-reactive material comprises the polymer of fusion or liquid form, any combination of dissolving or being dispersed in the powder in the solvent flashing.Fine and close thin layer is open in 2005/0059510 the U.S. Patent application at publication number more completely, by reference the full content of its disclosure is included in here.
The distribution of weight that can change the core that discloses here is to realize the parameter of some expectation, 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 use very soft inner core and adamantine intermediate core layer, core assembly has the low-down speed of rotation.Therefore, in the particular aspects of this embodiment, the moment of inertia (" MOI ") of the core assembly of being made up of inner core and intermediate core is 86gcm 2Or bigger, or 87gcm 2Or bigger, or 88gcm 2Or it is bigger.MOI measures in the MOI-005-104 the moment of inertia instrument that the Inertia Dynamics by Connecticut State Collinsville makes.This instrument connects PC, by the COMM port communication and by MOI instrument software 1.2 version drive.
Golf ball core of the present invention typically is 0.750 or bigger at the coefficient of resilience (" COR ") of 125ft/s, or 0.775 or bigger, or 0.780 or bigger, or 0.782 or bigger, or 0.785 or bigger, or 0.787 or bigger, or 0.790 or bigger, or 0.795 or bigger, or 0.798 or bigger, or 0.800 or bigger, or 0.810 or bigger, or 0.820 or bigger, or 0.830 or bigger, or 0.840 or bigger, or 0.850 or bigger.
The ball hardness of total core of golf ball core of the present invention typically within the range having a lower limit of 40 60 or 70 80 or 85 or 90 and on be limited in 100 or 105 or 110 or 115 the scope.
The multilayer core is sealed by shell, shell can be an individual layer, the shell of bilayer or multilayer, preferred gross thickness within the range having a lower limit of 0.010 or 0.015 or 0.020 or 0.025 or 0.030 or 0.040 or 0.045 inch and on be limited in 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 the scope, wherein the upper limit greater than lower limit (for example, instantly be limited at 0.040 o'clock, on be limited to 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 be single layer and its thickness within the range having a lower limit of 0.010 or 0.015 or 0.020 or 0.025 or 0.027 or 0.029 or 0.030 inch and on be limited in 0.030 or 0.033 or 0.034 or 0.035 or 0.040 or 0.050 inch the scope, and outer surface hardness within the range having a lower limit of 20 or 30 or 35 or 40 or 45 or 50 or 52 or 55 or 58 Shore D hardness and on be limited in the scope of 55 or 58 or 60 or 65 or 70 Shore D hardness, wherein the upper limit greater than lower limit (for example, when being limited to 58 Shore D hardness instantly, on be limited to 60 or 65 or 70 Shore D hardness), perhaps 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 within the range having a lower limit of 30 or 35 or 40 or 45 or 50 or 52 or 55 or 58 Shore D hardness and on be limited in the scope of 55 or 58 or 60 or 65 Shore D hardness, wherein the upper limit greater than lower limit (for example, when being limited to 58 Shore D hardness instantly, on be limited to 60 or 65 Shore D hardness).The shell composition preferably have according to ASTMD6272-98 rules B measure within the range having a lower limit of 5,000 or 12,000psi and on be limited to 24,000 or 50, the flexural modulus in the scope of 000psi.
In another specific embodiment, shell is bilayer or multilayered shell, and it comprises hypostracum or the subshell that is formed by ionomer compositions, and the outer shell that is 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 less than 65 Shore D hardness, or 50 to 65 Shore D hardness, or 57 to 60 Shore D hardness, perhaps 58 Shore D hardness, its thickness within the range having a lower limit of 0.010 or 0.020 or 0.030 inch and on be limited in 0.045 or 0.080 or 0.120 inch the scope.But outer shell is preferably formed by the copolymer or the blend of polyurethane that can cast or reaction injection molding(RIM), polyureas or polyurethane/polyurea.Described shell material is preferably heat cured, but also can be for 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 of this embodiment, the case hardness of outer shell within the range having a lower limit of 20 or 30 or 35 or 40 Shore D hardness and on be limited in the scope of 52 or 58 or 60 or 65 or 70 or 72 or 75 Shore D hardness.In another particular aspects of this embodiment, the surface thickness of outer shell within the range having a lower limit of 0.010 or 0.015 or 0.025 inch and on be limited in 0.035 or 0.040 or 0.045 or 0.050 or 0.055 or 0.075 or 0.080 or 0.115 inch the scope.
Suitable shell material includes but not limited to the blend of polyurethane, polyureas and polyurethane/polyurea; Ionomer resin and their blend are (for example,
Figure BSA00000436993200211
Ionomer resin and
Figure BSA00000436993200212
HPF 1000 and HPF 2000 can obtain from E.I.du Pont de Nemours and Company is commercial;
Figure BSA00000436993200213
Ionomer can obtain from ExxonMobil Chemical Company is commercial;
Figure BSA00000436993200214
IO ionomeric ethylene acrylic copolymer can obtain from The Dow Chemical Company is commercial; And
Figure BSA00000436993200215
Ionomer resin can obtain from A.Schulman Inc. is commercial); Polyethylene comprises for example 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 the part of ionomeric copolymers; Plastic body; Flexomer; Styrene/butadiene/styrene block copolymers; Styrene/ethylene-butylene/styrene block copolymer; The dynamic vulcanization elastomer; Ethylene vinyl acetate; Ethylene methyl acrylate; Corvic; Polyamide; Amide-ester elastomer, and the graft copolymer of ionomer and polyamide comprise, for example,
Figure BSA00000436993200216
Thermoplastic polyether block acid amides can obtain from Arkema Inc is commercial; Crosslinked using trans-polyisoprene and their blend; Based on the thermoplastic elastomer (TPE) of polyester, as
Figure BSA00000436993200217
Can obtain from E.I.du Pont de Nemours and Company is commercial; Based on the thermoplastic elastomer (TPE) of polyurethane, as Can obtain from BASF is commercial; Synthetic or natural vulcanized rubber; And their combination.
Polyurethane, polyureas and polyurethane-polyurea blend (being the blend and the copolymer of polyurethane and polyureas) are particularly suitable for forming shell of the present invention.When as the shell material, 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 the product by at least a polyisocyanates and at least a curing agent forms.Curing agent for example can comprise, one or more diamines, one or more polyalcohols or their combination.At least a polyisocyanates can combine with one or more polyalcohols and form prepolymer, and this prepolymer combines with at least a curing agent then.Thus, when describing polyalcohol here, their suitable being used in one or both components of polyurethane material are promptly as the part of prepolymer be used for curing agent.Curing agent comprises the polyalcohol curing agent, and it is preferably selected from: ethylene glycol; Diglycol; Polyethylene glycol; Propane diols; Polypropylene glycol; Low-molecular-weight polytetramethylene ether diol; 1, two (2-hydroxyl-oxethyl) benzene of 3-; 1, two [2-(2-hydroxyl-oxethyl) ethyoxyl] benzene of 3-; 1,3-pair 2-[2-(2-hydroxyl-oxethyl) ethyoxyl] and ethyoxyl } benzene; 1, the 4-butanediol; 1, the 5-pentanediol; 1, the 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 suits also comprises those that the product by at least a isocyanates and at least a curing agent forms, perhaps those that are formed by the product of at least a isocyanates, at least a polyalcohol and at least a curing agent.Preferred isocyanates comprises and is selected from following those: 4,4 '-methyl diphenylene diisocyanate, poly-4,4 '-liquid 4 of methyl diphenylene diisocyanate, carbodiimide modified, 4 '-methyl diphenylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanate, to phenylene vulcabond, toluene di-isocyanate(TDI), IPDI, to methyl dimethoxy phenylene diisocyanate, a methyl dimethoxy phenylene diisocyanate, adjacent methyl dimethoxy phenylene diisocyanate and their combination.Preferred polyhydric alcohols comprises and is selected from following those: PPG, hydroxyl terminated poly-butadiene, PEPA, PCL polyalcohol, polycarbonate polyol, and their combination.Preferred curing agent comprises polyamine curing agent, polyalcohol curing agent and their combination.Preferred especially polyamine curing agent.Preferably polyamine curing agent comprises, for example, 3,5-diformazan sulfenyl-2,4-toluenediamine or its isomers; 3,5-diethyl Toluene-2,4-diisocyanate, 4-diamines or its isomers; 4,4 '-two (Zhong Ding amino)-diphenyl methanes; 1, two (Zhong Ding amino) benzene, 4,4 of 4-'-methylene-two (2-chloroanilines); 4,4 '-methylene-two (3-chloro-2,6-diethylanilines); Two p-aminobenzoic acid 1, the ammediol ester; Polytetramethylene ether-two p-aminobenzoic acid ester; N, N '-dialkyl group MDA; P, p '-methylene dianiline (MDA); Phenylenediamine; 4,4 '-methylene-two (2-chloroanilines); 4,4 '-methylene-two (2, the 6-diethylaniline); 4,4 '-diaminourea-3,3 '-diethyl-5,5 '-dimethyl diphenyl methane; 2,2 ', 3,3 '-the tetrachloro MDA; 4,4 '-methylene-two (3-chloro-2,6-diethylanilines); And their combination.
The present invention is not limited to use specific polyisocyanates in the shell composition.Suitable polyisocyanates includes but not limited to, 4,4 '-liquid MDI, 4,4 '-the dicyclohexyl methyl hydride diisocyanate (" H of methyl diphenylene diisocyanate (" MDI "), polymeric MDI, carbodiimide modified 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, the 2-vulcabond; Tetramethylene-1, the 4-vulcabond; Cyclohexyl diisocyanate; 1,6-hexamethylene diisocyanate (" HDI "); Dodecane-1, the 12-vulcabond; Cyclobutane-1, the 3-vulcabond; Cyclohexane-1, the 3-vulcabond; Cyclohexane-1, the 4-vulcabond; 1-isocyanate group-3,3,5-trimethyl-5-isocyanate group methyl cyclohexylamine; Methyl cyclohexane support vulcabond; The triisocyanate of HDI; 2,4,4-trimethyl-1, triisocyanate, aphthacene vulcabond, naphthalene diisocyanate, the anthracene vulcabond of 6-hexane diisocyanate (" TMDI "); And their combination.Those skilled in the art know polyisocyanates and have NCO more than one, for example, 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 4,4 '-the liquid MDI of 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 than conventional vulcabond, and composition promptly of the present invention typically has and is less than about 0.1% free monomer group.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 a polyisocyanates should have and is less than 14% unreacted NCO group.Preferably, at least a polyisocyanates has and is no more than 8.5% NCO, and more preferably 2.5% to 8.0%, even more preferably 4.0% to 7.2%, and most preferably 5.0% to 6.5%.
The invention is not restricted in the shell composition, use specific polyalcohol.In one embodiment, the molecular weight of polyalcohol is about 200 to about 6000.Exemplary polyalcohol includes but not limited to, PPG, hydroxyl terminated poly-butadiene (derivative that comprises part/complete hydrogenation), PEPA, polycaprolactone polyol and polycarbonate polyol.Preferred especially polytetramethylene ether diol (" PTMEG "), polyethylene glycol propane diols, polyoxypropylene diols, and their combination.Hydrocarbon chain can have saturated or unsaturated bond and replacement 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, perhaps replaces or unsubstituted aryl and cyclic group.Suitable PCL polyalcohol includes but not limited to, 1, the PCL, 1 that the PCL that the PCL that the PCL that the 6-hexylene glycol causes, diethylene glycol (DEG) cause, trimethylolpropane cause, neopentyl glycol cause, the PCL that the 4-butanediol causes, and their combination.Hydrocarbon chain can have saturated or unsaturated bond, or replacement 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 replacement or unsubstituting aromatic yl and cyclic group.
The polyamine fixative is also suitable to be used in the curing agent of urethane composition, and has had been found that anti-cutting, shear resistant and the impact resistance that can promote the gained ball.Preferably the polyamine fixative includes but not limited to, 3, and 5-diformazan sulfenyl-2,4-toluenediamine and isomers thereof; 3,5-diethyl Toluene-2,4-diisocyanate, 4-diamines and isomers thereof, as 3,5-diethyl Toluene-2,4-diisocyanate, 6-diamines; 4,4 '-two (Zhong Ding amino)-diphenyl methanes; 1, two (Zhong Ding amino) benzene, 4,4 of 4-'-methylene-two (2-chloroanilines); 4,4 '-methylene-two (3-chloro-2,6-diethylanilines); Polytetramethylene ether-two p-aminobenzoic acid ester; N, N '-dialkyl group MDA; P, p '-methylene dianiline (MDA) (" MDA "); M-phenylene diamine (MPD) (" MPDA "); 4,4 '-methylene-two (2-chloroaniline) (" MOCA "); 4,4 '-methylene-two (2, the 6-diethylaniline); 4,4 '-diaminourea-3,3 '-diethyl-5,5 '-dimethyl diphenylmethane; 2,2 ', 3,3 '-the tetrachloro diaminodiphenyl-methane; 4,4 '-methylene-two (3-chloro-2,6-diethylanilines); Two p-aminobenzoic acid 1, the ammediol ester; And their combination.Preferably, curing agent of the present invention comprises 3,5-diformazan sulfenyl-2, and 4-toluenediamine and isomers thereof are as ETHACURE300.Suitable polyamine fixative comprises primary amine and secondary amine, and it preferably has scope in about 64 to about 2000 weight average molecular weight.
Can join in the urethane composition one of at least in glycol, triol, tetrol or the hydroxy-end capped fixative.Suitable glycol, three pure and mild tetrol groups comprise ethylene glycol; Diethylene glycol (DEG); Polyethylene glycol; Propane diols; Polypropylene glycol; The low-molecular-weight polytetramethylene ether diol; 1, two (2-hydroxyl-oxethyl) benzene of 3-; 1, two [2-(2-hydroxyl-oxethyl) ethyoxyl] benzene of 3-; 1,3-pair 2-[2-(2-hydroxyl-oxethyl) ethyoxyl] and ethyoxyl } benzene; 1, the 4-butanediol; 1, the 5-pentanediol; 1, the 6-hexylene glycol; Resorcinol-two (4-hydroxyethyl) ether; Quinhydrones-two (4-hydroxyethyl) ether; And their combination.Preferred hydroxy-end capped fixative comprises ethylene glycol; Diethylene glycol (DEG); 1, the 4-butanediol; 1, the 5-pentanediol; 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 weight, and those of ordinary skills understand like this.
Hydroxy-end capped and amine fixative can comprise one or more saturated, undersaturated, aromatics and groups ring-type.In addition, hydroxy-end cappedly can comprise one or more halogen groups with the amine fixative.Urethane composition can be formed by the blend or the mixture of curing agent.Yet if desired, urethane composition can be formed by single curing agent.
Any method that those of ordinary skills know may be used to make polyisocyanates of the present invention, polyalcohol and curing agent combination.A kind of common method is called as one step process in this area, comprises mixing polyisocyanates, polyalcohol and curing agent simultaneously.This method obtains the mixture of heterogeneous body (more random), and makes the producer lower to the control of the molecular structure of resulting composition.Preferred mixed method is called as prepolymer process.In the method, before adding curing agent, mix polyisocyanates and polyalcohol separately.This method provides the mixture than homogeneous, has obtained consistent polymer and has formed.
Suitable polyurethane further for example disclosing in the United States Patent (USP) 5,334,673,6,506,851,6,756,436,6,867,279,6,960,630 and 7,105,623, is included the full content of its disclosure in here by reference.Suitable polyureas is open in 60/401,047 the U.S. Patent application at for example United States Patent (USP) 5,484,870 and 6,835,794 and application number further, by reference the full content of its disclosure is included in here.Suitable polyurethane-polyurea shell material comprises the polyurethane/polyurea blend and comprises the copolymer of carbamate and urea segment, be disclosed in 2007/0117923 the U.S. Patent application as publication number, by reference the full content of its disclosure included in here.
The composition that comprises ionomer or two or more ionomeric blends also is particularly suitable for forming shell.Preferred ionomer shell composition comprises:
(a) comprise " high acid content ionomer (high acid ionomer) " (promptly having acid content) greater than 16wt%, as
Figure BSA00000436993200251
Composition;
(b) the non-ionomeric polymer that comprises high acid content ionomer and maleic anhydride graft (for example,
Figure BSA00000436993200252
Functionalized polymeric) composition.The blend of the polymer of particularly preferred high acid content ionomer and maleic anhydride graft is the Surlyn of 84wt%/16wt%
Figure BSA00000436993200253
With
Figure BSA00000436993200254
Blend.The blend of the polymer of high acid content ionomer and maleic anhydride graft further for example disclosing in the United States Patent (USP) 6,992,135 and 6,677,401, is included the full content of its disclosure in here by reference;
(c) comprise 50/45/5 The composition of blend, it preferably has the material hardness of 80 to 85 Shore C hardness;
(d) comprise 50/25/25
Figure BSA00000436993200256
The composition of blend, it preferably has the material hardness of about 90 Shore C hardness;
(e) comprise 50/50 The composition of blend, it preferably has the material hardness of about 86 Shore C hardness;
(f) comprise The composition of blend, it comprises melt flows modifier alternatively;
(g) comprise the composition of the first high acid content ionomer and the ionomeric blend of the second high acid content, the first high acid content ionomer cation neutralization different wherein (for example 50/50 with the second high acid content ionomer
Figure BSA00000436993200262
With
Figure BSA00000436993200263
Blend), comprise alternatively one or more melt flows modifier such as ionomer, ethene-acid copolymer or with the terpolymer of ester; And
(h) comprise the ionomeric composition of ethylene acid/ester of the first high acid content ionomer and ionomeric blend of the second high acid content and 0-10wt%, the wherein first high acid content ionomer cation different neutralization, ethylene acid/ester ionomer with the second high acid content ionomer use the cation neutralization identical with the first high acid content ionomer or the second high acid content ionomer or use with the first and second high acid content ionomers with the different cations (40-50wt% for example that neutralizes
Figure BSA00000436993200264
40-50wt%'s
Figure BSA00000436993200265
With 0-10wt%'s Blend).
Figure BSA00000436993200267
With
Figure BSA00000436993200268
Be the E/MAA copolymer of different brackets, wherein acid groups partly neutralizes with sodium ion.
Figure BSA00000436993200269
With
Figure BSA000004369932002610
Be the E/MAA copolymer of different brackets, wherein acid groups partly neutralizes with zinc ion.
Figure BSA000004369932002611
Be the E/MAA copolymer, wherein acid groups partly neutralizes with lithium ion.
Figure BSA000004369932002612
Be the magnesium ionomer of very low modulus, have medium acid content.
Figure BSA000004369932002613
Be the E/MAA copolymer resin, its methacrylic acid that is nominally with 15wt% makes.
Figure BSA000004369932002614
Ionomer,
Figure BSA000004369932002615
Polymer and
Figure BSA000004369932002616
Copolymer all can obtain from E.I.du Pont de Nemours and Company is commercial.
Ionomer shell composition can with the nonionic thermoplastic resin, specifically, this is in order to control the character of product.The example of suitable non-ionic thermal plastic resin includes but not limited to that polyurethane, polyether ester, polyamide ether, polyethers urea, thermoplastic polyether block acid amides are (for example
Figure BSA000004369932002617
Block copolymer, can obtain from Arkema Inc. is commercial), SBS, styrene (ethene-butylene)-styrene block copolymer, polyamide, polyester, polyolefin (for example, polyethylene, polypropylene, ethylene-propylene copolymer, polyethylene-(methyl) acrylate, polyethylene-(methyl) acrylic acid, has the functionalized polymeric of maleic anhydride graft
Figure BSA000004369932002618
Functionalized polymeric, can obtain from E.I.duPont de Nemours and Company is commercial, the polymer that epoxidation is functionalized, elastomer are (for example, 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, as, but be not limited to,
Figure BSA000004369932002619
Acid copolymer resin, especially
Figure BSA00000436993200271
Acid copolymer resin can obtain from E.I.du Pontde Nemours and Company is commercial.
Suitable ionomer shell material further for example disclosing in the United States Patent (USP) 6,653,382,6,756,436,6,894,098,6,919,393 and 6,953,820, is included the full content of its disclosure in here by reference.
The shell composition can comprise the filler of one or more kinds, as the above-mentioned filler that is used for rubber composition of the present invention that provides (for example, 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 that is formed by full-cream fat adoption urea.In another specific embodiment, shell is to be the simple layer that disclosed polyurea composition forms in 2009/0011868 the U.S. Patent application by being preferably selected from publication number, by reference the full content of its disclosure is included in here.
Suitable shell material and structure also comprise, but being not limited to, is 2005/0164810 U.S. Patent application, United States Patent (USP) 5,919 at publication number, 100,6,117,025,6,767,940 and 6,960,630 and publication number be those disclosed in the PCT application of WO00/23519 and WO00/29129, by reference the full content of its disclosure is included in here.
The aqueous vapor barrier layer is set between core and shell alternatively.The aqueous vapor barrier layer is further at for example 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 2003/0069082,2003/0069085,2003/0130062,2004/0147344,2004/0185963,2006/0068938,2006/0128505 and 2007/0129172 the U.S. Patent application, by reference the full content of its disclosure is included in here.
Golf ball layer except innermost layer and outermost one or more layers randomly be non-uniform thickness the layer.For purpose of the present disclosure, " layer of non-uniform thickness " is meant such layer, and it has projection, net, rib etc. and is positioned at and makes the varied in thickness of this layer on this layer.The layer of non-uniform thickness preferably has one or more in following: a plurality of projectioies placed on it, a plurality of vertical net, a plurality of horizontal net or a plurality of circle-shaped net.In a kind of specific embodiment, the layer of non-uniform thickness comprises a plurality of projectioies that place its outer surface and/or inner surface.Projection can be integrally manufactured with this layer, perhaps can make separately to be attached to then on this layer.Projection can have Any shape or section, include but not limited to trapezoidal, sinusoidal, dome shape, stairstepping, cylindrical, conical, frustroconical, rectangle, pyramid, truncation pyramid or polyhedron shape with polygon bottom surface.The shape and the section that suit inboard and outside projection also are included in United States Patent (USP) 6,293, and those disclosed in 877 is included the full content of its disclosure in here by reference.In another specific embodiment, the layer of non-uniform thickness comprises a plurality of inboards of setting thereon and/or the circular net in the outside.In the particular aspects of present embodiment, the existence of net has increased the rigidity of non-uniform thickness layer.Net can be vertical net, horizontal net or circle-shaped net.
The non-uniform thickness layer of golf of the present invention preferably has within the range having a lower limit of the thickness in 0.010 or 0.015 inch to 0.100 or 0.150 inch the scope, and preferably have be limited to down 5000 or 10000psi and on be limited to 80000 or the scope of 90000psi in flexural modulus.
The layer of non-uniform thickness is open in 2008/0248898 the U.S. Patent application at for example United States Patent (USP) 6,773,364 and publication number further, by reference the full content of its disclosure is included in here.
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, the ternary polymerization ionomer, Merlon, polyolefin, polyamide, copolyamide, polyester, polyesteramide, polyetheramides, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polyarylate, polyacrylate, polyphenylene oxide, impact modification polyphenylene oxide, the high-impact polystyrene, the diallyl phthalate polymer, the metallocene catalyst polymer, styrene-acrylonitrile (SAN), olefin-modified SAN, acrylonitrile-styrene-acrylonitrile, phenylethylene-maleic anhydride (S/MA) polymer, styrol copolymer, the functionalized styrene copolymer, the 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 the composition disclosed herein also comprises the resin that obtains in the following manner: (1) is dicarboxylic acids such as oxalic acid, adipic acid, decanedioic acid, terephthalic acid (TPA), M-phthalic acid or 1 (a), 4 cyclohexane dicarboxylic acids and (b) diamine such as ethylenediamine, butanediamine, pentanediamine, hexamethylene diamine or decamethylene diamine, 1, the polycondensation of 4-cyclohexyl diamines or m-xylene diamine; (2) ring-opening polymerisation of cyclic lactames such as epsilon-caprolactams or omega-lauric lactam; (3) polycondensation of amino carboxylic acid such as 6-aminocaprolc acid, 9 aminononanoic acid, 11-aminoundecanoic acid or 12; The perhaps copolymerization of (4) cyclic lactames and dicarboxylic acids and diamine.The object lesson of suitable polyamide comprises nylon, nylon MXD 6 and the nylon 46 of nylon 6, nylon 66, NYLON610, nylon 11, nylon 12, copolymerization.
Suitable other preferred materials as additional materials in the disclosed golf composition here comprise the Skypel polyester elastomer, can obtain from the SKChemicals of Korea S is commercial; Diblock and triblock copolymer can obtain from the Kuraray Corporation of Japanese Kurashiki is commercial; And
Figure BSA00000436993200291
Diblock and triblock copolymer can obtain from the KratonPolymers LLC in Houston, Texas city is commercial.
Ionomer also is suitable for and composition blend disclosed herein very much.Suitable ionomer comprises ionomer resin alpha-olefin/copolymers of unsaturated carboxylic acids type or the terpolymer type.Copolymers ionomers is by with in the metal ion and alpha-olefin and have the α of 3-8 carbon atom, obtaining to the small part carboxyl in the copolymer of beta-unsaturated carboxylic acid.Terpolymer type ionomer is by with in the metal ion and alpha-olefin, have the α of 3-8 carbon atom, beta-unsaturated carboxylic acid and have the α of 2-22 carbon atom, obtaining to the small part carboxyl in the terpolymer of beta-unsaturated carboxylic acid ester.The suitable example that is used for copolymer type and the ionomeric alpha-olefin of terpolymer type comprises ethene, propylene, 1-butylene and 1-hexene.The suitable example that is used for copolymer type and the ionomeric unsaturated carboxylic acid of terpolymer type comprises acrylic acid, methacrylic acid, ethylacrylic acid, α-Lv Daibingxisuan, butenoic acid, maleic acid, fumaric acid and itaconic acid.Copolymer type comprises having the different acid contents and the ionomer of sour degree of neutralization with terpolymer type ionomer, and they are by unit price described herein or bivalent cation neutralization.Be suitable for and can the comprising by the commercial ionomer that obtains of composition blend disclosed herein
Figure BSA00000436993200292
Ionomer resin can obtain from E.I.du Pont deNemours and Company is commercial, and
Figure BSA00000436993200293
Ionomer can obtain from ExxonMobilChemical Company is commercial.
Silicone material also is highly suitable for and composition blend disclosed herein.Suitable silicone material comprises monomer, oligomer, prepolymer and the polymer that adds or do not add reinforcer.One type of suitable silicone material can be in conjunction with at least 1 thiazolinyl with at least 2 carbon atoms in their molecule.The example of these thiazolinyls includes but not limited to, vinyl, pi-allyl, cyclobutenyl, pentenyl, hexenyl 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.Remaining in this component (for example, non-thiazolinyl) and the organic group of silicon bonding are independently selected from alkyl or the halo alkyl of the unsaturated part of not fatty family.These nonrestrictive example comprises: alkyl, as methyl, ethyl, propyl group, butyl, amyl group and hexyl; Cycloalkyl is as cyclohexyl and suberyl; Aryl is as phenyl, tolyl and xylyl; Aralkyl is as benzyl and phenethyl; And haloalkyl, as 3,3,3-three fluoro propyl group and chloro methyl.The alkyl that the another kind of type of suitable silicone material has the unsaturated part of not fatty family.Object lesson comprises: the dimethyl siloxane of trimethylsiloxy group end-blocking-methyl hexenyl silicone copolymers; The dimethyl siloxane of dimethyl hexenyl siloxy end-blocking-methyl hexenyl silicone copolymers; The dimethyl siloxane of trimethylsiloxy group end-blocking-methyl ethylene silicone copolymers; Methyl phenyl siloxane-the dimethyl siloxane of trimethylsiloxy group end-blocking-methyl ethylene silicone copolymers; The dimethyl polysiloxane of dimethyl ethene siloxy end-blocking; Dimethyl siloxane-methyl ethylene the silicone copolymers of dimethyl ethene siloxy end-blocking; The methyl phenyl silicone of dimethyl vinyl siloxy end-blocking; Methyl phenyl siloxane-dimethyl siloxane-methyl ethylene the silicone copolymers of dimethyl vinyl siloxy end-blocking; And above-mentioned listed copolymer, wherein at least one group is the dimethyl hydroxyl siloxy.Be suitable for composition blend disclosed herein can the commercial silicone that obtains example comprise
Figure BSA00000436993200301
Silicone rubber can obtain from the Dow Corning Corporation of state of Michigan Midland is commercial; Silicone rubber can obtain from the General Electric Company of New York Waterford is commercial; And
Figure BSA00000436993200303
Silicone can obtain from the Wacker Chemie AG of Germany is commercial.
The copolymer of other types also can join in the golf composition disclosed herein.For example, the suitable copolymer that comprises epoxy monomer comprises SBS, and wherein polybutadiene block comprises epoxy radicals, and SIS, and wherein polyisoprene blocks comprises epoxy radicals.Example that can the commercial epoxy-functional copolymer that obtains comprises ESBS A1005, ESBS A1010, ESBS A1020, ESBS AT018 and ESBS AT019 epoxidation vinyl benzene-butadiene-styrene block copolymer, can obtain from the Daicel ChemicalIndustries Inc. of Japan is commercial.
Be used to form each golf ball layer of the present invention from poly-composition can with the nonionic thermoplastic resin, specifically, this is in order 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,
Figure BSA00000436993200304
Thermoplastic polyether block acid amides (can obtain from Arkema Inc. is commercial), SBS, styrene (ethene-butylene) styrene block copolymer, polyamide, polyester, polyolefin are (for example, polyethylene, polypropylene, ethylene-propylene copolymer), ethene-(methyl) acrylate, ethene-(methyl) acrylic acid, have the abrasive flour of functionalized polymeric, elastomer (for example, the polyethylene of EPDM, metallocene catalyst) and the thermo-setting elastomer of maleic anhydride graft and epoxidation etc.
Composition disclosed herein can be foaming or fill with density controlling material, so that suitable golf Performance Characteristics to be provided.
The invention is not restricted to the technology of any specific formation golf ball layer.Should be appreciated that described each layer can form by any suitable technique, comprises injection moulding, compression moulding, casting and reaction injection molding(RIM).Especially, the thermosetting thin layer can form by the formation sulfuration of any conventional or the method for other cross-linked rubber thin layers, includes but not limited to compression molding, rubber injection mold, liquid rubber casting and lamination.
When adopting injection moulding, said composition can easily supply to the ball shape 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 the thermotank under 200 to 500 by screw melting and transmission.The composition of fusing finally is injected in the die cavity of sealing, and this die cavity can be at ambient temperature or cooling at elevated temperatures, but typically, and mold cools down to 50 is to 70 temperature.In the mould of sealing, stopped 1 second to 300 seconds, after preferred 20 seconds to 120 seconds, core and/or core are added that one or more additional wick or shell take out from mould, it is cooled off in the temperature of environment temperature or reduction, perhaps place the dry ice of cooling fluid such as water, frozen water, solvent etc.
When adopting compression molding to form core, said composition at first forms prefabricated component or blank material, and it typically is sphere cylindrical or roughly, and its weight overweights the desired wt of the core that is molded as slightly.Before this step, composition can be extruded earlier or otherwise melt and force it to pass through die head (die), is cut into cylindrical preform then.Then this prefabricated component is placed the compression mould chamber, and 150 to 400, preferred 250 to 400, more preferably 300 to 400 mold temperature lower compression.When compression molding is outer, form the casing half of layer material earlier by injection moulding.Then with golf assembly Bao Mi in two and half shells, be placed on then the compression mould chamber and the compression.
Reaction injection molding(RIM) technology is further at for example 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 2006/0247073 the U.S. Patent application, by reference the full content of its disclosure is included in here.
The thermoplastic layer here can handle in the mode of the hardness gradient that produces plus or minus.Used therein in the golf ball layer of the present invention of thermoset rubber, can adopt technology that produces gradient and/or the rubber compounding that produces gradient.The gradient technology and the prescription that produce gradient are 12/048 at the application number of for example submission on March 14th, 2008 more completely, 665, the application number of submitting on July 27th, 2007 is 11/829,461, the application number of submitting on July 3rd, 2007 is 11/772,903, the application number of submitting on August 1st, 2007 is 11/832,163, the application number of submitting on August 1st, 2007 is 11/832, open in 197 the U.S. Patent application, by reference the full content of its disclosure is included in here.
Golf of the present invention typically has more than 0.700, more preferably more than 0.750, and the more preferably COR more than 0.780.Here used COR determines according to known rules, and wherein golf or golf assembly (as, golf ball core) penetrate from air bubble with two given speed, and calculate under speed 125ft/s.The trajectory shadow shield between the air bubble of fixed range and steel plate to measure ball speed.When ball flew to steel plate, it excited each shadow shield, measured the time at each shadow shield place.The incident traveling time that this provides the incidence rate with ball to be inversely proportional to.Pellet impact steel plate and bounce-back are measured once more between each shadow shield and are advanced the required time by shadow shield.This provides the outgoing traveling time that is inverse ratio with the outgoing speed of ball.Then as the ratio calculating COR of outgoing traveling time with the incident traveling time, COR=V Go out/ V Go into=T Go into/ T Go out
The hardness that golf of the present invention has usually is 40 or bigger, perhaps within the range having a lower limit of 40 50 or 60 65 or 80 85 or 90 and on be limited in 80 or 85 or 90 or 100 or 110 or 115 or 120 the scope, wherein the upper limit greater than lower limit (for example, instantly be limited at 85 o'clock, on be limited to 90,100,110,115 or 120).Ball hardness is key factor in the golf design.For example, the hardness of core can influence spin rate and the feel that ball leaves rod (driver).Compressionby Any Other Name as JeffDalton, Science and Golf IV, Proceedings of the World ScientificCongress of Golf (Eric Thain ed., Routledge, 2002) disclosed in (" J.Dalton "), several diverse ways can be used to measure hardness, comprise Atti ball hardness, Riehle ball hardness, the load under different fixing load and skew (offset)/deflection is measured and effective modulus.For the purposes of the present invention, " ball hardness " is meant Atti ball hardness and uses Atti ball hardness test equipment to measure according to known method, and wherein, piston is used for ball is pressed to spring.The stroke of piston is that fix and deflection measuring spring.The measurement of spring deflection does not touch ball from spring; But when being roughly the spring deflection of first 1.25mm (0.05 inch), skew begins.The low-down core of rigidity can not make the spring deflection surpass 1.25mm, thereby obtains 0 ball hardness measurement value.Atti ball qualimeter is to be designed for that to measure diameter be 1.680 inches object; Thereby, the total height of the core bed hedgehopping to 1.680 of less object such as golf inch must be obtained accurate reading.Can Atti ball hardness be converted to Riehle (core), Riehle (ball), 100kg deflection, 130-10kg deflection or effective modulus according to formula given in J.Dalton.
Golf of the present invention typically has 60% or bigger, and preferred 65% or bigger, and more preferably 75% or bigger 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 within the range having a lower limit of 1.680 inches and on be limited in 1.740 or 1.760 or 1.780 or 1.800 inches the scope.
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 bigger, or 87gcm 2Or it is bigger.MOI measures in the moment of inertia instrument of the model MOI-005-104 that the Inertia of Connecticut State Collinsville Dynamics makes.This instrument connects PC, by the COMM port communication and by MOI instrument software 1.2 version drive.
The case hardness of golf ball layer is obtained from the relative mean value of repeatedly measuring of each hemisphere, notes avoiding in the separator bar of core or blemish such as hole or the prominence is measured.Hardness measurement is according to ASTMID-2240 " hardometer is measured the identation hardness of rubber and plastics ".Owing to be curved surface, should be noted that and guaranteed before carrying out the case hardness reading that golf or golf assembly are placed under the penetrator between two parties.Can reading be used for all hardness measurements, and read the hardness reading when being configured to obtain after the full-scale reading 1 second to the digital hardometer through calibration of 0.1 stiffness units.The numeral hardometer must be connected on the pedestal of automatic station (automatic stand), and its bottom also must be parallel to this pedestal.Weight on the hardometer and impact speed meet ASTM D-2240.
The central hardness of core obtains according to following rules.Lightly core is pressed in the hemisphere clamper of diameter that internal diameter is slightly less than core approximately, makes core be clamped in the hemispherical portion of clamper just, the geometric center plane of this core is exposed.Utilize friction that core is fixed in the clamper, it can not move in cutting and polishing step thus, but friction can not be too big 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, measure the diameter that becomes the core of 90 degree with this direction.Also measure the top of the bottom of clamper, think that calculating in the future provides reference point to core.Use band saw or other suitable cutting elements on geometric center, to carry out rough cut, guarantee that this step SMIS does not move in clamper a little more than the exposure of core.The remainder of the core in clamper still is fixed on the substrate of surface finish machine." slightly " surface finish that exposes is become the surface of smooth planar, the geometric center of exposing core, this can confirm to the height of core exposed surface from clamp base by measuring, guarantee the core original height that as above records accurate half ± 0.004 inch be removed.Core is stayed in the clamper, found the center of core with the central straight angle square, and careful mark, its hardness measured at the centre mark place according to ASTM D-2240.Then, carry out in the following manner apart from other hardness measurements at any distance place, center of core: from centre mark setting-out radially outward, and along this line in any distance, typically with the increment measurement hardness of distance center 2mm.Apart from the hardness of center specified distance should along respectively separately 180 ° or separately the radial arms of 90 ° of location measure at least 2 times, preferred 4 times, be averaged then.All all still carry out in clamper and when not upsetting its orientation at core passing the hardness measurement carried out on the plane of geometric center, make test surfaces be parallel to the bottom of clamper consistently, and therefore also are parallel to the suitably bottom of alignment of hardometer.
Should only measure hardness point one time in any specific geometric position.
For purpose of the present disclosure, the hardness gradient at center defines by the hardness measurement value at the central point of center outer surface and core." bear " and " just " refers to that the hardness number with the outer surface of golf assembly deducts the result of the inner most hardness number of this assembly.For example, if the outer surface at solid center than the hardness number low (being surface ratio center softness) at center, then hardness gradient is " bearing " gradient.During the hardness gradient of measuring center, central hardness is at first determined according to the rules of the central hardness of above-mentioned acquisition core.In case mark core the center and determined its hardness, carry out in the following manner apart from the hardness measurement at any distance place, center of core: from mark center setting-out radially outward, and typically with the increment measurement of 2mm and mark distance apart from the center.All all still carry out in clamper and when not upsetting its orientation at core passing the hardness measurement carried out on the plane of geometric center, make test surfaces be parallel to the bottom of clamper consistently.The difference of hardness in any precalculated position is calculated as the hardness that average surface hardness deducts suitable reference point on the core, thereby the core that the surface is softer than its center will have negative hardness gradient, described suitable reference point for single, solid core for example in the core center.
Hardness gradient is more completely at for example United States Patent (USP) 7,429,221, the application number of submitting to on November 14th, 2007 is 11/939,632, the application number of submitting on November 14th, 2007 is that the application number of submitting on November 14th, 11/939,634,2007 is that the application number of submitting on November 14th, 11/939,635 and 2007 is 11/939, open in 637 the U.S. Patent application, by reference the full content of its disclosure is included in here.
Be to be understood that " material hardness " and " the directly hardness of measuring " has essential distinction on golf.For purpose of the present disclosure, the hardness of material is measured according to ASTM D2240, and generally includes the hardness of flat " sheet " or " compressing tablet " of measuring this material formation.Directly go up the hardness of measuring and typically produce different hardness numbers at golf (or other spherical surfaces).This species diversity of hardness number is because of some factors, and the material that includes, but not limited to spherical structure (for example, the type of core, the quantity of core and/or shell etc.), ball (or spheroid) diameter and adjacent layer is formed.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, contained any combination that to use these numerical value.
Here all patents of quoting, publication, test procedure and other lists of references, comprise priority text, all intactly do not include the application in its disclosed content by reference, and described including in all carried out such including in all judicial districts that are allowed to the inconsistent degree of the present invention.
Though described exemplary embodiment of the invention in detail, should be understood that to those skilled in the art do not breaking away under purport of the present invention and the scope, other modification are obviously and easily to obtain.Therefore, be not intended to make appended claim scope to only limit to example given here and description, on the contrary, claim can be interpreted as comprising the feature of the patentability innovation that all the present invention have, and comprises that one skilled in the art of the present invention are considered as all features of equivalent feature.

Claims (20)

1. golf comprises:
By the following core of forming:
The center, it is formed by the first diene rubber composition, 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 The center) be 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 bigger; With
Outer sandwich layer, it is formed by the second diene rubber composition, and thickness is 0.010 inch to 0.100 inch, and outer surface hardness (SH Outward) be 80 Shore C hardness or bigger;
SH wherein OutwardGreater than SH The center
Highest hardness (the SH of this core wherein The peak) be positioned at 0.25mm to the 5.00mm distance of radially inwardly measuring from the outer surface of core; And,
SH wherein The peakBe higher than SH Outward10% or more; With
Thickness is 0.010 inch to 0.050 inch and the shell that formed less than the composition of 60 Shore D hardness by material hardness.
2. the golf of claim 1, wherein SH The peakBe higher than SH Outward20% or more.
3. the golf of claim 1, wherein SH The peakBe positioned at 0.50mm to the 5.00mm distance of radially inwardly measuring from the outer surface of core.
4. the golf of claim 1, wherein SH The peakBe positioned at 0.50mm to the 2.50mm distance of radially inwardly measuring from the outer surface of core.
5. the golf of claim 1, wherein SH The peakBe higher than SH Outward20% or more; And SH wherein The peakBe positioned at 0.50mm to the 5.00mm distance of radially inwardly measuring from the outer surface of core.
6. the golf of claim 1, wherein SH OutwardWith SH The centerDiffer 5 Shore C stiffness units or more.
7. the golf of claim 1, wherein SH OutwardWith SH The centerDiffer 10 Shore C stiffness units or more.
8. the golf of claim 1, wherein, described center has positive hardness gradient, and wherein the difference of the central hardness at center and case hardness is 10 to 45.
9. the golf of claim 1, wherein, the diameter at described center is 1.300 inches to 1.490 inches, the thickness of described intermediate core layer be 0.020 inch to 0.070 inch and described outside the thickness of sandwich layer be 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 bigger.
11. the golf of claim 1, the case hardness of wherein said intermediate core layer are 70 Shore D hardness or bigger.
12. the golf of claim 1, wherein SH OutwardBe 85 Shore C hardness or bigger.
13. the golf of claim 1, the thermoplastic compounds of wherein said intermediate core layer are selected from ionomers, and they two or more the blend of the ionomer of part neutralization and all neutralizations.
14. golf comprises:
By the following core of forming:
The center, it is formed by the first diene rubber composition, 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 The center) be 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 bigger; With
Outer sandwich layer, it is formed by the second diene rubber composition, and thickness is 0.020 inch to 0.050 inch, and outer surface hardness (SH Outward) be 85 Shore C hardness or bigger;
SH wherein OutwardGreater than SH The center
Highest hardness (the SH that has of this core wherein The peak) be positioned at 0.50mm to the 5.00mm distance of radially inwardly measuring from the outer surface of core; And, SH wherein The peakBe higher than SH Outward10% or more; With
Thickness is 0.010 inch to 0.050 inch and the shell that formed less than the composition of 60 Shore D by material hardness, and wherein the shell composition is selected from polyurethane, polyureas and polyurethane-polyurea blend.
15. the golf of claim 14, wherein SH The peakBe higher than SH Outward20% or more.
16. the golf of claim 14, wherein SH The peakBe positioned at 0.50mm to the 2.50mm distance of radially inwardly measuring from the outer surface of core.
17. the golf of claim 14, wherein SH The peakBe higher than SH Outward20% or more; SH wherein The peakBe positioned at 0.50mm to the 2.50mm distance of radially inwardly measuring from the outer surface of core.
18. the golf of claim 14, wherein SH OutwardWith SH The centerDifference be 5 Shore C stiffness units or more.
19. the golf of claim 14, wherein SH OutwardWith SH The centerDifference be 10 Shore C stiffness units or more.
20. the golf of claim 14, wherein, described center has positive hardness gradient, and the central hardness and the case hardness at wherein said center differ 10 to 45.
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CN104069624A (en) * 2013-03-25 2014-10-01 阿库施耐特公司 Golf ball compositions
CN104117183A (en) * 2013-04-29 2014-10-29 阿库施耐特公司 Golf balls having foam inner core and thermoset outer core layer
CN104338294A (en) * 2013-08-05 2015-02-11 阿库施耐特公司 Multi-layer core golf ball
CN105319532A (en) * 2015-07-03 2016-02-10 上海博冕科技有限公司 Bluetooth high-precision three-dimensional positioning system based on array-type directional antennas
CN114515420A (en) * 2020-11-20 2022-05-20 高仕利公司 Golf ball with at least one radar detectable mark

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CN1978006A (en) * 2005-12-05 2007-06-13 普利司通运动株式会社 Solid golf ball

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US5743816A (en) * 1996-04-01 1998-04-28 Kasco Corporation Solid golf ball
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104069624A (en) * 2013-03-25 2014-10-01 阿库施耐特公司 Golf ball compositions
CN104069624B (en) * 2013-03-25 2019-01-18 阿库施耐特公司 Golf component
CN104117183A (en) * 2013-04-29 2014-10-29 阿库施耐特公司 Golf balls having foam inner core and thermoset outer core layer
CN104338294A (en) * 2013-08-05 2015-02-11 阿库施耐特公司 Multi-layer core golf ball
CN104338294B (en) * 2013-08-05 2017-04-12 阿库施耐特公司 multi-layer core golf ball
CN105319532A (en) * 2015-07-03 2016-02-10 上海博冕科技有限公司 Bluetooth high-precision three-dimensional positioning system based on array-type directional antennas
CN105319532B (en) * 2015-07-03 2018-02-27 上海博冕科技有限公司 Bluetooth high-precision three-dimensional alignment system based on array directional aerial
CN114515420A (en) * 2020-11-20 2022-05-20 高仕利公司 Golf ball with at least one radar detectable mark
CN114515420B (en) * 2020-11-20 2024-01-05 高仕利公司 Golf ball with at least one radar detectable mark

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