JP2006102507A - Golf ball with non-ionomer casing layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide golf balls improved to be free from giving a rigid feeling to the players when hit with the club. <P>SOLUTION: Multi-layer golf balls 10 has an inner cover layer 22 including a blend of styrene-block copolymer and trans-polyisoprene, an outer cover layer 20 includes a polyurethane, a polyurea or their mixture, and a core 12 has thermosetting or thermoplastic materials. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a multi-layer golf ball comprising at least an inner cover layer, an outer cover layer and a core, the inner cover layer comprising a blend of styrene block copolymer and trans-polyisoprene.

  In general, golf balls can be divided into two comprehensive groups. They are solid balls and bobbin balls. These different groups may have significantly different play characteristics due to structural differences. Solid balls are very strong and are popular with golfers because they maximize flight distance. Solid balls are usually manufactured by wrapping a solid core made of a crosslinked rubber with a cover material. Typically, solid cores are made from polybutadiene that is chemically crosslinked with zinc diacrylate and / or similar crosslinking agents. In addition to a one-piece solid ball, as in the case of a dual core golf ball, the solid core may also include multiple outer layers. The cover is typically an ionomer material, such as SURLYN ™. SURLYN ™ is a product of E.I. I. Dupont de Nemours & Co. Is a trade name of the ionomer resin family manufactured by The cover may include one layer or multiple layers.

  A solid core and ionomer cover material can be combined to create a durable, friction-resistant ball. However, these materials are so stiff that they are accompanied by a hard “feel” when the ball is hit with a club. Similarly, due to its structure, these balls have relatively low spin and high initial velocity, resulting in a longer flight distance and improved accuracy regardless of the tee, but difficult to play on the green.

In recent years, manufacturers have studied the use of alternative polymers, such as polyurethane, for golf ball covers. For example, referring to US Pat. No. 6,132,324 here, a method of manufacturing a golf ball with a polyurethane cover is proposed. Polyurethane has been recognized as a useful material for golf ball covers since approximately 1960. The polyurethane formulation is the reaction product between the curing agent and the polyurethane prepolymer, and the polyurethane prepolymer itself is the reaction product between the polyal and the isocyanate. As disclosed in US Pat. No. 4,594,364, “polyal” is any organic compound having at least two hydrogen components and an average molecular weight of at least 62. Typical examples of such active hydrogen _{component, -COOH, -OH, NH 2,} = NH, -CONH 2, -SH, and it is -CONH-. Typical polyals are polyols, polyamines, polyamides, polymer captans, polybasic acids and the like. Curing agents used in the past are typically diamines and polyols. A catalyst is often employed to promote the reaction between the curing agent and the polyurethane prepolymer.

U.S. Pat. No. 4,123,061 discloses trifunctional polyols, tetrafunctional polyols, and diamine curing agents. U.S. Pat. No. 5,334,673 discloses the use of thermoset and thermoplastic polyurethanes to make golf covers. Specifically, thermoset polyurethanes are disclosed that are produced from blends consisting of polyurethane prepolymers, slow reacting amine curing agents and / or difunctional glycols.

The first polyurethane cover golf ball that was successful in the market is the Titleist Professional ™ ball, which was launched in 1993. Later, the Titleist Pro-V1 ™ ball was successfully launched in 2000, which had a solid elastic solid polybutadiene core, an ionomer case, and a polyurethane cover. For both professional and amateur golfers, the Pro-V1 ball extends the flight distance regardless of the driver and gives control to green side play.

  There remains a need to provide a non-ionomer casing layer on a multi-layer golf ball to have performance comparable to that of an ionomer casing golf ball.

  The present invention is directed to a multilayer golf ball including at least an inner cover layer, an outer cover layer, and a core. This inner cover layer is a non-ionomer material comprising a blend of styrene block copolymer and trans-polyisoprene. The golf ball preferably has a coefficient of restitution of at least 0.805. The coefficient of restitution of this core is preferably greater than 0.815.

  The cover layer blend ratio ranges from 99 parts trans-polyisoprene to 1 part styrene block copolymer to 50 parts trans-polyisoprene to 50 parts styrene block copolymer. The range of blend ratios for the cover layer is preferably a ratio of 75 parts trans-polyisoprene to 25 parts styrene block copolymer.

  The styrene block copolymer may be any one of styrene butadiene styrene, styrene ethylene butadiene styrene, styrene isobutylene styrene, styrene isoprene styrene, styrene methacrylate butadiene, styrene acrylonitrile, styrene acrylonitrile butadiene, styrene ethylene propylene acrylonitrile, styrene maleic anhydride and blends thereof. One. The most preferred styrene block copolymer is styrene butadiene styrene.

  The specific gravity of the inner cover layer is greater than 1.0, preferably greater than 3.0. The flexural modulus of the inner cover layer is greater than 50000 psi, preferably greater than 60000 psi. The inner cover layer has a hardness greater than Shore D60.

  The outer cover layer includes polyurethane, polyurea, or a mixture thereof, and the hardness of the outer cover layer is less than Shore D65. Polyurethanes and polyureas are prepared from suitable polyisocyanates. The polyurethane is prepared from a suitable polyol and the polyurea is prepared from a suitable polyamine.

  The core includes a thermosetting material or a thermoplastic material. The thermosetting material preferably comprises polybutadiene, a cis-trans catalyst, a free radical source, a crosslinking agent and a filler. The polybutadiene includes cis polybutadiene, trans polybutadiene, vinyl polybutadiene, or mixtures thereof. The cis-trans catalyst is composed of an organic sulfur compound, a metal-containing organic sulfur compound, a sulfur or metal-free substituted aromatic organic compound, a sulfur or metal-free unsubstituted aromatic organic compound, an inorganic sulfide compound, and an aromatic organic metal. A compound, a Group VIA element, or a mixture thereof. Crosslinking agents include zinc acrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate and mixtures thereof.

  The core thermoplastic material preferably comprises a polymer containing acidic groups, a suitable cation source, and a highly neutralized polymer produced by the reaction of an organic acid or salt thereof. A suitable cation source is present sufficient to neutralize the acid groups by about 80% or more, preferably sufficient to neutralize about 90% or more, and most preferably about 100% neutralized. There are enough to exist.

  HNP can also be partially (less than 80%) neutralized ionomer copolymer, ionomer terpolymer, ionomer precursor, thermoplastic, thermoplastic elastomer, grafted metallocene catalyst polymer, ungrafted metallocene catalyst polymer. Single-site polymers, highly crystalline acid polymers and their ionomers. Suitable organic acids or salts thereof include aliphatic organic acids, aromatic organic acids, saturated monofunctional organic acids, saturated bifunctional organic acids, saturated polyfunctional organic acids, non-functional organic acids, including less than 36 carbon base papers. Including any one or more of saturated monofunctional organic acids, unsaturated difunctional organic acids, unsaturated polyfunctional organic acids, and polyunsaturated monofunctional organic acids, such as stearic acid, behenic acid, Including erucic acid, oleic acid, linoleic acid, or dimerized derivatives thereof.

[Definition]
As used herein, substituted and unsubstituted “aryl” groups refer to hydrocarbon rings that contain a conjugated double bond system, typically containing 4n + 2B (where n is an integer) cyclic electrons. To do. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anisyl, tolyl, xylenyl. According to the invention, aryl groups can also include heteroaryl groups such as pyrimidine or thiophene. These aryl groups may also be substituted with any number of different functional groups. In addition to the functional groups described herein in connection with carbocyclic groups, the functional groups on the aryl group are hydroxy or metal salts thereof; mercapto or metal salts thereof; halogens; amino, nitro, cyano, and amides Carboxy and its metal salts including esters and acids; silyl; acrylate and its metal salts; sulfonyl or sulfonamides; and phosphates and phosphites; and combinations thereof.

  As used herein, the terms “Atti compression” and “compression” refer to NJ, the compression compression gauge (Attachment Gage, available commercially from Attic Engineering Corp. of Union City). It is defined as the deflection of the object or material relative to the deflection of the calibration spring, measured using the Atti Compression Gauge). Atch compression ratio is typically used to measure the compression ratio of a golf ball. The compressibility value depends on the diameter of the article to be measured. When using this hatch gauge to measure a core with a diameter of less than 1.680 inches, a metal or other suitable shim is used to produce the object having a diameter of 1.680 inches. Should be understood.

  As used herein, a substituted or unsubstituted “carbocyclic group” means a cyclic carbon-containing compound including, but not limited to, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and the like. Such cyclic groups can also contain various substituents in which one or more hydrogen atoms have been replaced by functional groups. Such functional groups include those described above and lower alkyl groups containing 1 to 28 carbon atoms. This cyclic group of the present invention may further contain a heteroatom.

  The term “cis-trans catalyst” as used herein means any component or combination thereof that will convert at least a portion of the cis-polybutadiene isomer to the trans-polybutadiene isomer at a given temperature. . It should be understood that the combination of the cis-isomer, the trans-isomer, and any vinyl-monomer measured at any given time constitutes 100% of the polybutadiene.

  As used herein, the term “coefficient of restitution” (COR) for a golf ball is defined as the ratio of the rebound velocity to the inbound velocity when the ball is fired onto a rigid plate. The inbound speed is understood to be 125 ft / s.

  As used herein, the term “dynamic stiffness” refers to the load divided by the deflection for an intrusion probe with a spherical radius of 1.4-mm that vibrates at 1 Hz with an amplitude of 100 μm. Is defined as This probe mechanically penetrates the surface of the sample material. A sample material with a spherical core cuts a 6 mm thick layer along the equator portion of the core to produce a 6 mm thick disk, one surface containing the geometric center of the core. It was prepared by doing. Dynamic stiffness can be measured by placing the probe at any selected radial position on the disk. Accurate dynamic measurements can be made by maintaining the material sample at a substantially uniform temperature. The dynamic stiffness was obtained using a dynamic mechanical analyzer, model DMA 2980, available from TA Instruments, DE, Newcastle. The settings for this device with respect to DMA 2980 were frequency 1-Hz, amplitude 100-μm, static load 0.3-N and self-distortion 105%. A probe with a sphere radius of 1.4-mm is available from TA Instruments as an accessory intrusion kit for DMA 2980. The DMA 2980 includes a temperature-controlled chamber that allows testing over a wide range of ambient temperatures.

  These methods and apparatus used to measure “dynamic stiffness” can also be used to measure loss tangent. Loss tangent is the ratio of loss modulus to storage modulus. The loss elastic modulus is an elastic modulus portion that does not coincide with the displacement, and the storage elastic modulus is an elastic modulus portion that coincides with the displacement. This DMA 2980 automatically calculates and outputs the loss tangent.

  As used herein, the term “fluid” includes a liquid, paste, gel, gas, or any combination thereof. As used herein, the term “Group VIA component” or “Group VIA element” means a component, including a sulfur component, a selenium component, or a tellurium component, or a combination thereof.

  As used herein, the term “sulfur component” means a component as elemental sulfur, polymeric sulfur, or a combination thereof. Further, “elemental sulfur” means a cyclic structure of S8, and “polymeric sulfur” should be understood to mean a structure including at least one sulfur with respect to the elemental sulfur. is there.

  The term “molecular weight” as used herein is defined as the absolute mass average molecular weight. The molecular weight is measured by the following method: About 20 mg of polymer is dissolved in 10 ml of tetrahydrofuran (THF). This dissolution can take several days at room temperature, depending on the molecular weight and distribution of the polymer. 1 L of THF was filtered and degassed before being placed in a high performance liquid chromatography (HPLC) reservoir. The HPLC flow rate was set to 1 mL / min for a Viscogel column. This non-flowable, mixed bed column model GMHHR-H, ID 7.8 mm and length 300 mm, is available from Viscotek Corp., TX, TX. The THF flow rate was set to 1 mL / min for at least 1 hour prior to the start of sample analysis or until a stable detector baseline was achieved. During purging of the column and detector, the internal temperature of this Biscotech TDA model 300 triple detector should be set to 40 ° C. This detector is also available from Viscotech. The three detectors (ie, refractive index, differential pressure and light scattering) and the column should be in thermal equilibrium, and these detectors should be purged, zeroed and A calibration system should be prepared according to the instructions given. A 100-μL aliquot of the sample solution can then be injected into the device and the molecular weight of each sample can be calculated by Viscotech's triple detector software. When the molecular weight of the polybutadiene material is measured, a dn / dc of 0.130 should always be used. It is understood that this device and these methods provide numerical values relating to the molecular weight described and claimed herein, and that other devices or methods do not necessarily give values equivalent to those used herein. Should.

  As used herein, the term “multilayer” means at least two layers and includes fluid or liquid center balls, wound balls, hollow center balls, and balls including at least two intermediate and cover layers.

  As used herein, the term “parts per hundred”, also known as “phr”, is defined as the number of parts by weight per 100 parts by weight of the total polymer component of a particular component present in the mixture. Mathematically this is expressed as the total mass of the polymer divided by the mass of a component multiplied by a factor of 100.

As used herein, the term “resilience index” refers to the loss tangent (tan δ) measured at 10 cpm and 100 cpm divided by 990 (frequency span) and multiplied by 100,000 (for normalization and unit convenience). Defined as the difference between This loss tangent is measured using RPA 2000, manufactured by Alpha Technologies, OH, Akron. The RPA 2000 is set to scan a range of 2.5 to 1000 cpm at a temperature of 100 ° C. using an arc of 0.5 degrees. An average of six loss tangent measurements is obtained at each frequency and the resulting average is used to calculate the resilience index. The resilience index is calculated as follows.
Resilience index = 100,000 · [(loss tangent at 10 cpm) − (loss tangent at 1000 cpm)] / 990

  As used herein, the term “substantially free” means less than about 5% by weight, preferably less than about 3% by weight, more preferably less than about 1% by weight and most preferably less than about 0.01% by weight. To do.

  As used herein, the term “flexural modulus” is measured approximately two weeks after the production of the polymer by a modified ASTM D 6272-98 Procedure B. As used herein, the term “stiffness” means this flexural modulus.

  The term “hardness” as used herein refers to the hardness of the material forming the particular layer of the ball discussed herein, as measured by ASTM D2240-00.

The present invention is directed to a multilayer golf ball having an inner cover layer, an outer cover layer, and a core.
In FIG. 1, golf ball 10 of the present invention includes an outer cover layer 20 having an outer surface 14, an intermediate layer 22, and a core 12, which may include one or more layers 16, 18. Optionally, the outer core 18 is a wound layer. The intermediate layer 22 may be a mantle layer, another outer core layer, or an inner cover layer. Here, the intermediate layer 22 is an inner cover layer.

  The inner cover layer 22 comprises a blend of styrene block copolymer and trans-polyisoprene; the outer cover layer 22 is polyurethane, polyurea, or mixtures thereof polyurethane, polyurea, or mixtures thereof w polyurethane, polyurea, or Including a mixture thereof; the core 16 includes either a thermoset material or a thermoplastic material. Preferably, the COR of the core 16 is larger than the COR of the ball 10. The golf ball according to the present invention achieves a high elastic modulus in order to extend the distance regardless of the tee after complying with the USGA golf rules.

In one embodiment, the golf ball 10 of the present invention is a multilayer golf ball including the following configuration.
(A) consisting of a blend of styrene block copolymer, trans-polyisoprene, and filler, such that the flexural modulus of the blend is greater than about 50,000 psi and the specific gravity of the blend is greater than about 1.0, preferably greater than about 3.0. Inner cover layer.
(B) An outer cover made of polyurethane, polyurea or mixtures thereof having a hardness less than Shore D 65.
(C) a core comprising either a thermosetting material such as polybutadiene cross-linked by ZDA, peroxide, and cis-trans catalyst, or a thermoplastic material such as highly or fully neutralized polymer A core having a diameter of less than 1.55 inches, a compression of less than about 85, a COR of about 0.815, and a golf ball rebound coefficient of less than 0.805.

  Depending on the predetermined characteristics, the ball produced according to the present invention has substantially the same or higher resilience, or coefficient of restitution, while reducing the compressibility or modulus of elasticity compared to a ball having a conventional configuration. (COR) can be realized. In addition, balls prepared according to the present invention can also achieve substantially higher resilience or COR without an increase in compression ratio compared to balls having a conventional configuration. Another measure of this resilience is the above “loss tangent” or tan δ, which is obtained when measuring the dynamic stiffness of an object. Loss tangent and the terminology associated with such dynamic properties are typically described in ASTM D4092-90. Thus, a lower loss tangent achieves higher resiliency and consequently higher jump performance. Low loss tangent means that most of the energy imparted to the golf ball from the golf club has been converted to dynamic energy, ie propulsion speed and longer flight distance obtained. The rigidity or compressive stiffness of a golf ball can be measured by, for example, the dynamic rigidity described above. Higher dynamic stiffness means higher compressive stiffness. In order to produce a golf ball with a predetermined compressive stiffness, the dynamic stiffness of the crosslinked polybutadiene reaction product should be less than about 50,000 N / m at -50 ° C. Preferably, this dynamic stiffness is in the range of about 10,000 to 40,000 N / m at -50 ° C, more preferably the dynamic stiffness is about 20,000 to 30,000 N / m at -50 ° C. Should be a range.

  The dynamic stiffness is similar in some respects to the dynamic modulus. Dynamic stiffness depends on the probe geometry as described herein, while dynamic modulus is an intrinsic material property that is independent of geometry. This measurement of dynamic stiffness has inherent properties that allow loss tangent measurements and dynamic elastic modulus quantitative measurements at different points of the sample article. In the case of the present invention, the article is at least part of a golf ball core. The polybutadiene reaction product preferably has a loss tangent of less than about 0.1 at -50 ° C, more preferably less than about 0.07 at -50 ° C.

  The inner cover layer 22 of the present invention comprises a blend of styrene block copolymer, trans-isoprene and filler. Examples of styrene block copolymers include, but are not limited to, styrene butadiene styrene, styrene ethylene butadiene styrene, styrene isobutylene styrene, styrene isoprene styrene, styrene methacrylate butadiene, styrene acrylonitrile, styrene acrylonitrile butadiene, styrene ethylene propylene acrylonitrile, styrene maleic anhydride And blends thereof. The most preferred styrene block copolymer is styrene butadiene styrene (“SBS”), commonly known as “SBS block copolymer”.

  As discussed in US 2003/0064828, other examples of styrene-based thermoplastic elastomers include, but are not limited to, styrene isoprene butadiene styrene (SIBS) block copolymers, or hydrogenated compounds thereof, styrene. Ethylene butadiene styrene (SEBS) block copolymer, styrene ethylene propylene styrene (SEPS) block copolymer, and styrene ethylene ethylene propylene styrene (SEEPS) block copolymer.

  SBS is a hard rubber often used in shoe soles, tires, and other places where durability is important. SBS is a copolymer whose backbone chain is made of a short chain of polystyrene, then a long chain of polybutadiene, and then a short chain of polystyrene. www. psrc. usm. edu / macrog / tpe. See "Thermoplastic Elastomer" from htm. As a result of this structural arrangement, the polystyrene blocks of the SBS copolymer tend to be related to other polystyrene blocks and form polystyrene clusters. See the same. In fact, polystyrene clusters act like crosslinks to polybutadiene blocks. Since polystyrene clusters break at high temperatures, SBS can be processed and reused like a non-crosslinked polymer. SBS is available from Eliochem under the PLIOLITE trade name. http: // elikem. com / prod_coatings_ple. See php.

  Another element of the inner cover layer blend of this invention is trans-polyisoprene. This is a synthetic balata material. Trans-polyisoprene is known as gutta percha and is a harder material than natural rubber. This is about 30% cis-polyisoprene. Steve Rotter, Eraser, 80 Chem. & Eng. News 33 (2002), http: // pubs. asc. org / cen / whatstuff / stuff / 8050eraser. See also html. Trans-polyisoprene is available from Kurrary Co. Available as TP-301.

  Styrene block copolymer and trans-polyisoprene blend from about 1% styrene block copolymer to about 99% trans-polyisoprene to about 50% styrene block copolymer to about 50% trans-polyisoprene ratio Is done. In a preferred embodiment, the inner cover is a blend of about 25% styrene block copolymer to about 75% trans-polyisoprene. The blend of styrene block and trans-polyisoprene has a flexural modulus greater than about 50,000 psi in 2 weeks. Preferably, the flexural modulus of the blend is greater than about 60000 psi.

  SBS and trans-isoprene may further include a density adjusting material, such as a filler, so that the specific gravity of the blend is greater than about 1.0. Preferably, the specific gravity of the blend is greater than about 3.0.

  Suitable fillers are those with a small particle size and low specific gravity, such as barite or tungsten. In order to increase the moment of inertia, the weight of the inner cover must be relatively large. In addition, the inner cover layer may include flakes and other fillers to form a tortuous path for water vapor so that the inner cover layer becomes a barrier to water vapor ingress. The water vapor barrier layer is fully disclosed in US Pat. No. 6,632,147, to which reference is made. In addition, the inner cover layer may be vulcanized when applied to the bobbin core or in a later step of the molding step. The outer surface of the inner cover layer may be halogenated, chemical surface modified or treated, UV irradiated, electron beam irradiated, microwave irradiated, coated (sprayed, dipped, or electrostatic applied), plasma, before the outer cover is applied. Or by one or more of corona discharges. These are disclosed in US Pat. No. 6,315,915, which is hereby incorporated by reference. Preferably, the treatment improves the adhesion of the inner cover layer to the outer cover. The treatment may activate the material to synthesize with the base material and perform similar preferred interactions with the outer cover to improve adhesion and the like. The treatment may also be used to activate the material, increase the softening point of the base material, and improve the temperature stability of the final product. The core preferably provides rigidity to the inner cover layer.

  When the ball diameter is 1.68 inches, the outer diameter of the inner cover layer is preferably from about 1.55 inches to about 1.67 inches. In one embodiment, the outer diameter is about 1.6 inches to about 1.64 inches. A typical inner cover layer has an outer diameter of 1.62 inches. In other embodiments, the outer diameter is between about 1.66 and about 1.67 inches. The thickness of the inner cover layer is preferably about 0.01 inches to about 0.1 inches, more preferably about 0.15 inches.

  In a preferred embodiment, the inner cover layer altitude is about 20 to about 80 Shore D, preferably about 50 to about 75 Shore D, and more preferably about 60 to about 75 Shore D.

１：該ブレンド比は、バラタ／Ｐｌｉｏｌｉｔｅによって行った。
２：ＳＧ変化を伴うブレンドは、９０バラタ／１０Ｐｌｉｏｌｉｔｅブレンドを用いて作成。
３：この５０／５０柔軟性は全て、テスト中に破損した。 The compression of the core and inner cover layer is typically from about 20 to about 100, preferably from about 40 to about 90. In a preferred embodiment, the compression of the core and inner cover layer is from about 50 to about 80. In one embodiment, the inner cover layer has a specific gravity of about 0.8 to about 1.3, preferably about 0.9 to about 1.2. In one embodiment, the partially formed golf ball including the inner cover layer has a weight of about 40 g to about 46 g. The loss tangent of the inner cover layer can be about 0.03 to about 0.08 from about −30 ° C. to about 20 ° C. in one embodiment. The elasticity and complex modulus of the inner cover layer can be about 5000 to about 12000 Kgf / cm ² at about −30 ° C. to about 20 ° C. The following table shows preferred inner cover layer materials and properties.

1: The blend ratio was determined by balata / Pliolite.
2: A blend with SG change was created using a 90 balata / 10 Pliolite blend.
3: All this 50/50 flexibility was broken during the test.

  The outer cover layer 20 of the present invention preferably comprises polyurethane, polyurea or mixtures thereof, the elevation of which is less than about Shore D65. In order to achieve the desired altitude, a filler is mixed into the polyurethane and polyurea. Suitable fillers are shown below.

Suitable cover materials include, but are not limited to:
(1) Polyurethanes, for example polyurethanes prepared from polyols and diisocyanates or polyisocyanates disclosed in US Pat. Nos. 5,334,673 and 6,506,851, and US Patent Application No. 10/194059.
(2) Polyureas, such as those disclosed in US Pat. No. 5,484,870 and US patent application Ser. No. 10 / 228,311.
(3) Polyurethane-polyurea hybrids, blends or copolymers containing urethane or urea segments.

  The outer cover layer preferably comprises a polyurethane composition comprising a reaction product of at least one polyisocyanate and at least one curing agent. The curing agent may include, for example, one or more diamines, one or more polyols, or combinations thereof. The polyisocyanate is combined with one or more polyols to form a prepolymer, which is further combined with at least one curing agent. As a result, the polyols described are suitable for use in one or both elements of polyurethane materials, i.e. prepolymer parts and curing agents.

  In yet another embodiment, the polyurethane composition comprises at least one isocyanate, at least one polyol, and more preferably at least one curing agent. Examples of polyisocyanates are 4,4'-diphenylmethane diisocyanate (MDI), polymeric MDI, carbodiimide-modified liquid MDI, 4,4'-dicyclohexylmethane diisocyanate (H12MDI), p-phenylene diisocyanate (PPDI), toluene diisocyanate (TDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), xylene diisocyanate (XDI), p-tetra Methylxylene diisocyanate (p-TMXDI), m-tetramethylxylene diisocyanate (m-TMXDI), ethylene diisocyanate, propylene-1 2-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexyl diisocyanate, 1,6-hexamethylene diisocyanate (HDI), dodecane-1,12-diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate Cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, methylcyclohexylene diisocyanate, HDI triisocyanate, 2,4,4-trimethyl-1,6- Including but not limited to hexane diisocyanate (TMDI), tetracene diisocyanate, naphthalene diisocyanate, anthracene diisocyanate, and mixtures thereof. Polyisocyanates are known to those skilled in the art as those having two or more isocyanate groups, ie di-, tri- and tetra-isocyanates. Preferably the polyisocyanate comprises MDI, PPDI, TDI or mixtures thereof, more preferably the polyisocyanate comprises MDI. As used herein, the term “MDI” includes 4,4′-diphenylmethane diisocyanate, polymeric MDI, carbodiimide-modified liquid MDI, and mixtures thereof, and the polyisocyanate used further includes “low free monomer Should be understood as having a "free" monomeric isocyanate group at a lower level than conventional diisocyanates, i.e. the formulations of the present invention. Typically contain less than about 0.1% free monomer groups. Examples of “low free monomer content” diisocyanates include, but are not limited to, Low Free Monomer MDI, Low Free Monomer TDI, and Low Free Monomer PPDI.

  Suitable polyisocyanates should contain less than about 14% unreacted NCO groups. Preferably, the at least one polyisocyanate does not exceed about 7.5% NCO groups, more preferably about 2.5% to about 7.5% NCO groups and most preferably about 4% to Contains NCO groups in the range of about 6.5%.

  The polyol component of the polyurethane may be a polyester polyol. Suitable polyester polyols are included in the polyurethane material of the present invention. Suitable polyester polyols include, but are not limited to, polyethylene adipate glycol, polybutylene adipate glycol, polyethylene propylene adipate glycol, o-phthalate-1,6-hexanediol, and mixtures thereof. The hydrocarbon chain can include saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups.

  Alternatively, the polyol element may be a polycaprolactone polyol. Suitable polycaprolactone polyols are included in the materials of the present invention. Suitable polycaprolactone polyols include 1,6-hexanediol-initiated polycaprolactone, diethylene glycol-initiated polycaprolactone, trimethylolpropane-initiated polycaprolactone, neopentyl glycol-initiated polycaprolactone, 1,4-butanediol-initiated polycaprolactone and these Including but not limited to mixtures. The hydrocarbon chain can include saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups.

  Alternatively, the polyol element may be a polycarbonate polyol. Suitable polycarbonate polyols are included in the polyurethane material of the present invention. Suitable polycarbonates include, but are not limited to, polyphthalate carbonate. The hydrocarbon chain can include saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups.

  The curing agent may include a polyol curing agent. Suitable polyol curing agents include, but are not limited to, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, low molecular weight polytetramethylene ether glycol, 1,3-bis (2-hydroxyethoxy) benzene; 3-bis [2- (2-hydroxyethoxy) ethoxy] benzene, 1,3-bis {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} benzene, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, resorcinol-di- (β-hydroxyethyl) ether, hydroquinone-di- (β-hydroxyethyl) ether, trimethylolpropane or mixtures thereof.

  Polyamine curing agents are also suitable for use with the curing agent in polyurethane formulations. This has also been found to improve the cutting resistance, shear resistance and impact resistance of the resulting ball. Preferred polyamine curing agents are 3,5-dimethylthio-2,4-toluenediamine and its isomer; 3,5-diethyltoluene-2,4-diamine and its isomer, such as 3,5-diethyltoluene-2,6- 4,4′-bis (2-chloroaniline); 4,4′-bis (sec-butylamino) -diphenylmethane; 1,4-bis (sec-butylamino) -benzene, 4,4′-methylene -Bis (2-chloroaniline); 4,4'-methylene-bis (3-chloro-2,6-diethylaniline); polytetramethylene oxide-di-p-aminobenzoate; N, N'-dialkyldiaminodiphenylmethane P, p'-methylenedianiline (MDA); m-phenylenediamine (MPDA); 4,4'-methylene- (4-chloroaniline) (MOCA); 4,4′-methylene-bis (2,6-diethylaniline); 4,4′-diamino-3,3′-diethyl-5,5′-dimethyldiphenylmethane; 2,2 ′, 3,3′-tetrachlorodiaminodiphenylmethane; 4,4′-methylene-bis (3-chloro-2,6-diethylaniline); trimethylene glycol di-p-aminobenzoate; and mixtures thereof Including, but not limited to. Preferably, the curing agent of the present invention comprises 3,5-dimethylthio-2,4-toluenediamine and its isomers, such as ETHACURE 300. Suitable polyamine curing agents, including both primary and secondary amines, preferably have a weight average molecular weight in the range of about 64 to about 2000.

  In addition, at least one diol, triol, tetraol, or hydroxy-terminated curing agent can be added to the polyurethane formulation described above. Suitable diol, triol and tetraol groups are ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, low molecular weight polytetramethylene ether glycol, 1,3-bis (2-hydroxyethoxy) benzene, 1,3- Bis [2- (2-hydroxyethoxy) ethoxy] benzene, 1,3-bis {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} benzene, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, resorcinol-di- (4-hydroxyethyl) ether, hydroquinone-di- (4-hydroxyethyl) ether and mixtures thereof. Preferred hydroxy-terminated curing agents include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane and mixtures thereof.

  Preferably, the hydroxy-terminated curing agent has a molecular weight in the range of about 48-2000. The hydroxy-terminated and amine curing agents may contain one or more saturated, unsaturated, aromatic and cyclic groups. The polyurethane composition may be produced with a blend or mixture of curing agents, or with one curing agent.

  The optional filler component can be selected to provide additional density to the blend of components previously described. The choice of the filler component depends on the intended golf ball characteristics. Examples of fillers used in the filler component of the polyurethane include those described herein in connection with the polybutadiene reactive component. Similar or identical additives, such as nanoparticles, fibers, glass spheres, and / or various metals, such as titanium and tungsten, in amounts required to improve one or more golf ball properties. It can also be added to the polyurethane formulation. Additional components that can be added to the polyurethane formulation include UV stabilizers and other dyes, as well as optical brighteners and fluorescent pigments and dyes. Such incidental ingredients can be added in any amount that will achieve its intended purpose.

  Any known technique can be used to combine the polyisocyanates, polyols, and curing agents of the present invention. One suitable technique is known in the art as a one-shot process, where the polyisocyanate, polyol, and curing agent are mixed simultaneously. This neat technique of mixing is known as the prepolymer process. In this method, the polyisocyanate and polyol are mixed separately prior to addition of the curing agent. This method achieves a more uniform mixing, resulting in a more uniform polymer composition.

  Due to the very thin nature, a very thin outer cover layer of a golf ball can be realized using a castable, reactive material applied in fluid form. Specifically, the castable, reactive liquid reacts to form a urethane elastomer material to achieve the desired very thin outer cover layer.

  The castable reactive liquid used to form the urethane elastomer material may be applied to the inner core using a variety of coating techniques such as spraying, dipping, spin coating or flow coating methods well known in the art. Applicable to above. An example of a suitable coating technique is "Method and Apparatus For Forming Polyurethane Cover On A Golf Ball" filed May 2, 1995, and "Method and Apparatus for Forming Polyurethane Cover On A Golf Ball". No. 5,733,428, the title of which is incorporated herein by reference. The entire disclosure of this patent is incorporated herein by reference.

  Similarly, US Pat. No. 5,0062,977 and US Pat. No. 5,334,673 disclose suitable molding techniques utilized for applying the castable, reactive liquid employed in this invention. See especially the disclosure of each patent. However, the method of the present invention is not limited to the use of these methods.

In one embodiment, the loss tangent of the cover is typically from about -30 ° C to 20 ° C and from about 0.16 to about 0.075. In one embodiment, the complex modulus of the cover layer on the ball is about 1000 to about 2800 Kgf / cm ² at −30 ° C. to 20 ° C. In one embodiment, the cover material has a specific gravity of about 1 to about 2, and preferably about 1.1 to about 1.4. In one preferred embodiment, the cover material has a specific gravity of about 1.10 to about 1.25.

  The material hardness of the outer cover layer should be about 20 to about 60 Shore D, preferably about 30 to about 50 Shore D, more preferably about 45 Shore D, as measured by ASTM D2240-00. It is. When the hardness of the outer cover material is measured directly on the golf ball surface, the value tends to be greater than the material hardness. The hardness of the outer cover is preferably about 45 to about 60 Shore D as measured on the golf ball surface. The material hardness of the inner cover layer is preferably from about 50 to about 70 Shore D, more preferably from about 60 to about 65 Shore D.

  As described above, the core can be (a) a thermosetting material such as polybutadiene, ZDA, peroxide and cis-trans catalyst, or (c) a thermoplastic material such as a fully neutralized highly neutralized polymer. The core diameter is at least about 1.55 inches, the compression is less than about 85, and the COR is greater than 0.815.

If the core is made from a thermoset material, the core composition preferably includes at least one rubber material having a resilience index of at least less than about 40. Preferably, the resilience index is at least about 50. A comparison of many polybutadiene polymers is listed in Table 1 below. Polymers that produce elastic golf balls and, therefore, suitable for use in the center or other portion of a golf ball according to the present invention are, but not limited to, CB23, CB22, BR60, and 1207G.

  The thermosetting material in the core has a reaction product comprising a cis-trans catalyst, an elastic polymer element comprising butadiene, a free radical source, an optional crosslinker, a filler or both. Preferably, the polybutadiene reaction product is used to form at least a portion of the core of the golf ball, and the core is provided in connection with this example as further discussed below. Preferably, the first dynamic stiffness measured at −50 ° C. of the reaction product is less than about 130% of the second dynamic stiffness measured at 0 ° C. More preferably, the first dynamic stiffness is less than about 125% of the second dynamic stiffness. Most preferably, the first dynamic stiffness is less than about 110% of the second dynamic stiffness.

  For cis-trans conversion, cis-trans catalysts, such as organic sulfur or metal-containing organic sulfur compounds, sulfur or metal free substituted or unsubstituted aromatic organic compounds, inorganic sulfide compounds, aromatic organometallic compounds, or A mixture of these is necessary. The cis-trans catalyst element may include one or more cis-trans catalysts described herein. Specifically, the cis-trans catalyst may be a blend of an organic sulfur compound and an inorganic sulfur compound.

  Preferred organic sulfur elements are 4,4'-diphenyl sulfide, 4,4'-ditolyl disulfide, or 2,2'-benzaminodiphenyl disulfide, or mixtures thereof. More preferred organic sulfur elements include 4,4'-ditolyl disulfide. The organic sulfur cis-trans catalyst, if present, preferably provides an amount sufficient to produce the reactive organism so that the reaction product contains at least about 12 percent trans-polybutadiene isomer. Typically, it gives more than about 32% trans-polybutadiene isomer based on the total elastic polymer element. In other embodiments, metal-containing organic sulfur elements can be used in this invention. Suitable metal-containing organosulfur elements include, but are not limited to, cadmium, copper, lead, and tellurium analogs of diethyldithiocarbamate, diamyldithiocarbamate and dimethyldithiocarbamate, or mixtures thereof. Suitable additional examples can be found in US patent application Ser. No. 10 / 40,592.

  A cis-trans catalyst or organosulfur compound, preferably a halide, is a compound containing cis-trans catalyst activity or sulfur atoms (or both) and is present in the polymer composition by at least about 0.01 phr, preferably at least Present at about 0.05 phr, more preferably at least about 0.1 phr, even more preferably greater than about 0.25 phr, optionally greater than about 2 phr, such as greater than about 2.2 phr, Further present is greater than about 2.5 phr, provided that it is less than about 10 phr, preferably less than about 5 phr, more preferably less than about 2 phr, even more preferably less than about 1.1 phr, such as less than about 0.75. Less than about 0.6 phr. Useful compounds in this category include those disclosed in U.S. Pat. Nos. 6,525,141, 6,465,578, 6,184,301, 6,139,447, 5,697,856, 5,816,944, and 5,252,652, for details. Please refer to.

  One group of suitable organosulfur compounds are halogenated thiophenols and their metal salts, examples of which are pentafluorothiophenol, 2-fluorothiophenol, 3-fluorothiophenol, 4-fluorothiophenol, 2, 3-fluorothiophenol, 2,4-fluorothiophenol, 3,4-fluorothiophenol, 3,5-fluorothiophenol, 2,3,4-fluorothiophenol, 3,4,5-fluorothiophenol, 2,3,4,5-tetrafluorothiophenol, 2,3,5,6-tetrafluorothiophenol, 4-chlorotetrafluorothiophenol, pentachlorothiophenol, 2-chlorothiophenol, 3-chlorothiophenol 4-chlorothiophenol, 2,3-chlorothio Enol, 2,4-chlorothiophenol, 3,4-chlorothiophenol, 3,5-chlorothiophenol, 2,3,4-chlorothiophenol, 3,4,5-chlorothiophenol, 2,3, 4,5-tetrachlorothiophenol, 2,3,5,6-tetrachlorothiophenol, pentabromothiophenol, 2-bromothiophenol, 3-bromothiophenol, 4-bromothiophenol, 2,3-bromo Thiophenol, 2,4-bromothiophenol, 3,4-bromothiophenol, 3,5-bromothiophenol, 2,3,4-bromothiophenol, 3,4,5-bromothiophenol, 2,3 , 4,5-tetrabromothiophenol, 2,3,5,6-tetrabromothiophenol; pentaiodothiophenol 2-iodothiophenol, 3-iodothiophenol, 4-iodothiophenol, 2,3-iodothiophenol, 2,4-iodothiophenol, 3,4-iodothiophenol, 3,5-iodothiophenol, 2,3,4-iodothiophenol, 3,4,5-iodothiophenol, 2,3,4,5-tetraiodothiophenol, 2,3,5,6-tetraiodothiophenol and zinc salts thereof As well as mixtures thereof. The metal ion, if present, is related to thiophenol and is selected from zinc, calcium, magnesium, cobalt, nickel, iron, copper, sodium, potassium, lithium and others. Halogenated thiophenols associated with organic cations such as ammonium can also be utilized in this invention.

  More specifically, effective halogenated thiophenols are pentachlorothiophenol, pentachlorothiophenol zinc, pentachlorothiophenol magnesium, pentachlorothiophenol cobalt, pentafluorothiophenol, pentafluorothiophenol zinc and blends thereof. including. Preferred candidates are pentachlorothiophenol (available from Structol), pentachlorothiophenol zinc (available from eChinachem), and blends thereof.

  Another group of suitable organic sulfur compounds are organic disulfides, which include, without limitation, perhalogenated (ie, fully halogenated) organic disulfides and organometallic disulfides. The perhalogenated compound is preferably perfluoride, perchloride and / or perbromide. Perhalogenated organic disulfides include any, perhalogenated derivatives of organic sulfides known or available to those skilled in the art, such as ditolyl disulfide, diphenyl disulfide, quinolyl disulfide benzoyl disulfide, and Including bis (4-acryloxy benzene) disulfide and others. A specific example is perchloroditolyl sulfide. Organometallic disulfides include any metal cation disclosed herein and any organic disulfide combination disclosed herein. A specific example is zinc ditolyl disulfide.

Suitable substituted or unsubstituted aromatic organic compounds that do not include sulfur or metal are, but are not limited to, 4,4′-diphenylacetylene, azobenzene, or mixtures thereof. The aromatic organic group is preferably C ₆ to C ₂₀ in size, more preferably C ₆ to C ₁₀ in size. Suitable inorganic sulfide compounds include, but are not limited to, titanium sulfide, manganese sulfide, and sulfurized analogs of iron, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, tin, and bismuth.

  The cis-trans conversion catalyst can also include a Group VIA component. Elemental sulfur and polymer sulfur are commercially available, for example, from Elastochem, Inc. of Chardon, OH. Examples of sulfur catalyst compounds include PB (RM-S) -80 elemental sulfur and PB (CRST) -65 polymer sulfur, each of which is available from Elastchem. An example of tellurium catalyst under the trade name TELLOY and an example of selenium catalyst under the trade name VANDEX are each commercially available from RT Vanderbilt.

  A free radical source, often referred to as a free radical initiator, is required in the formulations and methods of the present invention. This free radical source is typically a peroxide and is preferably an organic peroxide. Suitable free radical sources include di-t-amyl peroxide, di (2-t-butylperoxyisopropyl) benzene peroxide, 3,3,5-trimethylcyclohexane, a-a bis (t-butylperoxy) diisopropylbenzene. 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, dicumyl peroxide, di-t-butyl peroxide, 2,5-di- (t-butylperoxy) -2, 5-dimethylhexane, n-butyl-4,4-bis (t-butylperoxy) valerate, lauryl peroxide, benzoyl peroxide, t-butyl hydroperoxide, and the like and mixtures thereof.

  A cross-linking agent is included to increase the altitude of the reaction product. Suitable crosslinkers include one or more metal salts of unsaturated fatty acids or monocarboxylic acids, such as zinc, aluminum, sodium, lithium, nickel, calcium, or magnesium acrylate salts, and the like, and mixtures thereof. Preferred acrylates include zinc acrylate, zinc diacrylate (ZDA), zinc methacrylate, and zinc dimethacrylate (ZDMA) and mixtures thereof. The crosslinker must be included in an amount sufficient to crosslink a portion of the polymer chain in the elastic polymer element. This can be accomplished, for example, by varying the amount of crosslinking agent and is well known to those skilled in the art.

  The composition of the present invention may also include a filler added to the polybutadiene material to adjust the density and / or specific gravity of the core or cover. The filler is typically a polymer or appendix particle. Examples of fillers are precipitated hydrated silica, clay, talc, asbestos, glass fiber, aramid fiber, mica, calcium metasilicate, barium sulfate, zinc sulfide, lithopone, silicate, silicon carbide, diatomaceous earth, polyvinyl chloride, carbonate Salts such as calcium carbonate, magnesium carbonate, metals such as titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, lead, copper, boron, cobalt, beryllium, zinc, tin, alloys such as steel, brass, bronze Boron carbide whiskers, tungsten carbide whiskers, metal oxides such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide, particulate carbonaceous materials such as graphite, carbon black, cotton floc, natural bitumen ,cellulose Lock, comprising leather fibers, microballoons, for example, glass, ceramics, fly ash, and combinations thereof.

  Antioxidants may optionally be included in the polybutadiene in the center produced according to the present invention. The antioxidant is a compound that eliminates or prevents deterioration due to oxidation of polybutadiene. Antioxidants useful in this invention are, but not limited to, anhydrous quinoline antioxidants, amine type antioxidants, and phenol type antioxidants.

  Other optional components, such as accelerators, specifically tetramethylthiuram, peptizers, processing aids, plasticizers, dyes and pigments, and other additives well known to those skilled in the art, are made according to the present invention. An amount sufficient to achieve the purpose for which they are used may be used.

  The compression of a golf ball core or core portion prepared according to the present invention is typically about 15 to 100. In one embodiment, the compression is below about 50, more preferably below about 25. In a preferred embodiment, the compression is about 60 to 90, more preferably about 70 to 85. There are various equivalent ways to measure compression. For example, 70 Atti compression (previously called “PGA compression”) is equivalent to a central hardness of 3.2 mm deflection with a 100 kg load, a “spring constant” of 36 Kgf / mm. In one embodiment, the deflection of the golf ball core is about 3.3 mm to 7 mm in a 130 kg-10 kg test.

  Alternatively, the core of the present invention is thermoplastic, essentially a highly neutralized polymer (“HNP”), comprising acid groups on the polymer and organic acids or corresponding salts. Including those produced by reaction with a suitable cation source. The included organic acid or salt thereof is in an amount sufficient to neutralize the polymer by about 80%. In a preferred embodiment, the polymer may be about 90% neutralized. In other preferred embodiments, the polymer may be about 100% neutralized.

  HNP is an ionomer copolymer, ionomer terpolymer, ionomer precursor, thermoplastic, thermoplastic elastomer, grafted metallocene catalyst polymer, ungrafted metallocene catalyst polymer, single site polymer, highly crystallized acid polymer, and more Ionomers, cationic ionomers and mixtures thereof.

  Examples of organic acids of HNP include, but are not limited to, aliphatic organic acids, aromatic organic acids, saturated monofunctional organic acids, saturated bifunctional organic acids, saturated polyfunctional organic acids, unsaturated monofunctional Including organic acids, unsaturated difunctional organic acids, unsaturated polyfunctional organic acids and polysaturated monofunctional fatty acids.

  Appropriate cations can be used to neutralize the organic acid of HNP. Suitable cations include, but are not limited to, barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin, or Contains calcium.

  Alternatively, fatty acid salts can be used to neutralize the organic acid of HNP. These fatty acids include, but are not limited to, caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid, or dimerized derivatives thereof.

  Examples of HPN thermoplastic ionomer resins include a cross-metal bond between a polymer of monoolefin and at least one selected from the group consisting of unsaturated mono-, dicarboxylic acids and esters thereof having 3 to 12 carbon atoms. Acquired by granting. The polymer contains 1 to 50% by weight of unsaturated mono- or dicarboxylic acids and / or esters thereof. More specifically, low modulus ionomers, such as acid-containing ethylene copolymer ionomers, include E / X / Y copolymers, where E is ethylene and X is 5-35 (preferably 10-35) of the polymer. Most preferably 15-35, making the ionomer a highly oxidized ionomer) by weight percent acrylic acid or methacrylic acid, and Y is 0-50 (preferably 0-25, most preferably 0- 2) Only a weight percent of a softening copolymer such as acrylate or methacrylate, wherein the acid moiety is 1-100% (preferably at least 80%, most preferably about 100%) of a cation such as lithium, sodium, potassium, magnesium, calcium, Barium, lead, tin, zinc or aluminum or a combination of these cations Allowed by, it is neutralized to form an ionomer. In other examples, lithium, sodium, potassium, magnesium, calcium and zinc are preferred cations.

  Examples of HNPs suitable for this invention are specific acid-containing ethylene copolymers, which include ethylene / acrylic acid, ethylene / methacrylic acid, ethylene / acrylic acid / n-butyl acrylate, ethylene / methacrylic acid. Acid / n-butyl acrylate, ethylene / methacrylic acid / methyl acrylate, ethylene / methacrylic acid / methyl acrylate, ethylene / methacrylic acid / methyl methacrylate, or ethylene / acrylic acid / n-butyl methacrylate. Preferred acid-containing ethylene copolymers include ethylene / methacrylic acid, ethylene / acrylic acid, ethylene / methacrylic acid / n-butyl acrylate, ethylene / acrylic acid / n-butyl acrylate, ethylene / methacrylic acid / methyl acrylate or ethylene / acrylic acid. / Methyl acrylate copolymer. The most preferred acid-containing ethylene copolymers are ethylene / methacrylic acid, ethylene / acrylic acid, ethylene / (meth) acrylic acid / n-butyl acrylate, ethylene / (meth) acrylic acid / ethyl acrylate, or ethylene / (meth) acrylic acid / Methyl acrylate copolymer.

  Other HNPs suitable for use in this invention are described in WO 00/23519, WO 01/29129, US patent applications 10/877344, and 10/882130, to which reference is made for details.

  Optionally, a filler element may be selected to add additional density to the previously described blend of elements, and this selection can be achieved by selecting parts (eg multi-layer core or cover in ball, mantle, core, center, middle layer) ) And the type of golf ball desired (eg, one-piece, two-piece, three-piece or multi-piece ball) and will be fully described below. Generally, the filler is an inorganic material greater than about 4 grams / cubic centimeter (gm / cc), preferably greater than 5 gm / cc, based on 0 to about 60 wt. % Amount is included. Examples of useful fillers include those described herein. Preferably, the filler material is non-reactive or hardly reactive and is not hard or does not increase compression and does not significantly reduce the coefficient of restitution.

In addition, other additives useful in the practice of this invention are acid copolymer waxes (eg, Allied Wax AC143 is ethylene / 16-18% acrylic acid coparylene, with an average molecular weight of 2040). Helps to prevent the reaction between the filler material (eg ZnO) and the acid part of the ethylene coparimer. Other additional additives include TiO _2, which bleaches, brighteners, surfactants, used as a processing aid.

  HNP ionomers may be blended with conventional ionomer copolymers (di-, ter-, etc.) and the product properties are adjusted to the desired one using well-known techniques. Even after blending, the hardness is still lower and the modulus of elasticity is higher than when blending based on conventional ionomers.

[Experimental example]
The resulting golf ball typically has a coefficient of restitution of greater than about 0.7, preferably greater than about 0.75, and more preferably greater than about 0.78. The golf ball's Atti compression (previously referred to as PGA compression) is typically at least about 40, preferably about 50 to 120, and more preferably about 60 to 100.

  Other things in the working examples, or all numerical ranges, quantities, values, percentages, such as those for the quantity of material, and others in the specification, even if not explicitly stated, even if the value, quantity or Even if the term “about” is not displayed in relation to a range, it can be read as if “about” is placed in front of it. Accordingly, unless indicated otherwise, the numerical parameters set forth in the specification and claims are approximate, depending on the desired characteristics that are contemplated by the present invention. Change. At a minimum, of course, it does not limit the application of the doctrine of equivalents, but each number of parameters should be interpreted in the light of the number of significant digits recorded and the normal rounding process.

  Although the numerical ranges and parameters representing the broad scope of the invention are approximate, the numerical values shown in the examples were recorded as accurately as possible. Arbitrary numerical values nevertheless include word elements that inevitably result from the standard deviation found in each test measurement. Further, it should be understood that any combination of values, including the exemplified values, can be used where numerical ranges of various scopes are indicated.

  While it will be appreciated that the exemplary embodiments of the invention described herein will satisfy preferred embodiments of the invention, it should be understood that various modifications and other embodiments can occur to those skilled in the art. Examples of such changes include slight changes in the numerical values described above. Accordingly, the numerical values recited above and in the claims include such numerical values and include values that are close to or very close to the values described above and recited in the claims. Accordingly, the claims are intended to cover all such modifications and other embodiments, and are to be understood as falling within the spirit and scope of this invention.

It is sectional drawing of the 1st Example of the golf ball of this invention.

Claims (28)

A multilayer golf ball comprising at least an inner cover layer, an outer cover layer and a core,
The inner cover layer is a non-ionomer material comprising a blend of styrene block copolymer and trans-polyisoprene;
A multilayer golf ball having a coefficient of restitution of at least 0.805.   The multilayer golf ball of claim 1, wherein the core has a coefficient of restitution of greater than 0.815.   The blend ratio range is from 99 parts trans-polyisoprene to 1 part styrene block copolymer to 50 parts trans-polyisoprene to 50 parts styrene block copolymer. Multi-layer golf ball.   4. The multi-layer golf ball of claim 3, wherein the inner cover layer blend has a ratio of 75 parts trans-polyisoprene to 25 parts styrene block copolymer.   The styrene block copolymer is a group consisting of styrene butadiene styrene, styrene ethylene butadiene styrene, styrene isobutylene styrene, styrene isoprene styrene, styrene methacrylate butadiene, styrene acrylonitrile, styrene acrylonitrile butadiene, styrene ethylene propylene acrylonitrile, styrene maleic anhydride and blends thereof. The multilayer golf ball according to claim 1, which is one selected from the group consisting of:   The multilayer golf ball of claim 1, wherein the styrene block copolymer is styrene butadiene styrene.   The multilayer golf ball of claim 1, wherein the specific gravity of the inner cover layer is greater than 1.0.   The multilayer golf ball of claim 7, wherein the specific gravity of the blend of the inner cover layer is greater than 3.0.   The multilayer golf ball of claim 1, wherein the inner cover layer has a flexural modulus greater than 50000 psi.   The multi-layer golf ball of claim 9, wherein the flexural modulus of the blend of the inner cover layer is greater than 60000 psi.   The multilayer golf ball of claim 1, wherein the inner cover layer has a hardness greater than Shore D60.   The multilayer golf ball according to claim 1, wherein the outer cover layer is made of polyurethane, polyurea, or a mixture thereof, and the hardness of the outer cover layer is less than Shore D65.   The polyurethane and the polyurea are prepared from polyisocyanate, which is 4,4′-diphenylmethane diisocyanate, polymeric 4,4′-diphenylmethane diisocyanate, carbodiimide-modified liquid 4,4′-diphenylmethane diisocyanate, 4 4'-dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, p-tetramethylxylene diisocyanate , M-tetramethylxylene diisocyanate, ethylene diisocyanate, propylene , 2-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexyl diisocyanate, 1,6-hexamethylene diisocyanate, dodecane-1,12-diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, methylcyclohexylene diisocyanate, triisocyanate of hexamethylene diisocyanate, 2,4,4-trimethyl-1,6- Consists of hexane diisocyanate triisocyanate, tetracene diisocyanate, naphthalene diisocyanate, anthracene diisocyanate, and mixtures thereof Multilayer golf ball of claim wherein one selected from the loop.   The polyurethane is prepared from a polyol, and the polyol is ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, low molecular weight polytetramethylene ether glycol, 1,3-bis (2-hydroxyethoxy) benzene; 1,3 -Bis [2- (2-hydroxyethoxy) ethoxy] benzene, 1,3-bis {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} benzene, 1,4-butanediol, 1,5-pentane 6. One selected from the group consisting of diol, 1,6-hexanediol, resorcinol-di- (β-hydroxyethyl) ether, hydroquinone-di- (β-hydroxyethyl) ether, and mixtures thereof. 12 description Multi-layer golf ball.   The polyurea is prepared from a polyamine, which is 3,5-dimethylthio-2,4-toluenediamine, 3,5-diethyltoluene-2,4-diamine, 4,4′-bis (sec-butylamino). ) -Diphenylmethane; 1,4-bis- (sec-butylamino) -benzene, 4,4′-methylene-bis (2-chloroaniline), 4,4′-methylene-bis (3-chloro-2,6) -Diethylaniline), polytetramethylene oxide-di-p-aminobenzoate, N, N'-dialkyldiaminodiphenylmethane, p, p'-methylenedianiline, m-phenylenediamine, 4,4'-methylene-bis (2 -Chloroaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4'-diamino-3,3'-diethyl 5,5′-dimethyldiphenylmethane, 2,2 ′, 3,3′-tetrachlorodiaminodiphenylmethane, 4,4′-methylene-bis (3-chloro-2,6-diethylaniline), trimethylene glycol di-p The multi-layer golf ball according to claim 12, which is one selected from the group consisting of aminobenzoate and a mixture thereof.   The multilayer golf ball of claim 1, wherein the core comprises a thermosetting polymer.   The multilayer golf ball of claim 16, wherein the thermosetting material comprises polybutadiene, a cis-trans catalyst, a free radical source, a cross-linking agent and a filler.   The multilayer golf ball of claim 17, wherein the polybutadiene comprises cis polybutadiene, trans polybutadiene, vinyl polybutadiene, or a mixture thereof.   The cis-trans catalyst is an organic sulfur compound, a metal-containing organic sulfur compound, a substituted aromatic organic compound that does not contain sulfur or metal, an unsubstituted aromatic organic compound that does not contain sulfur or metal, an inorganic sulfide compound, or an aromatic organic metal. The multilayer golf ball of claim 17, wherein the golf ball is one selected from the group consisting of a compound, a Group VIA element, and a mixture thereof.   The multilayer golf ball of claim 1, wherein the cross-linking agent is one selected from the group consisting of zinc acrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate, and mixtures thereof.   The filler is precipitated hydrated silica, clay, talc, asbestos, glass fiber, aramid fiber, mica, calcium metasilicate, barium sulfate, zinc sulfide, lithopone, silicate, silicon carbide, diatomaceous earth, polyvinyl chloride, calcium carbonate , Magnesium carbonate, titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, lead, copper, boron, cobalt, beryllium, zinc, tin, steel, brass, bronze, boron carbide whisker, tungsten carbide whisker, zinc oxide, oxidation From iron, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide, graphite, carbon black, cotton flock, natural bitumen, cellulose flock, leather fiber, glass, ceramic, fly ash, and combinations thereof Multilayer golf ball of claim 17, wherein one selected from the group that.   The multilayer golf ball of claim 1, wherein the core comprises a thermoplastic polymer.   The thermoplastic material includes a polymer containing acidic groups, a suitable cation source, and a highly neutralized polymer produced by the reaction of an organic acid or its circle, wherein the suitable cation source contains the acidic group. The multilayer golf ball of claim 22, wherein the multilayer golf ball is present in an amount sufficient to neutralize 80% or more.   24. The multi-layer golf ball of claim 23, wherein the suitable cation source is present sufficient to neutralize 90% or more of the acidic groups.   24. The multi-layer golf ball of claim 23, wherein the suitable cation source is present in an amount sufficient to neutralize the acidic groups by 100%.   The highly neutralized polymers further include ionomer copolymers, ionomer terpolymers, ionomer precursors, thermoplastics, thermoplastic elastomers, grafted metallocene catalyst polymers, ungrafted metallocene catalyst polymers, single site polymers. 24. The multilayer golf ball of claim 23, comprising a highly crystalline acid polymer and its ionomer, a cationic ionomer, and mixtures thereof.   The above organic acids are aliphatic organic acids, aromatic organic acids, saturated monofunctional organic acids, saturated bifunctional organic acids, saturated polyfunctional organic acids, unsaturated monofunctional organic acids, unsaturated bifunctional organics. 24. The multi-layer golf ball of claim 23, wherein the multi-layer golf ball is one selected from the group consisting of acids, unsaturated polyfunctional organic acids, and polyunsaturated monofunctional organic acids.   The organic acid salts are barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin, or calcium, caproic acid 24. The multilayer golf ball of claim 23, comprising a fatty acid salt of, caprylic acid, capric acid, lauric acid, stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid, or dimerized derivatives thereof.

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