CN103657012A

CN103657012A - Golf balls having dual-layered cores comprising metal-containing and thermoplastic compositions

Info

Publication number: CN103657012A
Application number: CN201310405677.9A
Authority: CN
Inventors: 迈克尔·J·沙利文; 马克·L·比内特
Original assignee: Acushnet Co
Current assignee: Acushnet Co
Priority date: 2012-09-12
Filing date: 2013-09-09
Publication date: 2014-03-26
Also published as: US20140073457A1

Abstract

Multi-piece golf balls containing a dual-core structure are provided. The core structure includes a small, heavy inner core (center) comprising a metal material, for example, copper, steel, brass, tungsten, titanium, aluminum, and alloys thereof, and having a relatively high specific gravity. A surrounding outer core layer is disposed about the inner core and has a relatively low specific gravity. The outer core layer preferably is formed from a thermoplastic composition preferably an ethylene acid copolymer ionomer resin. The core structure may have different hardness gradients. The resulting ball has high resiliency and good spin control.

Description

The golf with double-deck core that comprises containing metal and thermoplastic compounds

background of invention

Invention field

The present invention relates generally to multi-layer golf ball, it has at least two-layer solid core and the coating of one deck at least.In a preferred embodiment, this bag is containing double-deck core, and it has the inner core (center) of the little weight that contains metal material.Outer sandwich layer is positioned at around this inner core.This outer sandwich layer comprises the ethylene acid copolymer that thermoplastic for example highly neutralizes.This sandwich layer has different hardness gradients and rate of specific gravity provides the final ball with high resilience and rotation control performance.

association area summary

Multilayer solid golf ball today, the two used by occupation and amateurish golfer.Conventionally the solid inner core that this golf comprises coating protection.Described core is the elastic main source of golf, and is often known as " engine " of ball.The resilience of golf (or golf component for example core) or recovery coefficient (" COR ") represent when ball is when air bubble is transmitted into hardboard, the ratio of the rebound velocity of ball and its initial admission velocity.The COR of golf is written as the fractional value between 0-1.Golf can have different COR values at different initial velocities.United States Golf Association (USGA) has set the limit of the initial velocity of ball, and golf ball manufacturers target is to make the COR under these conditions maximum like this.The ball (or core) with high rebound velocity has relatively high COR value.Such golf resilience is faster, has kept larger gross energy while impacting with club, and has the longer flying distance of ball of lower COR value.These performances are for long distance projection particular importance.The ball for example with high resilience and COR value when by striking rod when ball seat impacts, tend to the distance far away of flying.The speed of rotation of ball is also an important performance.The ball with the relatively high speed of rotation is extraordinary writs people expectation for the relative short range transmission being produced with tapered shaft by iron.Professional and high-level amateurish golfer can easierly apply reverse on such ball.Rotation by applying correct amount on ball with contact, golfer can better control launch accuracy and position.This is particular importance near the transmitting that approaches green plants, and contributes to improve score performance.

Conventionally, the golf using today has core individual layer or multilayer.Conventionally, this sandwich layer is to be made as the ethylene acid copolymer (HNP) highly neutralizing as styrene butadiene, polybutadiene, poly-(cis-isoprene) or poly-(trans isoprene) or other polymeric materials by the natural or tartan of high resilience.This coating can be list or multilayer, and for example such as HNP, polyamide, polyester, polyurethane or polyureas, is made by durable material.Golf ball manufacturers is used different structure (for example 3 layers, 4 layers and 5 layers of ball) to give this ball property and feature.

For many years, golf ball manufacturers is conceived to adjust the speed of rotation that density in golf multilayer or proportion are controlled it always.Conventionally the gross weight of golf must meet the weight limit that United States Golf Association (" USGA ") sets.Although the gross weight of golf has requirement, the distribution of weight in ball can change.Towards ball center or towards outer surface of ball, redistribute the weight of golf or flight and the verticity that quality has changed it.

For example this weight can shift to improve the speed of rotation towards ball center, described in the United States Patent (USP) 4625964 of Yamada.This ' 964 patents in, core composition preferably comprises the polybutadiene rubber of 100 weight portions; The zinc acrylate resin of 10-50 weight portion or zinc methacrylate; The zinc oxide of 10-150 weight portion; The peroxide as crosslinking agent or curing agent with 1-5 weight portion.The proportion of inner core is at least 1.50, and object is to make the speed of rotation of ball suitable with the ball of coiling.This ball further comprises coating, the intermediate layer between core and coating, and wherein the proportion in this intermediate layer is lower than core.

The people's such as Chikaraishi United States Patent (USP) 5048838 discloses a kind of three layer golf balls that contain two-layer solid core and a coating.The diameter of this inner core is 15-25mm, and weight is 2-14g, and proportion is that 1.2-4.0 and hardness are 55-80JISC.The proportion of this outer sandwich layer is than the little 0.1-3.0 of the proportion of inner core.Be less than the proportion of inner core.This interior and outer sandwich layer is formed by rubber composition.

The United States Patent (USP) 5104126 of Gentiluomo discloses a kind of three layers of ball, and it has by steel, lead, brass, zinc, the fine and close inner core of copper one-tenth and the elastomer of filling, and wherein the proportion of this core is at least 1.25.This inner core is sealed by low-density syntactic foam composition, and this cored structure is sealed by ionomer coating.

The people's such as Yabuki United States Patent (USP) 5482285 discloses a kind of three layer golf balls, has inner core and the outer core with ionomer coating, sealed.Reduce the proportion of this outer core, so that its decline 0.2-1.0.Adjust the proportion of inner core, so that the gross weight of inside/outside core falls in the scope of 32.0-39.0g.

The United States Patent (USP) 6277934 of Nesbitt and Binette discloses a kind of multi-layer golf ball of non-winding, the spherical metal core components that it contains the about 1.5-of proportion about 19.4; Be positioned at described spherical metal core components outer sandwich layer around, wherein the proportion of this sandwich layer is less than 1.2.This metal-cored metal being selected from below that preferably comprises: steel, titanium, brass, lead, tungsten, molybdenum, copper, nickel, iron and combination thereof.The polybutadiene rubber composite that contains metal dust can be used to form this core.The preferred recovery coefficient of this core assembly is at least 0.730.

The United States Patent (USP) 6494795 of Sullivan discloses a kind of golf, and it comprises and packs the inner core that the proportion in the first covering that surrounds this inner core is greater than 1.8 into.This first covering of a part comprises the low specific gravity layer that proportion is less than 0.9.This core can be made by the high desnity metal or the metal dust that pack in polymer adhesive.Can use high desnity metal for example steel, tungsten, lead, brass, bronze, copper, nickel, molybdenum or alloy.Surround this inner core blanket layer can by thermosetting or thermoplastic, for example epoxy, carbamate, polyester, polyurethane or polyureas be made.

The United States Patent (USP) 6692380 of Sullivan discloses a kind of golf, and it comprises proportion at least 3, the inner core that the about 0.40-of diameter is about 0.60 inch, and this inner core preferably comprises the polymer substrate of polyurethane, polyureas or its mixture.This outer core can be made by polybutadiene rubber.The proportion of said composition can be by adding filler to adjust as metal dust, metal alloy powders, metal oxide, metallic stearate, particulate and carbonaceous material.

The United States Patent (USP) 6986717 of Morgan and Jones discloses a kind of golf, and it contains the high specific gravity astrosphere being encapsulated in soft and resilience shell, and it is preferably formed by polybutadiene rubber.This shell is wound around to form the core of winding subsequently with flexible line preferably.Then the core of this winding uses clad material as natural gum, gutta-percha, ionomer or ionomer mixture, polyurethane, polyurea based composition and epoxy-urethane-based composition covering.This ball is formed by metal dust and thermosetting or thermoplastic adhesive materials.Can use metal as tungsten, steel, brass, titanium, lead, zinc, copper, bismuth, nickel, molybdenum, iron, bronze, cobalt, silver, platinum and gold.Preferably the proportion of this metal ball be at least 6.0 and diameter be less than 0.5 inch.

Although the cored structure of some conventional multiple stratifications can effectively provide high resilience golf conventionally, still continue to need improved cored structure in golf.Concrete, be desirable to the cored structure of the multiple stratification with selective proportion and mass density, provide and there is the ball that good flying distance and rotation are controlled.The invention provides cored structure and the golf with such performance and other favorable characteristics and benefit.

Summary of the invention

The invention provides multilayer (piece) golf, it comprises and has solid (solid) core of one deck at least and have at least coating of one deck.This golf can have different structures.The invention provides multi-layer golf ball, it comprises and has the solid core of one deck at least and have at least coating of one deck.This golf can have different structures.For example in one embodiment, this golf comprises: i) comprise the inner core (center) of metal material, this inner core has diameter and the outer surface hardness (H of about 1.100 inches of about 0.100- _{center table} _face) and core rigidities (H _{center material}), H wherein _{center surface}be greater than H _{center material}make this inner core there is positive hardness gradient; And ii) comprise for example ionomeric outer sandwich layer of ethylene acid copolymer of thermoplastic, and this outer sandwich layer have the thickness of about 1.200 inches of about 0.200-and the outer surface hardness (H of 40-85 Shao Shi D _{the outer surface of outer core}) and the inner surface hardness (H of 42-87 Shao Shi D _{the inner surface of outer core}), (H wherein _{the outer surface of outer core}) be equal to or less than (H _{the inner surface of outer core}) make this outer core there is zero or negative hardness gradient; Inner core proportion (SG _in) be greater than outer core proportion (SG _outward); Be less than the thickness of this outer sandwich layer with the diameter of inner sandwich layer.In a kind of scheme, the positive hardness gradient of this inner core is the about 20 Shao Shi D units of about 3-.In another kind of scheme, zero or negative hardness gradient of this outer core is the approximately negative 15 Shao Shi D units of about 0-.In an example, the core proportion of this multilayer is 1.10-5.75g/cc equally.

This inner core can comprise metal for example copper, steel, brass, tungsten, aluminium, magnesium, molybdenum, cobalt, nickel, iron, tin, bronze, silver, gold and platinum and alloy and combination.In a kind of scheme, the diameter of this inner core is about 0.500 inch of about 0.100-, and proportion is the about 6.25g/cc of about 1.60-, and core rigidities (H _{center material}) be the about 74 Shao Shi D of about 44-.In another kind of scheme, the diameter of this inner core is that about 0.80 inch of about 0.30-is the about 5.00g/cc of about 1.80-with proportion.This outer core can be by for example ethylene acid copolymer ionomer, polyester, polyamide, polyurethane and polyureas formation of thermoplastic.For example this ethylene acid copolymer can comprise acid groups so that 70% or less acid groups be neutralized.In another example, be greater than 70% and be greater than more specifically 90% acid groups and be neutralized.This acid groups can with metal cation salt, for example zinc, sodium, lithium, potassium, calcium, magnesium, nickel, manganese, copper, titanium and aluminium neutralize.Suitable ethylene acid copolymer comprises for example ethene/(methyl) acrylic acid/n-butyl acrylate; Ethene/(methyl) acrylic acid/ethyl acrylate; Ethene/(methyl) acrylic acid/methyl acrylate; Ethene/(methyl) acrylic acid/n-butyl acrylate; And ethene/(methyl) acrylic acid/isobutyl acrylate.In a kind of scheme, the thickness of this outer core is about 0.750 inch of about 0.250-, and proportion is the about 4.10g/cc of about 0.60-, and outer surface hardness (H _{the outer surface of outer core}) be the about 70 Shao Shi D of about 40-.

Equally, this golf can have multiple coat structure.For example this coating can be the individual layer of about 0.090 inch of the about 0.15-of thickness, and is formed by thermoplasticity or thermoset composition.In another embodiment, this coating comprises interior and outer covering layer.The case hardness of outer covering layer can be stiffer than or be softer than the case hardness of internal layer.

In another kind of scheme, the core that this golf comprises multilayer, it comprises the outer sandwich layer of the thermoplasticity that has the metallic inner core of positive hardness gradient and have positive hardness gradient.Selectable, in another kind of scheme, this golf can comprise the core of multilayer, and it comprises the outer sandwich layer of the thermoplasticity that has the metallic inner core of zero or negative hardness gradient and have zero or negative hardness gradient.In another scheme still, this golf can comprise the core of multilayer, and it comprises the outer sandwich layer of the thermoplasticity that has the metallic inner core of zero or negative hardness gradient and have positive hardness gradient.In each of these examples, inner core proportion is preferably greater than outer sandwich layer proportion.

Accompanying drawing explanation

The distinctive novel feature of the present invention is illustrated in additional claim.But the preferred embodiment of the invention and further target and associated advantages are in conjunction with the drawings, and the understanding that can be best with reference to detailed description below, therein:

Fig. 1 is the cross-sectional view with three layer golf balls of double-deck core manufactured according to the present invention; With

Fig. 2 is the cross-sectional view with four layer golf balls of double-deck core manufactured according to the present invention.

The specific embodiment

Golf ball structure

The golf with different structure can be manufactured according to the present invention.For example can manufacture the golf having with 3 layers, 4 layers and 5 layers structure of the clad material of list or multilayer.As used herein, any spherical part of term " layer " ordinary representation golf.More specifically, in a kind of scheme, 3 layer golf balls with twin-core and coating have been manufactured.This twin-core comprises inner core (center) and the outer sandwich layer surrounding.In another kind of scheme, 4 layer golf balls that comprise twin-core and duplex coating (internal coated layer and outer covering layer) have been manufactured.In another structure still, can manufacture 4 layers or 5 layer golf balls of core, centre (packing) layer and the coating with multilayer.As used herein, term " intermediate layer " represents the layer of the ball between core and coating.This intermediate layer also can represent packing or blanket layer.The diameter of different layers and thickness and performance for example hardness and compressibility can change according to the exercise performance of the structure of golf and expectation.

Referring to Fig. 1, a kind of golf of scheme can be manufactured according to the present invention, and it is typically expressed as (12).The core (14) that ball (12) comprises the multilayer of being surrounded by the coating of individual layer (16), the core of this multilayer has inner core (center) (14a) and outer sandwich layer (14b).The volume of inner core (14a) is relatively little, and general diameter is about 1.10 inches of about 0.10-.More specifically, the preferred diameter dimension lower limit of inner core (14a) is that about 0.15 or 0.25 or 0.35 or 0.45 or 0.55 inch and the upper limit are about 0.60 or 0.70 or 0.80 or 0.90 inch.In a kind of preferred scheme, the diameter of inner core (14a) is about 0.080 inch of about 0.025-, and more preferably about 0.030-is about 0.075 inch.Its China and foreign countries' sandwich layer (14b) common thickness is that about 0.010-about 0.250 inch and preferred lower limit are that 0.010 or 0.020 or 0.025 or 0.030 inch and the upper limit are 0.070 or 0.080 or 0.100 or 0.200 inch.In a kind of preferred scheme, the thickness of this outer sandwich layer is about 0.170 inch of about 0.040-, and more preferably about 0.060-is about 0.150 inch.Referring to Fig. 2, in another kind of scheme, golf (18) comprises twin-core (20), and it has inner core (center) (20a) and outer sandwich layer (20b).The coating (22) that twin-core (20) is had the multilayer of internal coated layer (22a) and outer covering layer (22b) surrounds.

According to the present invention, the golf of manufacturing can be any size, although USGA requires contest, with the diameter of golf, is at least 1.68 inches.For the match outside United States Golf Association (USGA) rule, golf can be reduced size.Conventionally, golf requires to manufacture according to USGA, and diameter is about 1.80 inches of about 1.68-.Conventionally, multilayer core structure (14) has the integral diameter of scope below: lower limit is that about 1.00 or 1.20 or 1.30 or 1.40 inches and the upper limit are about 1.58 or 1.60 or 1.62 or 1.66 inches and more preferably about 1.3-1.65 inches.In one embodiment, the diameter of this core assembly (14) is about 1.62 inches of about 1.45-.

So lower further discussion, different compositions can be for the manufacture of the twin-core structure of golf of the present invention.This golf can comprise proportion and the weight that some filler is adjusted sandwich layer as required.Conventionally the specific gravity range lower limit of this inner core (center) be about 1.18 or 1.50 or 2.00 or 2.50g/cc and the upper limit be about 3.00 or 3.50 or 4.00 or 4.50 or 5.00g/cc.In a preferred embodiment, the proportion of this inner core is the about 3.50g/cc of about 1.20-, more preferably about about 3.00g/cc of 1.25-.Wherein this outer sandwich layer (14b) preferably has relatively low proportion.The common specific gravity range lower limit of outer sandwich layer (14b) be about 0.080 or 0.100 or 0.400 or 0.600 or 0.800g/cc and the upper limit be about 1.00 or 1.10 or 1.20g/cc.Adjust the amount of filler used in said composition, so that the weight of golf is no more than the limit that USGA rule sets.USGA has set up the maximum weight of 45.93g (1.62 ounces).For the out-of-spec match of USGA, this golf can be heavier.In a preferred embodiment, the weight of the core of multilayer is the about 38g of about 28-.

Cored structure

As mentioned above, this core preferably has double-deck structure, the outer sandwich layer that it comprises inner core and encirclement.The hardness of this core assembly is an important performance.Conventionally, the core with relatively high hardness number has higher compression ratio, and tends to have good durability and resilience.But some high compression balls are hard, and this can have a negative impact to emission control.These harder proclivities are more for example in having the low speed of rotation, and this makes this ball more be difficult to control.When produce close to green plants approaching transmitting time, this can be particularly troublesome.Therefore need to reach the optimum balance of hardness in core assembly.

In a kind of preferred golf, inner core (center) has " just " hardness gradient (that is, interior core outer surface is stiffer than its geometric center) and outer sandwich layer has " just " hardness gradient (that is, outer sandwich layer outer surface is stiffer than outer sandwich layer inner surface).Inner core and outer sandwich layer all have in the such situation of " just " hardness gradient therein, and outer sandwich layer outer surface hardness is preferably greater than the material hardness at inner core (center).In a kind of selectable scheme, inner core can have positive hardness gradient and (outer sandwich layer can have " zero " hardness gradient, the hardness number of outer sandwich layer outer surface and outer sandwich layer inner surface is basic identical) or " bearing " hardness gradient (that is, outer sandwich layer outer surface is softer than outer sandwich layer inner surface).

In another kind of scheme, this inner core (center) has zero or negative hardness gradient, and outer sandwich layer has positive hardness gradient.In another scheme still, inner core and outer sandwich layer all have zero or negative hardness gradient.Such hardness gradient further describes in the people's such as Bulpett United States Patent (USP) 7537529 and 7410429, and its disclosure is hereby incorporated by.Below further more detailed description measure the inner core of golf and the hardness of outer sandwich layer and other layers and measure the method for the hardness gradient of described layer.

This sandwich layer has defined positive and negative or zero hardness gradient of hardness measurement, this hardness measurement be interior core outer surface (or outer sandwich layer outer surface) upper with inwardly towards inner core center (or inner sandwich layer inner surface) radially on carry out.Described in method of testing below, these measurements are typically to be carried out with 2mm increment.Conventionally this hardness gradient is that the hardness number that the hardness number of the outer surface (for example interior core outer surface or outer sandwich layer outer surface) by the parts with measured deducts the penetrale (for example inner core center or outer sandwich layer inner surface) of measured parts is measured.

positive hardness gradient.if for example the hardness number of the outer surface of inner core is greater than the hardness number (that is, the surface of this inner core is stiffer than Ta center) of inner core geometric center, this hardness gradient will be considered to " just " (large number reduces number and equals positive number).If for example the hardness of interior core outer surface is that the hardness at 58 Shao Shi D and inner core center is 50 Shao Shi D, this inner core has 8 positive hardness gradient.If same outer sandwich layer outer surface has than the larger hardness number of outer sandwich layer inner surface, this outer sandwich layer will be considered to have positive hardness gradient.

negative hardness gradient.on the other hand, if the hardness number of the outer surface of inner core is less than the hardness number (that is, the surface of this inner core is softer than Ta center) of inner core geometric center, this hardness gradient will be considered to " bearing ".If for example the hardness of interior core outer surface is that the hardness at 68 Shao Shi C and inner core center is 70 Shao Shi C, this inner core has 2 negative hardness gradient.If same outer sandwich layer outer surface has than the less hardness number of outer sandwich layer inner surface, this outer sandwich layer will be considered to have negative hardness gradient.

zero hardness gradient.in another example, if the hardness number of the outer surface of inner core equals the hardness number (that is, the surface of this inner core and center have roughly the same hardness) of inner core geometric center substantially, this hardness gradient will be considered to " zero ".If for example the hardness at interior core outer surface and inner core center is 65 Shao Shi C, this inner core has zero hardness gradient.If same outer sandwich layer outer surface has the hardness number roughly the same with outer sandwich layer inner surface, this outer sandwich layer will be considered to have zero hardness gradient.

More specifically, as used herein, term " positive hardness gradient " represents that hardness gradient is positive 3 Shao Shi D or larger, preferred 7 Shao Shi D or larger, more preferably 10 Shao Shi D, and even more preferably 20 Shao Shi D or larger.As used herein, term " zero hardness gradient " represents that hardness gradient is less than 3 Shao Shi D, is preferably less than 1 Shao Shi D, and can have values zero or the negative 10 Shao Shi D of negative 1-.As used herein, term " negative hardness gradient " represents that hardness number is less than zero, for example, be negative 3, negative 5, negative 7, negative 10, negative 15 or negative 20 or negative 25.Term " zero hardness gradient " and " negative hardness gradient " can be used alternatingly to represent at this hardness gradient of negative 1-negative 10.

The preferred geometric center hardness (H of this inner core (center) _{center material}) be that about 25 Shao Shi D or larger and preferred scope are that lower limit is that about 26 or 30 or 34 or 36 or 38 or 42 or 48 or 50 or 52 Shao Shi D and the upper limit are about 54 or 56 or 58 or 60 or 62 Shao Shi D.Core rigidities (the H of this inner core _{center material}) as Shao Shi C unit, to measure preferred lower limit be that about 38 or 44 or 52 or 58 or 60 or 70 or 74 Shao Shi C and the upper limit are about 76 or 78 or 80 or 84 or 86 or 88 or 90 or 92 Shao Shi C.Outer surface hardness (H about inner core _{center surface}), this hardness is about 25 Shao Shi D or larger preferably, and preferred scope lower limit is that about 26 or 30 or 34 or 36 or 38 or 42 or 48 or 50 or 52 Shao Shi D and the upper limit are about 54 or 56 or 58 or 60 or 62 Shao Shi D.

The preferred outer surface hardness of this outer sandwich layer (H wherein _{the outer surface of outer core}) be about 40 Shao Shi D or larger, and preferred scope lower limit be about 40 or 42 or 44 or 46 or 48 or 50 or 52 and the upper limit be about 54 or 56 or 58 or 60 or 62 or 64 or 70 or 74 or 78 or 80 or 82 or 85 or 87 or 88 or 90 Shao Shi D.Outer surface hardness (the H of outer sandwich layer _{the outer surface of outer core}) as the measured preferred lower limit of Shao Shi C unit, be about 63 or 65 or 67 or 70 or 73 or 76 Shao Shi C, and the upper limit is about 78 or 80 or 85 or 87 or 89 or 90 or 92 or 95 Shao Shi C, and outer in-core surface (H _{the inner surface of outer core}) preferred hardness is about 40 Shao Shi D or larger, and preferred scope lower limit be about 40 or 42 or 44 or 46 or 48 or 50 or 52 and the upper limit be about 54 or 56 or 58 or 60 or 62 or 64 or 70 or 74 or 78 or 80 or 82 or 85 or 87 or 88 or 90 Shao Shi D.

Interior core composition

Preferably this interior core composition comprises metal material for example such as copper, steel, brass, tungsten, titanium, aluminium, magnesium, molybdenum, cobalt, nickel, iron, lead, tin, bronze, silver, gold and platinum and alloy and combination.This metal material can be dispersed in polymer substrate, preferably in thermoset rubber material.This metal material is dispersed in the composition that basic homogeneous is provided in polymer substrate.This metal material is fully sneaked into and in polymer substrate, prevented from forming agglomerate and aggregation.Formed metallic composition is used to form to the core arrangement with relatively high proportion, the ball with the following lower rotary inertia of further discussing is provided thus.

Can be natural and synthetic rubber as the suitable thermoset rubber material of polymeric adhesive material, include but not limited to polybutadiene, polyisoprene, ethylene propylene rubber (" EPR "), ethylene-propylene-diene (" EPDM ") rubber, SBR styrene butadiene rubbers, styrene block copolymer rubber (for example " SI ", " SIS ", " SB ", " SBS ", " SIBS " etc., here " S " is styrene, " I " is that isobutene and " B " are butadiene), polyalkenamer (polyalkenamer) for example, such as the poly-cyclo-octene (polyoctenamer) of open loop, butyl rubber, halobutyl rubber, polystyrene elastomer, polyethylene elastomer, polyurethane elastomer, SPUA, the elastomer of metallocene catalysis and thermoplastic elastomer (TPE), isobutene and the copolymer to ring-alkylated styrenes, isobutene and the halo copolymer to ring-alkylated styrenes, the copolymer of butadiene and acrylonitrile, polychloroprene, alkyl acrylate rubber, the isoprene rubber of chlorination, the isoprene rubber of Chlorination of Acrylonitrile with and two or more mixture.

Preferably this rubber composition comprises polybutadiene.Conventionally polybutadiene is the homopolymers of 1,3-butadiene.The attack that two keys in 1,3-butadiene monomer are subject to catalyst generates polymer chain and the polybutadiene polymers that forms the molecular weight with expectation.Any suitable catalyst can be for the synthesis of polybutadiene rubber, and this depends on the performance of expectation.Conventionally, by transition metal complex (for example neodymium, nickel or cobalt) or metal alkyl for example lithium alkylide as catalyst.Other catalyst include but not limited to aluminium, boron, lithium, titanium and combination thereof.This catalyst has generated the polybutadiene rubber with different chemical structures.In cis bonding configuration, the main interpolymer chain of polybutadiene appears at the same side of carbon-to-carbon double bond contained in polybutadiene.In trans bonding configuration, main interpolymer chain in polybutadiene in the opposition side of carbon-to-carbon double bond.This polybutadiene rubber can have the various combination of cis and trans bonding structure.A kind of Isosorbide-5-Nitrae cis linkage content of preferred polybutadiene rubber is at least 40%, is preferably greater than 80% and more preferably greater than 90%.The polybutadiene rubber conventionally with high Isosorbide-5-Nitrae cis linkage content has high tensile strength.This polybutadiene rubber can have relatively high or low Mooney viscosity.

The example that can be used in commercially available polybutadiene rubber of the present invention includes but not limited to BR01 and BR1220, and it is available from the BST Elastomers of Bangkok, THA; SE BR1220LA and SE BR1203, available from the DOW Chemical Co of state of Michigan Midland; BUDENE1207,1207s, 1208 and 1280, available from the Goodyear in city, Akron, Ohio, Inc; BR01,51 and 730, available from the Japan Synthetic Rubber (JSR) of Tokyo; BUNA CB21, CB22, CB23, CB24, CB25, CB29MES, CB60, CB Nd60, CB55NF, CB70B, CB KA8967 and CB1221, available from the Lanxess Corp. of Pennsylvania Pittsburgh; BR1208, available from the LG Chemical of South Korea Seoul; UBEPOL BR130B, BR150, BR150B, BR150L, BR230, BR360L, BR710 and VCR617, available from the UBE Industries of Tokyo, Ltd.; EUROPRENE NEOCIS BR60, INTENE60AF and P30AF and EUROPRENE BR HV80, available from the Polimeri Europa of Rome, ITA; AFDENE50 and NEODENE BR40, BR45, BR50 and BR60, available from Karbochem (PTY) Ltd. of South Africa Bruma; KBR01, NdBr40, NdBR-45, NdBr60, KBR710S, KBR710H and KBR750, available from the Kumho Petrochemical Co. of South Korea Seoul; DIENE55NF, 70AC and 320AC, available from the Firestone Polymers in city, Akron, Ohio; With PBR-Nd Group II and Group III, available from the Nizhnekamskneftekhim of the Nizhnekamsk of Tartarstan Republic, Inc..

The consumption of polybutadiene rubber is at least about 5 % by weight, based on composition total weight, and common amount is that about 5%-is about 100%, or weight range lower limit be 5% or 10% or 20% or 30% or 40% or 50% and the upper limit be 55% or 60% or 70% or 80% or 90% or 95% or 100%.Preferably polybutadiene rubber concentration is about 95 % by weight of about 40-.If expectation, other thermosets of small amount can be sneaked in this basis rubber.Such material comprises above-mentioned rubber such as cis-polyisoprene, using trans-polyisoprene, natural gum, polychloroprene, polynorbornene, the poly-cyclo-octene (polyoctenamer) of open loop, the poly-cyclopentene (polypentenamer) of open loop, butyl rubber, EPR, EPDM, styrene-butadiene etc.

In another kind of scheme, thermoplastic can be used as polymer adhesive, in inner core composition used.These thermoplastic polymers comprise the ethylene acid copolymer (it is neutralization at least partly) that for example contains acid groups.Preferably degree of neutralization is greater than 70%, and more preferably at least 90% and even more preferably at least 100%.Like this have 70% or the so-called senior middle school of ethylene acid copolymer of larger degree of neutralization and polymer (HNP).Can be used in the so-called ethene of suitable ethylene acid copolymer, the C that form the present composition ₃-C ₈α, the copolymer of the unsaturated list of β-olefinic or dicarboxylic acids and optional soft monomer.Copolymer can include, without being limited to ethylene acid copolymer, ethene/(methyl) acrylic acid for example, ethene/(methyl) acrylic acid/maleic anhydride, ethene/(methyl) acrylic acid/maleic acid monoesters, ethene/maleic acid, ethene/maleic acid monoesters, ethene/(methyl) acrylic acid/(methyl) n-butyl acrylate, ethene/(methyl) acrylic acid/(methyl) isobutyl acrylate, ethene/(methyl) acrylic acid/(methyl) methyl acrylate, ethene/(methyl) acrylic acid/(methyl) ethyl acrylate terpolymer etc.Can use other thermoplastic polymers as polyamide, polyamide-ether and polyamide-ester, polyurethane, polyureas, polyurethane-polyurea heterocomplex, polyester, polyolefin, polystyrene and composition thereof.

As mentioned above, the composition that is used to form inner core comprises metal material.In a kind of scheme, this metal material can form whole inner core.That is, this metal material comprises 100% the composition for the manufacture of inner core.This metal material is preferably in the medicine ball form of ball bearing for example.This metal ball can be used as inner core (center), and the outer sandwich layer of polymer can be positioned at around this metal center.Selectable, metal packing, as described further below, can be dispersed in polymer adhesive and form metallic composition, and it can be for the manufacture of this inner core.Can use the metal material of the weight of phase counterweight, for example, such as the metal being selected from below: copper, nickel, tungsten, brass, steel, magnesium, molybdenum, cobalt, lead, tin, silver, gold and platinum alloy.Suitable Steel material comprises for example chromium steel, stainless steel, carbon steel and alloy thereof.Selectable or except this heavy metal, can use relative light weight metal material for example titanium and aluminium alloy, limit this inner sandwich layer and there is required proportion.Metal packing is joined in composition with enough, obtain below the further proportion of described expectation.

If the size of this inner core (center) is little, and use fine and close metal material as tungsten, the required tungsten amount of proportion that obtains expectation will be relatively low.The weight of such compact metal material is further concentrated, so that need material more in a small amount.On the other hand, if use low density-metal material as aluminium, reaching the required aluminium amount of required proportion will be relatively high.Conventionally, the amount of this metal packing in composition is about 1%-about 60%.Preferably the amount of this metal packing in composition is 20wt% or lower, 15wt% or lower, or 12wt% or lower, or 10wt% or lower, or 6wt% or lower, or 4wt% or lower, the weight based on polymer in composition.

The whole proportion of this cored structure (inner core and outer sandwich layer) is 1.8g/cc at least preferably, more preferably at least 2.00g/cc and most preferably 2.50g/cc at least.Conventionally the proportion of this inner core is at least about 1.00g/cc and normally about 1.00-about 20.00.Preferably the proportion lower limit of this inner core be about 1.10 or 1.20 or 1.50 or 2.00 or 2.50 or 3.50 or 4.00 or 5.00 or 6.00 or 7.00 or 8.00g/cc and the upper limit be about 9.00 or 9.50 or 10.00 or 10.50 or 11.00 or 12.00 or 13.00 or 14.00 or 15.00 or 16.00 or 17.00 or 18.00 or 19.00 or 19.50g/cc.In a preferred embodiment, the proportion of this inner core is the about 5.50g/cc of about 1.20-, more preferably about about 3.25g/cc of 1.25-.

Wherein this outer sandwich layer preferably has relatively low proportion.So proportion (SG of inner sandwich layer _in) be preferably greater than outer sandwich layer proportion (SG _outward).The specific gravity range lower limit that for example this outer sandwich layer can have is about 0.80,0.90g/cc, 1.00 or 1.25 or 2.00 or 2.50 or 3.00 or 3.50 or 4.00,4.25 or 5.00 and the upper limit be about 6.00 or 6.50 or 7.00 or 7.25 or 8.00 or 8.50 or 9.00 or 9.25 or 10.00g/cc.In a preferred embodiment, SG _inbe preferably greater than SG _outward0.5g/cc at least, more preferably 0.75g/cc or larger and even more preferably 1.00g/cc or larger.In one embodiment, SG _inand SG _outwardbetween difference be the about 2.0g/cc of about 0.5g/cc-.

The preferred rate of specific gravity of suitable metal packing that can join in the polymer substrate that is used to form inner core is about 1.5-about 19.5, with comprise for example metal (or metal alloy) powder, metal oxide, metallic stearate, particulate, sheet etc. and composition thereof.The example of useful metal (or metal alloy) powder includes but not limited to bismuth meal end, boron powder, brass powder, bronze powder, cobalt dust, copper powders, iron powder, molybdenum powder, nickel by powder, powder of stainless steel, titanium metal powder, Zirconium oxide powder, aluminium flake, tungsten metal dust, beryllium metal dust, zinc metal dust or tin metal powder.The example of metal oxide includes but not limited to zinc oxide, iron oxide, aluminium oxide, titanium dioxide, magnesia, zirconia and tungstic acid.This rubber composition can comprise conventional additives as radical initiator, crosslinking agent, soft fast agent and antioxidant, and said composition can with below further described conventional system solidify.

Rubber of the present invention or other thermoset compositions can solidify with conventional curing.Suitable curing comprises for example peroxide cure, sulfur curable, high-energy radiation and combination thereof.Preferably this rubber composition comprises the radical initiator being selected from below: organic peroxide, high-energy radiation source and the combination thereof that can produce free radical.In a kind of preferred scheme, this rubber composition is peroxide cure.Suitable organic peroxide includes but not limited to dicumyl peroxide; 4,4-bis-(tert-butyl hydroperoxide) n-butyl pentanoate; 1,1-bis-(tert-butyl hydroperoxide) 3,3,5-trimethyl-cyclohexane; 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane; Di-tert-butyl peroxide; Two t-amyl peroxy things; Tert-butyl peroxide; Tert-butyl group cumyl peroxide; 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexin-3; Two (2-tert-butyl hydroperoxide isopropyl) benzene; Dilauroyl peroxide; Dibenzoyl peroxide; Tert-butyl hydroperoxide; And combination.In a kind of specific embodiment, radical initiator is dicumyl peroxide, includes but not limited to

city is sold by Akzo Nobel.The peroxide radical initiator conventionally amount in rubber composition is at least 0.05 weight portion, total rubber based on every 100 parts, or weight weight range lower limit is 0.05 part or 0.1 part or 1 part or 1.25 parts or 1.5 parts or 2.5 parts or 5 parts, total rubber based on every 100 parts, with upper weight limit be 2.5 parts or 3 parts or 5 parts or 6 parts or 10 parts or 15 parts, the total rubber based on every 100 parts.Concentration is every hundred parts of a (phr) units, unless otherwise directed.As used herein, term " portions of every hundred parts ", also referred to as " phr " or " pph ", is defined as the polymers compositions with respect to 100 weight portions, the parts by weight of the concrete component existing in mixture.Arithmetically, this can be expressed as the weight of composition divided by the gross weight of polymer, is multiplied by the factor 100.

This rubber composition may further include reactive co-crosslinker.Suitable co-crosslinker includes but not limited to have the slaine of the unsaturated carboxylic acid of 3-8 carbon atom; Unsaturated ethylene alkenyl compound and polyfunctional monomer (for example trimethylol-propane trimethacrylate); Phenylene BMI; And combination.The concrete example of suitable slaine includes but not limited to one or more slaines of acrylate, diacrylate, methacrylate and dimethylacrylate, and wherein this metal is selected from magnesium, calcium, zinc, aluminium, lithium and nickel.In a kind of specific embodiment, co-crosslinker is selected from the zinc salt of acrylate, diacrylate, methacrylate and dimethylacrylate.In another specific embodiments, this reagent is dizinc acrylate resin (ZDA).When this co-crosslinker is dizinc acrylate resin and/or zinc dimethacrylate, the weight range lower limit that this co-crosslinker typically accounts for rubber composition is 1 or 5 or 10 or 15 or 19 or 20 weight portions, total rubber based on every 100 parts, with the upper limit be 24 or 25 or 30 or 35 or 40 or 45 or 50 or 60 weight portions, the basic rubber based on every 100 parts.

Free radical quencher is halo organic sulfur, organic disulfide or can add in rubber composition without organic disulfide compound for example.These compounds also can serve as " soft fast agent ".As used herein, " soft fast agent " represents to manufacture any compound or its mixture of core: when the of equal value core prepared with there is no soft fast agent compared, 1) at constant " recovery coefficient " (COR) time more soft (having low compression); And/or 2) faster (when equal compression, thering is higher COR).The salt that preferred halo organosulfur compound includes but not limited to pentachlorothiophenol (PCTP) and PCTP is pentachlorothiophenol zinc (ZnPCTP) for example.In golf inner core, use PCTP and ZnPCTP to contribute to produce more soft inner core faster.PCTP and ZnPCTP compound contribute to increase resilience and the recovery coefficient of core.In a kind of specific embodiment, this soft fast agent is selected from ZnPCTP, PCTP, ditolyl two sulphur, diphenyl disulfide, bis-xylene base two sulphur, 2-nitro-resorcinol and combination thereof.

As mentioned above, prepare composition of the present invention and there is specific gravity balance, so that they can be used in some core component that forms golf.Except above-mentioned metal packing, this rubber composition can comprise other additives.The example of useful filler includes but not limited to carbonaceous material for example graphite and carbon black.Graphite fibre, precipitated hydrated silica, clay, talcum, glass fibre, aramid fiber, mica, calcium metasilicate, barium sulfate, zinc sulphide, silicate, diatomite, calcium carbonate, magnesium carbonate, rubber is abrasive (it is the uncured elastomeric material of recirculation, by its mixing and grinding), cotton short fiber, bitumen, cellulose fluff peacekeeping leather fiber again.Also can use micro-balloon filler for example glass and pottery and flying dust filler.

Of this embodiment concrete aspect, this rubber composition comprises the filler being selected from below: carbon black, nanofiber are (for example

with nanofiber, city is sold by Southern Clay Products, Inc., and

with

nanofiber, city is sold by Nanocor, Inc.), talcum (for example

high-aspect-ratio talcum, city is sold by Luzenac America, Inc.), glass (for example sheet glass, abrading glass and micro-glass), mica and mica-based pigment (for example pearlescent pigment, city is sold by The Merck Group) and combination.

In addition, this rubber composition can comprise that antioxidant prevents elastomer fracture.Equally, processing aid can add in said composition as HMW organic acid and salt thereof.Suitable organic acid is aliphatic organic acid, aromatics organic acid, saturated mono official energy organic acid, unsaturated simple function organic acid, how unsaturated simple function organic acid and dimerization derivative thereof.The concrete example of suitable organic acid includes but not limited to caproic acid, sad, turn sour, and laurate, stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid, myristic acid, benzoic acid, palmitic acid, phenylacetic acid, naphthoic acid and dimerization derivative thereof.This organic acid is aliphatic, simple function (saturated, unsaturated or how unsaturated) organic acid.These organic acid salt also can be used.Organic acid salt comprises the salt of barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, caesium, iron, nickel, silver, aluminium, tin or calcium, and aliphatic acid is the salt of stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid or its dimerization derivative particularly.Preferably organic acid of the present invention is relative nonmigratory (they can not be penetrated into polymer surfaces at ambient temperature) and nonvolatile (they are non-volatile in the required temperature of melt mixed) with salt.

Other compositions for example accelerator (for example tetra methylthiuram), processing aid, dyestuff and other known additives of pigment, wetting agent, surfactant, plasticizer, colouring agent, fluorescer, chemical bubbling and blowing agent, defoamer, stabilizing agent, softening agent, impact modifying agent, antioxidant, antiozonant and prior art can add in this rubber composition.

Outer core composition

As mentioned above, this inner core can be formed by metal filled thermosetting or thermoplastic, and preferably by metal filled thermoset rubber, is formed.Equally, this outer sandwich layer can be formed by thermosetting or thermoplastic.Preferably this outer sandwich layer is formed by thermoplastic compounds.In one embodiment, the identical thermoplastic compounds (except for proportion is adjusted to the metal packing of aspiration level) that is used to form inner core also can be used to form outer sandwich layer.Therefore the interior and outer sandwich layer of each can be formed by the ethylene acid copolymer composition of part or highly neutralization.But the proportion of this inner core and outer sandwich layer will be different; Therefore in composition separately, for adjusting concentration and/or the type of the metal packing of proportion, will be different.In one embodiment, this outer sandwich layer even can not comprise any metal material.In another embodiment, this outer sandwich layer can comprise the metal packing of relative small concentration, and the metal packing that this inner core comprises large concentration.

Preferably this outer sandwich layer is formed by ionomer compositions, the ethylene acid copolymer that it comprises the acid groups that contains at least part of neutralization.As discussed further below, preferably degree of neutralization is greater than 70%, and more preferably at least 90% and even more preferably at least 100%.Can be used in the so-called ethene of suitable ethylene acid copolymer, the C that form the present composition ₃-C ₈α, the copolymer of the unsaturated list of β-olefinic or dicarboxylic acids and optional soft monomer.Copolymer can include, without being limited to ethylene acid copolymer, ethene/(methyl) acrylic acid for example, ethene/(methyl) acrylic acid/maleic anhydride, ethene/(methyl) acrylic acid/maleic acid monoesters, ethene/maleic acid, ethene/maleic acid monoesters, ethene/(methyl) acrylic acid/(methyl) n-butyl acrylate, ethene/(methyl) acrylic acid/(methyl) isobutyl acrylate, ethene/(methyl) acrylic acid/(methyl) methyl acrylate, ethene/(methyl) acrylic acid/(methyl) ethyl acrylate terpolymer etc.As used herein, term " copolymer " comprises the polymer with two types of monomers, have three types monomer those and there are those of monomer that are greater than three types.Preferred α, the unsaturated list of β-olefinic or dicarboxylic acids are (methyl) acrylic acid, ethylacrylic acid, maleic acid, crotonic acid, fumaric acid, itaconic acid.(methyl) acrylic acid is most preferred.As used herein, " (methyl) acrylic acid " represents methacrylic acid and/or acrylic acid.Equally, " (methyl) acrylate " represents methacrylate and/or acrylate.

When comprising soft monomer, such copolymer is known as E/X/Y type copolymer at this, and wherein E is ethene; X is C ₃-C ₈α, the unsaturated list of β-olefinic or dicarboxylic acids; With Y be soft monomer.This soft monomer is typical (methyl) alkyl acrylate, and wherein this alkyl has 1-8 carbon atom.Preferred E/X/Y type copolymer is those, wherein X is that (methyl) acrylic acid and/or Y are selected from (methyl) acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) methyl acrylate and (methyl) ethyl acrylate.Preferred E/X/Y type copolymer is ethene/(methyl) acrylic acid/n-butyl acrylate, ethene/(methyl) acrylic acid/methyl acrylate and ethene/(methyl) acrylic acid/ethyl acrylate.

In this acid copolymer, the content of ethene is typically at least 15wt%, preferred 25wt% at least, more preferably at least 40wt% and even more preferably 60wt% at least, the gross weight based on copolymer.C ₃-C ₈α, the unsaturated list of β-olefinic or the content of dicarboxylic acids in acid copolymer are typically 1wt%-35wt%, preferred 5wt%-30wt%, more preferably 5wt%-25wt%, and even more preferably 10wt%-20wt%, the gross weight based on copolymer.In acid copolymer, the amount of optional soft comonomer is typically 0wt%-50wt%, preferred 5wt%-40wt%, and more preferably 10wt%-35wt%, and even more preferably 20wt%-30wt%, based on copolymer gross weight.Can use " low acid " and " peracid " ionomer polymer and so ionomeric mixture.Conventionally low acid ionomer is considered to contain those of 16wt% or acid moieties still less, and high acid ionomer is considered to contain those of acid moieties that are greater than 16wt%.

Acidic-group in copolymers ionomers is partially or completely with cationic source, to neutralize.Suitable cationic source comprises metal cation and salt thereof, organic amine compound, ammonium and combination thereof.Preferred cationic source is metal cation and salt thereof, wherein preferably lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminium, manganese, nickel, chromium, copper or its combination of this metal.As discussed further below, this metal cation salt provides cation, and it can neutralize (with variable level (at varying level)) if the carboxylic acid of ethylene acid copolymer and the aliphatic acid while existing.They comprise sulfate, carbonate, acetate, oxide or the hydroxide salt of for example lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminium, manganese, nickel, chromium, copper or its combination.Preferred metal cation salt is calcium and magnesium base salt.High surface cation particle for example micron and the cation particle of nano-scale is preferred.In described composition cationic consumption easily based on expectation neutralization levels determine.

For example can use neutralization to the ionomer resin with acid groups of about 10%-about 100%.In a kind of ionomer compositions, acid groups is part neutralization.That is, degree of neutralization is that about 10%-is about 70%, more preferably 20%-60% and most preferably 30-50%.These ionomer compositions (contain neutralization to 70% or less acid groups) can be called the ionomer with relatively low degree of neutralization.

On the other hand, the acid groups that ionomer compositions can comprise height or neutralize completely.These polymer that highly neutralize (HNP) are preferred for forming at least one sandwich layer of the present invention.In these HNP, degree of neutralization is greater than 70%, and preferably at least 90% and even more preferably at least 100%.In another embodiment, can use excessive nertralizer, that is, be greater than the amount of the required stoichiometry of the described acid groups of neutralization.That is, acid groups can neutralize 100% or larger, and for example 110% or 120% or larger.In a preferred embodiment, the methacrylic acid that contains about 19-20wt% or acrylic acid peracid ethylene acid copolymer are neutralized to 95% degree of neutralization with zinc and sodium cation.

" ion plasticizer " be organic acid or organic acid salt, particularly aliphatic acid for example, can add as required in this ionomer resin.Such ion plasticizer is by larger machinable for the manufacture of conventional ionomer compositions, and described in the people's such as Rajagopalan United States Patent (USP) 6756436, its disclosure is hereby incorporated by.In a preferred embodiment, this thermoplasticity ionomer compositions (contain neutralization to 70% or less acid groups) do not comprise aliphatic acid or its salt or any other ion plasticizer.On the other hand, this thermoplasticity ionomer compositions (containing neutralization to the acid groups that is greater than 70%) comprises ion plasticizer, particular fatty acid or its salt.For example the addition of this ion plasticizer can be 0.5-10pph, more preferably 1-5pph.This organic acid can be aliphatic, single or multifunctional (saturated, unsaturated or how unsaturated) organic acid.Also can use these organic acid salt.Suitable soap comprises such as metallic stearate, laureate, oleate, palmitate, pelargonate etc.Such as using soap such as zinc stearate, calcium stearate, dolomol, barium stearate etc.The aliphatic acid that the salt of aliphatic acid normally neutralizes with metal ion.This metal cation salt provides and can neutralize (with the cation of the hydroxy-acid group of variable level (at varying level) aliphatic acid.Example comprises metal for example sulfate, carbonate, acetate and the hydroxide salt of barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, caesium, iron, nickel, silver, aluminium, tin or calcium, and composition thereof.Preferably this organic acid is relative nonmigratory (they can not be penetrated into polymer surfaces at ambient temperature) and nonvolatile (they are non-volatile in the required temperature of melt mixed) with salt.

As mentioned above, final ionomer compositions can comprise other material for example such as a small amount of ion plasticizer, and it is effective especially improving aspect ionomeric processability highly neutralizing.For example the passable addition of this ion plasticizer can be 0.5-10pph, more preferably 1-5pph.Except above-mentioned aliphatic acid and soap, other suitable ion plasticizer comprise for example polyethylene glycol, wax, bis-stearamides, mineral and phthalate.In another embodiment, preferably, except metal cation, use amine or pyridine compounds.Suitable example comprises such as ethamine, methylamine, diethylamine, tert-butylamine, lauryl amine etc.

This ionomer compositions can comprise multiple filler widely, and these fillers of some can be as required for adjusting the proportion of composition.Can use high surface area fillers, the acid groups in itself and ionomer has affinity.Concrete suitable filler is for example particulate, fiber or the sheet with cationic property, and they also can be for neutralizing this ionomer like this.For example can use aluminium oxide, zinc oxide, tin oxide, barium sulfate, zinc sulfate, calcium oxide, calcium carbonate, zinc carbonate, brium carbonate, tungsten, tungsten carbide and lead silicate filler.Equally, can use silica, fumed silica and precipitated silica, those that for example sold by PPG Industries under trade (brand) name HISIL, carbon black, carbon fiber and nano-sized materials be nanotube, nanometer sheet, Nano filling and nanofiber for example.Other additives and filler include but not limited to chemical bubbling and blowing agent, fluorescent whitening agent, colouring agent, fluorescer, brightening agent, UV absorbent, light stabilizer, defoamer, processing aid, antioxidant, stabilizing agent, softening agent, aroma constituent, plasticizer, impact modifying agent, titanium dioxide, acid copolymer wax, surfactant, rubber abrasive (core material of recirculation), clay, mica, talcum, sheet glass, abrading glass and composition thereof again.Suitable additive is described in the U.S. Patent Application Publication No.2003/0225197 such as people such as Rajagopalan more fully, and its whole content is hereby incorporated by.In a kind of specific embodiment, the additive existing in final thermoplasticity ionomer compositions and the total amount of filler are 15wt% or less, or 12wt% or less, or 10wt% or less, or 9wt% or less, or 6wt% or less, or 5wt% or less, or 4wt% or less, or 3wt% or less, the gross weight based on ionomer compositions.

The consumption of this ethylene acid copolymer is at least about 5 % by weight, based on composition total weight, and common amount is that about 5%-is about 100%, or the scope lower limit of amount be 5% or 10% or 20% or 30% or 40% or 50% and the upper limit be 55% or 60% or 70% or 80% or 90% or 95% or 100%.The concentration of optimal ethylene acid copolymer is about 95 % by weight of about 40-.Other suitable thermoplastic polymers that can be used in formation core arrangement include but not limited to polymer (comprising homopolymers, copolymer and derivative thereof) below.

(a) polyester, special in compatibility group for example sulphonic acid ester or phosphonate-modified those, comprise poly-(propylene glycol ester terephthalate) of poly-(ethylene glycol terephthalate) of modification, poly-(mutual-phenenyl two acid bromide two alcohol ester) of modification, modification, poly-((ethylene naphthalate)) that gather (trimethylene terephthalate), modification of modification, with be disclosed in U.S. Patent No. 6353050, those in 6274298 and 6001930, its whole disclosure is hereby incorporated by, and the mixture of two or more;

(b) polyamide, polyamide-ether and polyamide-ester, and those disclosed in U.S. Patent No. 6187864,6001930 and 5981654, its whole content is hereby incorporated by, and the mixture of two or more;

(c) polyurethane, polyureas, polyurethane-polyurea heterocomplex, and the mixture of two or more;

(d) fluoropolymer, for example U.S. Patent No. 5691066,6747110 and 7009002 those disclosed, its whole content is hereby incorporated by, and the mixture of two or more;

(e) polystyrene, for example poly-(styrene-copolymerization-maleic anhydride), acrylonitrile-butadiene-styrene (ABS), poly-(styrene sulfonate), polystyrene ethene, and the mixture of two or more;

(f) polyvinyl chloride and grafting polyvinyl chloride, and the mixture of two or more;

(g) Merlon, PC/Abs mixture, Merlon/polyurethane mixture, polycarbonate/polyester mixture, and the mixture of two or more;

(h) polyethers, poly (arylene ether) for example, polyphenylene oxide, the block copolymer of alkenyl aromatic hydrocarbon and vinyl-arene and polyamines ester, and the mixture of two or more;

(i) polyimides, polyether-ketone, polyamidoimide, and the mixture of two or more; With

(j) polycarbonate/polyester copolymer and mixture.

These thermoplastic polymers can itself make for forming this inner core with them together, or can use and comprise above-mentioned polymer and the ionomeric thermoplastic polymer mixtures of ethylene acid copolymer.Be recognized that equally this ionomer compositions can comprise two or more ionomeric mixtures.For example said composition can comprise the mixture of the ethylene/methacrylic acid of the different height neutralization of two kinds of 50/50wt%.In another kind of scheme, said composition can comprise the mixture of the non-ionomer polymer of one or more ionomers and maleic anhydride graft.This non-ionomer polymer can be the polymer of metallocene catalysis.In another kind of scheme, said composition comprises highly the poly mixture of the ethylene/methacrylic acid of neutralization and the metallocene catalysis of maleic anhydride graft.In another scheme still, said composition comprises such material, and it is selected from the highly ionomer of neutralization, the optional non-ionomer polymer that is mixed with maleic anhydride graft; Polyester elastomer; Polyamide elastomer; And the mixture of two or more.

As mentioned above, inner sandwich layer proportion (SG _in) be preferably greater than outer sandwich layer proportion (SG _outward).Conventionally object separately the proportion of layer affect the rotary inertia (MOI) of this object.Conventionally ball (or other objects) is about referring to the rotary inertia of dead axle to change the difficulty that this ball rotates around described axle to be how many.If the quality of ball is concentrated (proportion of central core is higher than skin) towards center, need less power to change its rotating speed, and this ball have relatively low rotary inertia.In such ball, most of quality is positioned near ball rotating shaft, needs less power to produce rotation.Therefore this ball has the high speed of rotation conventionally.On the contrary, if the quality of ball towards outer surface concentrated (outer field proportion is higher than central core), needs larger power to change its rotating speed, and this ball has relatively high rotary inertia.That is,, in such ball, most of quality is arranged away from the rotating shaft of ball, and is needed larger power to produce rotation.Such ball has the low speed of rotation conventionally.

The golf with above-mentioned cored structure of the present invention shows good resilience and rotation is controlled the two.Formed ball has relatively high recovery coefficient (COR), and this allows it when impacting with golf club, to reach high speed.Therefore, this proclivity is in the long distance of operation, and this is particular importance for the driving transmitting of leaving ball seat.Meanwhile, this ball has soft sense of touch and sensation.Therefore golfer has better control for ball, and it is particular importance that near this lofting mashie using green plants produces while approaching transmitting.Golfer can touch batting, so that it hurtles down and stops on green plants.In addition, professional and high-level amateurish golfer can be even more accurately and emission control reverse is applied on ball.For such golfer, correct rotation and Exposure can be easy to be applied on ball.This ball more can impact, and the such ball of use that golfer can be more comfortable.Golfer can bat, and the correct distance so that it flies keeps the control for flight path, rotation and position simultaneously.

More specifically, described in the people's such as the United States Patent (USP) 6494795 of Sullivan and Ladd United States Patent (USP) 7651415, formula for the rotary inertia of the ball of any diameter is CRC standard mathematical table the 24th edition, and 1976 provide in 20 pages (below CRC lists of references).As used herein, term " proportion " has its common and common implication, that is, the ratio of material density and 4 ℃ of water densities, water is 1g/cm in the density of this temperature ³.Proportion can be measured according to ASTM test specification ASTM D-792-98.In addition, the typical COR of core of the present invention is about 0.75 or larger; Preferably approximately 0.80 or larger.The compression of this core is approximately 50-about 130 and more preferably about 70-about 110 preferably.

Coat structure

Golf ball core of the present invention can be sealed with one or more coating.In a kind of scheme, this golf comprises the coating of the multilayer that comprises interior and outer covering layer.This internal coated layer is preferably formed by such composition, and it comprises ionomer or two or more ionomeric mixtures, and it contributes to give ball hardness.In a kind of specific embodiment, this internal coated layer is to be formed by the composition that comprises high acid ionomer.A kind of specially suitable high acid ionomer is

(DuPont).

be the copolymer of ethene and methacrylic acid, acid content is 19wt%, and it is 45% use sodium neutralization.In another specific embodiments, this internal coated layer is that the composition by the non-ionomer polymer that comprises high acid ionomer and maleic anhydride graft forms.A kind of specially suitable maleic anhydride grafted polymer is

(DuPont).

be ethylene-butene copolymer a kind of maleic anhydride graft, metallocene catalysis, it has the maleic anhydride on this copolymer that is grafted to of about 0.9wt%.The mixture of a kind of particularly preferred high acid ionomer and maleic anhydride grafted polymer is 84wt%/16wt%

with mixture.The mixture of high acid ionomer and maleic anhydride grafted polymer is for example further disclosed in U.S. Patent No. 6992135 and 6677401, and its whole disclosure is hereby incorporated by.

This internal coated layer can also be by comprising 50/45/5

the composition of mixture forms, and in a kind of particularly preferred embodiment, the material hardness of said composition is 80-85 Shao Shi C.In another scheme still, this internal coated layer is by comprising 50/25/25

the composition of mixture forms, and preferred material hardness is about 90 Shao Shi C.This internal coated layer also can be by comprising 50/50

the composition of mixture forms, and preferred material hardness is about 86 Shao Shi C.Can also use and to comprise 50/50

with

the composition of mixture.

be a kind of E/MAA copolymer, MAA acid groups partly neutralizes with sodium ion therein. with

be the E/MAA copolymer of two kinds of different brackets, MAA acid groups partly neutralizes with zinc ion therein.

nominally be a kind of E/MAA copolymer resin made from the methacrylic acid of 15wt%.

Multiple material can be used to form outer covering layer widely, comprises for example polyurethane; Polyureas; The copolymer of polyurethane and polyureas, mixture and heterocomplex; Olefin-based copolymer ionomer resin (for example

ionomer resin and

with city is sold by DuPont;

ionomer, city is sold by ExxonMobil Chemical Company;

iO ethylene acrylic acid co polymer ionomer, city is sold by The Dow Chemical Company; With

ionomer resin, city is sold by A.Schulman Inc.); Polyethylene, comprises for example low density polyethylene (LDPE), LLDPE and high density polyethylene (HDPE); Polypropylene; The olefin polymer of rubber reinforcement; Acid copolymer, for example, gather (methyl) acrylic acid, and it does not become a part for ionomeric copolymers; Thermoplastic elastomer (TPE); Flexibility agent; Styrene/butadiene/styrene block copolymers; Styrene/ethylene-butylene/styrene block copolymer; The elastomer of dynamic vulcanization; Ethene and vinyl acetate copolymer; Ethene and methacrylate copolymer; Corvic; Polyamide, poly-(amide-ester) elastomer, and the graft copolymer of ionomeric copolymers and polyamide, for example comprise

thermoplastic polyether block amides, city is sold by Arkema Inc; Crosslinked cis-polyisoprene and composition thereof; Polyester-based thermoplastic elastomer (TPE) for example city be sold by DuPont or

city is sold by Ticona Engineering Polymers; Polyurethane-base thermoplastic elastomer (TPE) for example

city is sold by BASF; Synthesize or natural vulcanized rubber; And combination.The polyurethane that Ca is stable, polyureas and polyurethane-polyurea heterocomplex are to make us especially expectation, because these materials can be for the manufacture of the golf with high resilience and soft feel.With term " polyurethane and polyureas heterocomplex ", represent to comprise its copolymer and mixture.

The mixture of polyurethane, polyureas and polyurethane/polyurea, copolymer and heterocomplex are also particularly suitable for forming coating.When as clad material, polyurethane and polyureas can be thermosetting or thermoplastic.Thermosets can be cast or reaction injection molding(RIM) technology formation golf ball layer by routine.Thermoplastic can form golf ball layer by conventional compression moulding or injection molding technology.

The preferred material hardness scope of this internal coated layer lower limit is that 70 or 75 or 80 or 82 Shao Shi C and the upper limit are 85 or 86 or 90 or 92 Shao Shi C.It is 0.035 or 0.045 or 0.080 or 0.120 inch with the upper limit that the preferred scope lower limit of intermediate layer thickness is 0.010 or 0.015 or 0.020 or 0.030 inch.The preferred material hardness of outer covering layer is 85 Shao Shi C or less.It is 0.035 or 0.040 or 0.055 or 0.080 inch with the upper limit that the preferred scope lower limit of thickness of this outer covering layer is 0.010 or 0.015 or 0.025 inch.For measuring the method for golf middle level hardness, be discussed in further detail below.

As mentioned above, cored structure of the present invention can be sealed with one or more coating.In one embodiment, formed in comprising and the coating of the multilayer of outer covering layer, here the thickness of this internal coated layer is about 0.01 inch-about 0.06 inch, more preferably about 0.015 inch-about 0.040 inch, and most preferably about 0.02 inch-about 0.035 inch.In this scheme, this internal coated layer is to be formed by the ionomer partly or completely neutralizing, and it is about 55 that its Shao Shi D hardness is greater than, more preferably greater than about 60 be most preferably greater than about 65.This outer covering layer preferred thickness in this embodiment is about 0.015 inch-about 0.055 inch, more preferably about 0.02 inch-about 0.04 inch, most preferably about 0.025 inch-about 0.035 inch, hardness is about Shao Shi D80 or less, more preferably 70 or less, and most preferably about 60 or less.In this scheme, internal coated layer is stiffer than outer covering layer.Preferred outer covering layer be calcium stable or reaction injection molded polyurethane, polyureas or its copolymer, mixture or a heterocomplex, there is the Shao Shi D hardness of about 40-about 50.In another multilayered coating, twin-core embodiment, this outer covering layer and internal coated layer material and thickness are identical, but hardness range is contrary, that is and, outer covering layer is stiffer than internal coated layer.For this harder outer covering layer/softer internal coated layer embodiment, above-mentioned ionomer resin is preferably used as outer covering layer material.

Golf ball structure

The solid core of golf of the present invention can be manufactured with any suitable routine techniques, for example, such as compression moulding or injection moulding.Typically, this inner core is by uncured or slight curing polybutadiene rubber material of compression moulding, to become spherical structure to form.The outer core that surrounds inner core forms by molding compounds on inner core.Can use compression moulding or injection molding technology.Then intermediate layer applied and/or coating.Before this step, cored structure can surface treatment improve its outer surface and will be administered to the tack between the ensuing layer on this core.Such surface treatment can comprise the outer surface of machinery or this core of chemical grinding.For example this core can carry out corona discharge, Cement Composite Treated by Plasma, impregnating with silane or other processing methods well known by persons skilled in the art.

This coating is by suitable technology, to form core or ball component (cored structure and be positioned at this core any intermediate layer around) are upper, such as such as compression moulding, baffle plate molding (flip-molding), injection moulding, retractable pin injection moulding, reaction injection molding(RIM) (RIM), liquid injection molding, casting, injection, powder coated, vacuum forming, flow coat, dipping, spin coating etc.Preferably each coating forms respectively on ball component.For example ethylene acid copolymer ionomer compositions can injection moulding be produced half shell.Selectable, this ionomer compositions can be put into compression mould, and produces hemispherical shell in enough pressure, temperature and time lower mould.Then the hemispherical Shell of this smooth surface is placed in around the ball component of compression tool.Under enough heating and pressure, this shell melting is combined to form the internal coated layer that surrounds described assembly.In another method, use retractable pin injection moulding that this ionomer compositions is directly injected on core.The outer covering layer that comprises polyurethane or polyurea composition can form with casting method.

For example, in a kind of scheme of casting method, the liquid mixture of reactive polyurethane prepolymers and chain extender (curing agent) is poured in lower and upper die cavity.Then golf assembly is fallen into this reactive mixture with controlled speed.Ball sucker can remain on this ball component on appropriate location via decompression or partial vacuum.After the enough gelations of this reactive mixture, (about 12 seconds of typical approximately 4-), removes vacuum, and this intermediate is discharged in die cavity.Then under enough pressure and heating by upper cavity with lower mode cavity is close joins.When this polyurethane prepolymer and chain extender mix, there is exothermic reaction, and this last till this clad material seal and be set in this ball component around till.Finally, this molded ball is cooling in mould, and remove when this molded coating is enough hard, so that it can indeformablely be processed.

After this golf is removed from mould, they can use the known technology of prior art to carry out such as flash distillation finishing, surface treatment, mark, coating etc. of modification step.For example, in traditional color white golf, with the coating of Chinese white, can use suitable method for example such as corona, plasma or ultraviolet (UV) light, to process to carry out surface treatment.Then, mark can be used bat printing (pad-printing), ink jet printing, dye sublimation or other suitable printing processes to be printed onto on the coating of ball as trade mark, symbol, marking pattern, letter etc.Clear top coat (for example priming paint and finishing coat, it can comprise fluorescent whitening agent) is administered on coating.Formed golf club is glossy and durability facing.

In another method of modifying, this golf is painted with one or more paints.For example first white primer can be administered to the surface of ball, then white face japanning be can be applied on this priming paint.Certainly, this golf can be by other colors as red, blue, orange and yellow japanning.As mentioned above, for example trade mark and marking pattern can be applied on the japanning coating of this golf mark.Finally, clear top coat can be applied to this coating any marking pattern and other marks that print on glossy appearance and protection ball is provided.

Different spherical structures can be manufactured with cored structure of the present invention, as shown in above-mentioned Fig. 1 and 2.Such golf design comprises for example 3 layers, 4 layers and 5 layers of design.Be to be understood that the golf shown in Fig. 1 and 2 is only used for illustrative object, does not represent restrictive.Other Golf ball structures can be manufactured according to the present invention.

Method of testing

hardness.the core rigidities of core is to obtain according to program below.This core is pressed in the hemispherical bearing that internal diameter is roughly slightly smaller than this core diameter gently, so that this core remains on the appropriate location of this bearing hemispherical portion, leaves the geometric center plane of the core exposing to the open air simultaneously.By friction, this core is fixed in this bearing, so that it will not move in cutting and grinding steps process, but this friction can not be excessive, to such an extent as to will cause the natural shape of described core to be distorted.Fix this core, so that a minute suture for this core is roughly parallel to bearing top.Before fixing, on these direction 90 degree, measure the diameter of described core.Also carried out the measurement from rest base to core top, the reference point of calculating is in the future provided.Use geometric center that band saw or other suitable cutting tools expose to the open air at this core to locate to have carried out rough lumber on slightly and cut, guarantee that this core does not move in this step process in bearing.This core still remainder in bearing is fixed on the base of surface grinding machine." coarse " surface grinding exposing to the open air is become to smooth flat surfaces, the geometric center of exposing this core, it can verify by measuring the surperficial height expose to the open air from rest base to described core, guarantee upper planar survey this core elemental height accurate half be removed in 0.004 inch.This core is stayed in bearing, with center square, found out Gai Xin center, and careful mark, at this centre mark place, according to ASTM D-2240, measure hardness.The other hardness measurement apart from any distance place, Gai Xin center then can as under carry out: the line that draws radial outward from this centre mark, and measure along the hardness of any given distance of this line, be typically Cong Gai center and measure with 2mm increment.The hardness of Cong Gai center specified distance should be along laying respectively at 180 ° separately or 90 ° of at least two of separating, and preferably four radiation arms are measured, then average.Carried out whole hardness measurements of carrying out in the plane by geometric center, this core still in bearing, and is not upset its orientation simultaneously, and test surfaces is parallel to rest base always like this, and is therefore also parallel to the bottom that hardometer is suitably arranged.

The outer surface hardness of golf ball layer is to measure in the actual external surface of this layer, and be by average the obtaining of a plurality of measured values of obtaining on contrary hemisphere, be careful and avoid on the jointing line of described core or in blemish as measured in hole or projection.Hardness measurement is carried out according to ASTM D-2240 " Indentation Hardness of Rubber and Plastic by Means of a Durometer ".Owing to being curved surface, must carefully guarantee before obtaining case hardness reading, golf or golf assembly are placed in the middle under indentation hardness tester.Use a kind of digital hardometer (can read 0.1 stiffness units) of correction for hardness measurement.This digital hardometer must be connected to, and its bottom is parallel to the bottom of automatic station.Weight on hardometer and erosion rate meet ASTM D-2240.

In certain embodiments, can be higher or lower than by this gradient and its outermost and the line matching of interior hardness number along measured one or more of " just " or " bearing " gradient.In a kind of selectable preferred embodiment, along the hardest point of precipitous especially " just " or " bearing " gradient can higher than inner core (geometric center) or outside the value of sandwich layer (inner surface) penetrale, as long as outermost point (, interior core outer surface) be greater than (for " just ") or this innermost point (lower than (for " bearing "), the geometric center of inner core or the inner surface of outer sandwich layer) so that should " just " and " bearing " gradient keep intact just.

As mentioned above, the hardness gradient direction of golf ball layer is different definition of hardness measurement value difference by obtaining in the outer and inner surface of concrete layer.The core rigidities of inner core in single core ball and the hardness of interior core outer surface or outer sandwich layer are easy to measure according to the test program providing above.If measured, be to carry out before the sandwich layer with other surrounds described layer, in twin-core ball, inner sandwich layer (or other optional intermediate core layer) outer surface is also easily measured for measuring the program of golf ball layer outer surface hardness according to given here.Once other sandwich layer has surrounded the layer of paying close attention to, any interior and outer surface hardness interior or intermediate layer can be difficult to measure.So in the present invention, while needing the interior of sandwich layer or outer surface hardness after internal layer is surrounded by another sandwich layer, use the test program of the above-mentioned point for 1mm place, measuring distance interface.

Be to be understood that equally the difference that exists principle on golf between " material hardness " and " hardness of directly measuring ".In the present invention, material hardness is measured according to ASTM D2240, and generally includes the hardness of measuring smooth " sheet " or " button " that formed by this material.Directly in the upper case hardness of measuring of golf (or other spherical surfaces), typically produced different hardness numbers.The difference of " case hardness " and " material hardness " value, owing to several factors, includes but not limited to that the material of spherical structure (that is, core type, core and/or coating number etc.), ball (or spheroid) diameter and adjacent layer forms.It should also be understood that two kinds of measuring techniques are not linear correlations, therefore a kind of hardness number can not be easy to relevant to another.Shore hardness (for example Shao Shi C or Shao Shi D hardness) is measured according to method of testing ASTM D-2240.

compression.as the Compression by Any Other Name of Jeff Dalton, Science and Golf IV, Proceedings of the World Scientific Congress of Golf (Eric Thain ed., Routledge, 2002) described in (" J.Dalton "), several diverse ways can, for measuring compression, comprise Atti compression, Riehle compression, in the load/deflection of a plurality of firm demands and skew place, measure and effective modulus.In the present invention, " compression " refers to Atti compression, and is according to known program, with Atti compression verification device, measures, and wherein with piston, carrys out compressed ball on spring.Advancing of fixed piston, and the deflection of measuring spring.The measurement of spring deflection is not contacted beginning with ball by it; But exist the compensation of about 1.25mm (0.05 inch) of spring deflection.The core of very low rigidity will not cause that spring deflection is greater than 1.25mm, so have zero compression measured value.Design Atti compression tester is measured the object of diameter 42.7mm (1.68 inches); Therefore for example golf ball core must the padded total height to 42.7mm for less object, obtains pin-point reading.From Atti compression, to the conversion of Riehle (core), Riehle (ball), 100kg deflection, 130-10kg deflection or effective modulus, can carry out according to the formula providing J.Dalton.Compression can be measured as described in the people's such as McNamara United States Patent (USP) 7777871, and its disclosure is hereby incorporated by.

recovery coefficient (" COR ").cOR is according to known program determination, wherein golf or golf assembly (for example golf ball core) is launched from air bubble with two given speed, by the speed of 125ft/s, calculates.Trajectory shadow shield is measured ball speed between air bubble and the steel plate in fixed range.When ball moves towards steel plate, it has activated each shadow shield, and measures ball in the time of each shadow shield.This provides the introducing inversely proportional with the introducing speed of ball to pass through the time.Pellet impact steel plate and resilience, it is again through shadow shield like this.When resilience ball has activated each shadow shield, measure the ball time at each shadow shield place.This provide rate of departure with ball inversely proportional leave the time of passing through.Then COR leaves by time and ball and introduces the recently calculating (COR=V by the time as ball _leave/ V _introduce=T _introduce/ T _leave).

When setting forth numerical lower limits and numerical upper limits here, be contemplated that any combination that can use these values.Be different from operation embodiment, or unless otherwise expressly provided, otherwise whole number ranges, amount, value and percentage can be treated as by wording " approximately " prefix and understand as those of the material for description and other amount, even if wording " approximately " can clearly not occur together with described value, amount or scope.Therefore unless the contrary indication, otherwise the digital parameters described in description and additional claim is similar to, and its performance that can seek according to the present invention the expectation that obtains changes.

Whole patents, open source literature, test program and other lists of references of quoting here, comprising preference document, is to be fully incorporated herein by reference with such degree,, the disclosure document does not contradict with the present invention, and the whole authority allowing for such introducing.

Be to be understood that described here and shown in composition and golf product only represented embodiments more of the present invention.It will be appreciated by those skilled in the art that and can carry out different changes and increase to described composition and product, and do not depart from the spirit and scope of the invention.Its object is to cover all such embodiments by additional claim.

Claims

1. a golf with the core of multilayer, it comprises:

I) inner core that comprises metal material, this inner core has diameter, the proportion (SG of about 1.100 inches of about 0.100- _in) and outer surface hardness (H _{center surface}) and core rigidities (H _{center material}), this H _{center surface}be greater than H _{center material}positive hardness gradient is provided;

Ii) the outer sandwich layer that comprises thermoplastic, this outer sandwich layer is positioned at inner core around, and has thickness, the proportion (SG of about 1.200 inches of about 0.200- _outward) and outer surface the hardness ((H of 40-85 Shao Shi D _{outer core} _{outer surface}) and the inner surface hardness (H of 42-87 Shao Shi D _{the inner surface of outer core}), this H _{the outer surface of outer core}be equal to or less than H _{in outer core} _surfacezero or negative hardness gradient, wherein SG are provided _inbe greater than SG _outward, and the diameter of this inner sandwich layer is less than the thickness of this outer sandwich layer; With

Iii) coating, it has at least one deck around the core that is positioned at this multilayer.

2. the golf of claim 1, wherein the metal material of this inner core is the metal being selected from below: copper, steel, brass, tungsten, titanium, aluminium, magnesium, molybdenum, cobalt, nickel, iron, tin, bronze, silver, gold and platinum and alloy thereof and combination.

3. the golf of claim 1, wherein the diameter of this inner core is that about 0.100-about 0.500 inch and proportion are the about 6.25g/cc of about 1.60-.

4. the golf of claim 1, wherein the diameter of this inner core is that about 0.30-about 0.80 inch and proportion are the about 5.00g/cc of about 1.80-.

5. the golf of claim 1, wherein H _{center material}the about 74 Shao Shi D of about 44-.

6. the golf of claim 1, wherein this outer sandwich layer comprises the thermoplastic being selected from below: ethylene acid copolymer ionomer, polyester, polyamide, polyamide-ether, polyamide-ester, polyurethane, polyureas, fluoropolymer, polystyrene, polypropylene, polyethylene, polyvinyl chloride, polyvinyl acetate, Merlon, polyvinyl alcohol, polyethers, polyimides, polyether-ketone, polyamidoimide and composition thereof.

7. the golf of claim 6, wherein this thermoplastic is the ethylene acid copolymer that contains acid groups so that 70% or acid groups be still less neutralized.

8. the golf of claim 6, wherein this thermoplastic is the ethylene acid copolymer that contains acid groups, so that be greater than 70% acid groups, is neutralized.

9. the golf of claim 8, wherein 90% or larger acid groups be neutralized.

10. claim 7 or 8 golf, wherein this acid groups neutralizes with metal cation salt.

The golf of 11. claims 10, wherein this metal cation is selected from Zn, Na, Li, K, Ca, Mg, Ni, Mn, Cu, Ti and Al and composition thereof.

12. claims 7 or 8 golf, wherein this ethylene acid copolymer is selected from ethene/(methyl) acrylic acid/n-butyl acrylate, ethene/(methyl) acrylic acid/ethyl acrylate, ethene/(methyl) acrylic acid/methyl acrylate; Ethene/(methyl) acrylic acid/n-butyl acrylate and ethene/(methyl) acrylic acid/isobutyl acrylate copolymer.

The golf of 13. claims 1, wherein the thickness of this outer sandwich layer is that about 0.750 inch of about 0.250-is the about 4.10g/cc of about 0.60-with proportion.

The golf of 14. claims 1, wherein H _{the outer surface of outer sandwich layer}the about 70 Shao Shi D of about 40-.

The golf of 15. claims 1, wherein the proportion of the core of this multilayer is the about 5.75g/cc of about 1.10-.

The golf of 16. claims 1, wherein the positive hardness gradient of this inner core is the about 20 Shao Shi D units of about 3-.

The golf of 17. claims 1, wherein zero the or negative hardness gradient of this outer core is the approximately negative 15 Shao Shi D units of about 0-.

The golf of 18. claims 1, wherein this coating is that thickness is the individual layer of about 0.090 inch of about 0.015-, and is formed by thermoplasticity or thermosets.

The golf of 19. claims 1, wherein this coating comprises internal coated layer and outer covering layer, and each coating has case hardness, and wherein the case hardness of internal coated layer is greater than the case hardness of outer covering layer.

The golf of 20. claims 1, wherein this coating comprises internal coated layer and outer covering layer, and each coating has case hardness, and wherein the case hardness of outer covering layer is greater than the case hardness of internal coated layer.

21. 1 kinds of golf with the core of multilayer, it comprises:

Ii) the outer sandwich layer that comprises thermoplastic, this outer core material is positioned at inner core around, and has thickness, the proportion (SG of about 1.200 inches of about 0.200- _outward) and outer surface the hardness ((H of 43-88 Shao Shi D _{outer core} _{outer surface}) and the inner surface hardness (H of 40-85 Shao Shi D _{the inner surface of outer core}), this H _{the outer surface of outer core}be greater than H _{the inner surface of outer core}provide positive hardness gradient, wherein SG _inbe greater than SG _outward, and the diameter of this inner sandwich layer is less than the thickness of this outer sandwich layer; With

The golf of 22. claims 21, wherein the metal material of this inner core is the metal being selected from below: copper, steel, brass, tungsten, titanium, aluminium, magnesium, molybdenum, cobalt, nickel, iron, tin, bronze, silver, gold and platinum and alloy thereof and combination.

The golf of 23. claims 21, wherein the diameter of this inner core is that about 0.500 inch of about 0.100-is the about 6.25g/cc of about 1.60-with proportion.

The golf of 24. claims 21, wherein the thickness of this outer sandwich layer is that about 0.750 inch of about 0.250-is the about 4.10g/cc of about 0.60-with proportion.

25. 1 kinds of golf with the core of multilayer, it comprises:

I) inner core that comprises metal material, this inner core has diameter, the proportion (SG of about 1.100 inches of about 0.100- _in) and outer surface hardness (H _{center surface}) and core rigidities (H _{center material}), this H _{center surface}be equal to or less than H _center _materialzero or negative hardness gradient are provided; With

The golf of 26. claims 25, wherein the metal material of this inner core is the metal being selected from below: copper, steel, brass, tungsten, titanium, aluminium, magnesium, molybdenum, cobalt, nickel, iron, tin, bronze, silver, gold and platinum and alloy thereof and combination.

The golf of 27. claims 25, wherein the diameter of this inner core is that about 0.500 inch of about 0.100-is the about 6.25g/cc of about 1.60-with proportion.

The golf of 28. claims 25, wherein the thickness of this outer sandwich layer is that about 0.750 inch of about 0.250-is the about 4.10g/cc of about 0.60-with proportion.

29. 1 kinds of golf with the core of multilayer, it comprises:

Ii) the outer sandwich layer that comprises thermoplastic, this outer sandwich layer is positioned at inner core around, and has thickness, the proportion (SG of about 1.200 inches of about 0.200- _outward) and outer surface the hardness ((H of 43-88 Shao Shi D _{outer core} _{outer surface}) and the inner surface hardness (H of 40-85 Shao Shi D _{the inner surface of outer core}), this H _{the outer surface of outer core}be greater than H _{the inner surface of outer core}provide positive hardness gradient, wherein SG _inbe greater than SG _outward, and the diameter of this inner sandwich layer is less than the thickness of this outer sandwich layer; With

The golf of 30. claims 29, wherein the metal material of this inner core is the metal being selected from below: copper, steel, brass, tungsten, titanium, aluminium, magnesium, molybdenum, cobalt, nickel, iron, tin, bronze, silver, gold and platinum and alloy thereof and combination.

The golf of 31. claims 29, wherein the diameter of this inner core is that about 0.500 inch of about 0.100-is the about 6.25g/cc of about 1.60-with proportion.

The golf of 32. claims 29, wherein the thickness of this outer sandwich layer is that about 0.750 inch of about 0.250-is the about 4.10g/cc of about 0.60-with proportion.