JP2005046613A - Golf ball with water vapor barrier layer and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid core golf ball capable of preventing deterioration of ball characteristics caused by absorbing water vapor or moisture. <P>SOLUTION: The golf ball has a core, a barrier layer for wrapping the core, and a cover for wrapping the barrier layer. The barrier layer has water vapor permeability lower than that of the cover. The barrier layer contains a thermoplastic or thermosetting composition formed by dispersing microparticles in a binder. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  This invention relates to golf balls, and more particularly to new formulations and structures for golf balls.

  The United States Golf Association ("USGA") has established five rules to maintain the consistency of golf balls. In particular, the weight of the golf ball must be less than 1.62 ounces (45.9 g) and its dimensions must be less than 1.68 inches (4.27 cm) in diameter. The initial ball velocity must not exceed 255 ft / sec (77.7 m / sec) when tested on a USGA machine at a set club head speed. The total flight distance of a ball tested at a launch angle of 10 degrees at 160 ft / sec (48.8 m / sec) with a driver specified by the USGA must not exceed 296.8 yards (271.4 m). In addition, a symmetry test managed by the USGA must be passed. Under these guidelines, one skilled in the art can change the formulation, structure and surface morphology of various parts of the ball to achieve a given combination of performance characteristics.

  Solid core golf balls are well known in the art and are made of a polybutadiene rubber material which, along with its high crosslink density, provides a source of elasticity for the golf ball. Disadvantages of solid cores such as solid cores based on peroxides and / or zinc diacrylate cross-linked polybutadiene (s) are accompanied by undesirable changes in absorption of water vapor and moisture, which The elasticity is reduced and other ball characteristics such as compression rate, initial velocity, and coefficient of restitution are degraded. For this reason, the solid core is usually covered with a cover and shielded from the ingress of moisture to keep the ball characteristics optimal. Typical cover materials include balata (polyisoprene), ionomer resins, polyurethane, polyurea, and others. Polyurethane and polyurea covers are preferred for their softness, but have poor moisture barrier properties. Therefore, a serious problem arises when a ball consisting of a polybutadiene core and a polyurethane or polyurea cover is placed under high density and high temperature for a long time.

  Several prior patents address the water vapor absorption problem. U.S. Pat. No. 5,820,488 discloses a barrier layer that has a lower water vapor transmission rate than the cover. This barrier layer is formed from polyvinylidene chloride, vermiculite, or a barrier generating material that is deposited on the core through its own reaction. U.S. Pat. No. 5,875,891 discloses an impermeable packaging that restricts the golf ball from absorbing moisture during storage. U.S. Pat. Nos. 5,885,172 and 6,132,324 provide a thin, hard, ionomer-based inner cover that blocks water vapor penetration to some extent without adversely affecting other properties of the ball Is disclosed. US Pat. No. 6,232,389 discloses a barrier layer for an air-filled or gas-filled game ball, which is produced from an aqueous solution of elastomer, a dispersed drilling layer filler, and a surfactant. U.S. Pat. No. 6,398,668 discloses an oxygen barrier layer composed of an ethylene vinyl alcohol copolymer.

  However, there is still a need for other balls with improved barrier layers, and there is still a need for improved methods of depositing such barrier layers in golf balls.

  The present invention is directed to a golf ball that includes a core, a barrier layer that encloses the core, and a cover that encloses the barrier layer, and the barrier layer has a smaller water vapor transmission rate than the cover. The barrier layer may comprise microparticles such as fibers, whiskers, metal flakes, mica particles, nanoparticles, or combinations thereof, synthetic rubber, natural rubber, polyolefins, styrene polymers, single site catalyst polymers, or combinations thereof. Produced from a thermoplastic or thermoset formulation dispersed in a containing binder. Suitable styrene polymers include styrene-butadiene copolymers, poly (styrene-co-maleic anhydride), acrylonitrile-butylene-styrene copolymers, styrene-olefin block copolymers, poly (styrene sulfonate), and combinations thereof. Particularly preferred are styrene-olefin block copolymers. Suitable metal flakes (preferably leafing) include aluminum flakes, iron oxide flakes, copper flakes, bronze flakes, and combinations thereof, with aluminum flakes containing aluminum oxide being particularly preferred. As a means for generating a water-repellent tortuous path across the barrier layer, microparticles with a particle size of about 4 microns to about 335 microns use about 50 phr to about 250 phr by weight relative to the binder. Preferably, the weight ratio of particles to binder is about 1 to about 2.

  The formulation of the barrier layer can be integrated with the cross-linking agent and becomes thermosetting. Suitable cross-linking agents include polyolefin polyols, such as hydrogenated polybutadiene polyols. This is at least about 10 parts, preferably at least about 20 parts per 100 parts by weight of the binder. The formulation may further include a catalyst, a coupling agent, or both. Coupling agents are used to bind the microparticles to a rubber binder or directly adhere to the underlying substrate (core or layer) and / or cover or layer disposed above the barrier layer. The thickness of the barrier layer is preferably less than about 0.02 inches, preferably about 0.001 to about 0.01 inches, and most preferably about 0.002 inches to about 0.007 inches.

  The barrier layer is produced from such a formulation and preferably has a water vapor transmission rate less than about 0.95 grams / mm / (square meters / day), more preferably 0.65 grams / mm / (square meters. Day), the Sward hardness is about 5 to about 20, the pencil hardness is about 5B to about F, and the specific gravity is about 1 g / cc to about 1.5 g / cc, more preferably the core Is greater than the specific gravity of at least about 0.1 g / cc. Preferred methods of coating the barrier layer include spraying or dipping, in which case the formulation is dispersed in a non-aqueous solvent system comprising an aromatic hydrocarbon, ketone, acetate, alcohol, ester or combinations thereof. . The solvent-borne dispersion preferably comprises at least about 15%, more preferably at least about 30% solid content, and the viscosity is preferably from about 300 cps to about 1500 cps.

  In a preferred embodiment, the core diameter is at least about 1.55 inches, preferably about 1.62 inches, the barrier layer thickness is less than about 0.02 inches, and the cover thickness is about 0. 0.08 inches, preferably less than about 0.03 inches. The core may be a single piece solid core comprising polybutadiene having a Mooney viscosity greater than about 35, an amount of crosslinker greater than about 15 parts per 100 parts by weight of polybutadiene, and an optional plasticizer. . The diameter of the single piece core is preferably 1.62 inches to about 1.64 inches, the compressibility is less than about 100, the amount of deflection at 100 kg is greater than about 1.5 mm, and the coefficient of restitution is about 0. Greater than 78, specific gravity less than about 1.4 g / cc, and ambient hardness is at least about 5 Shore C greater than the center hardness.

  Alternatively, the core includes a center and an outer core layer surrounding the center. The center consists of polybutadiene having a Mooney viscosity greater than about 35, a crosslinking agent in an amount of about 15 to about 40 parts per 100 parts by weight of polybutadiene, a ligrind or filler, and an optional plasticizer. The center has a diameter of about 0.5 inch to about 1.6 inch, a compression ratio of about 10 to about 100, and a deflection amount at 100 kg is larger than about 1.5 mm. The outer core layer has a material hardness greater than about 60 Shore C, a polybutadiene having a Mooney viscosity greater than about 35, an amount of cross-linking agent of about 25 to about 55 parts per 100 parts by weight of polybutadiene, and a ligrind or poly Consists of isoprene or filler and optional plasticizer.

  The cover preferably comprises a blend of thermoplastic polyurethane, thermosetting polyurethane, thermoplastic polyurea or thermosetting polyurea. The cover formulation preferably has a material hardness of about 25 Shore D to about 65 Shore D and has a flexural modulus of at least about 2000 psi. The cover preferably has about 250 to about 450 dimples on its outermost surface. The resulting golf ball preferably has a compression ratio less than about 110, a coefficient of restitution greater than about 0.79, a moment of inertia less than about 84 g · square cm, and a deflection at 100 kg Is greater than about 1.5 mm.

[Definition]

  The term “polyal” or “reactive polyal” as used herein refers to any one compound or mixture of compounds containing multiple active hydrogen components per molecule. Illustrative examples of such active hydrogen components are —OH (hydroxy group), —SH (thiol group), —COOH (carboxyl group), —NHR (amine group), where R is hydrogen, alkyl, Aryl or epoxy, all of which are primary or secondary. These active hydrogen components react with free isocyanate groups to form corresponding bonds depending on urethane, urea, thiourea or the active hydrogen component with which it reacts. The polyal may be a monomer, a homo-oligomer, a co-oligomer, a homopolymer, or a copolymer. Oligomers and polymer polyals having at least one NCO-reactive group at each end of the backbone are typically employed as soft segments in reaction products such as polyureas and polyurethanes. Depending on the terminal group, oligomers and polymer polyals are recognized as polyols (-OH ends only), polyamines (-NHR ends only) or amino alcohol oligomers or polymers (both -OH and -NHR ends). Such relatively low molecular weight (less than about 5000) and a wide range of monomer polyals are used as curing agents. Polyals are generally liquids or individuals that dissolve at relatively low temperatures.

  The term “saturated” or “substantially saturated” as used herein means that the subject compound or material is sufficiently saturated (ie, does not contain a double bond, triple bond or aromatic ring structure). Or that the degree of unsaturation is negligible, for example, the bromine number according to ASTM E234-98 is less than 10, preferably less than 5. Saturated compounds include aliphatic, cycloaliphatic and fully hydrogenated compounds.

  The term “percent NCO” or “% NCO” refers herein to the weight percent of free, reactive, unreacted isocyanate functional groups in the isocyanate functional molecules or materials. The total formula weight of all NCO groups in the molecule or material divided by its total molecular weight multiplied by 100 is equal to the percent NCO.

  The term “equivalent” is defined here as the number of moles of functional groups in a given amount of material and is calculated from the weight of the material divided by the equivalent weight. The latter refers to the molecular weight per functional group. For isocyanate, the equivalent weight is (4210 grams) /% NCO, and for polyol is (56100 grams) / OH #.

  The term “flexural modulus” or “modulus” here refers to the ratio of stress to strain within the elastic limit of the material (when measured in bending mode) and is similar to tensile modulus. This property is used to indicate the bending stiffness of the material. Flexural modulus is typically reported in pascals ("Pa") or pounds per square inch (psi) and is derived from ASTM D6267-02.

  The term “Water Vapor Transition Rate” (“WPTR”) here refers to the amount of water vapor that diffuses through a material of a given thickness under a unit area, unit time, specific temperature, and humidity. . Standard tests for WVTR include ASTM E96-00, ASTM F1249-90, ASTM F372-99, etc.

  The term “aspect ratio” is here the ratio of the lateral dimension of the platelets to the thickness. The term “effective aspect ratio” refers to the aspect ratio of flake particles dispersed in a binder such as rubber or polymer structure. The flakes are not separated as a single flake, but rather will exist in many forms, for example, tens or hundreds of bundles known as agglomerates. The aspect ratio (ie, effective aspect ratio) of the bundle or agglomerate is usually much smaller than that of a single flake and directly affects the barrier properties of the flake in the binder.

  The term “material hardness” here is the indentation hardness of a non-metallic material in the form of a slab or button, measured with a durometer. The durometer has a spring-loaded indenter, and this indenter places a pushing load on the slab and measures its hardness. Material hardness indirectly affects other material properties such as tensile modulus, resilience, plasticity, compression resistance and elasticity. Standard measurements of material hardness include ASTM D2240-02b. Unless otherwise noted, material hardness is expressed in Shore D units. Material hardness is distinguished from the hardness of the golf ball portion, which is measured directly on the golf ball surface (or other spherical mirror surface). The numerical differences are primarily based on the structure, size, thickness, and material composition underlying the portion of the golf ball component (ie, center, core and / or layer). It will be readily apparent to those skilled in the art that the material hardness and the hardness measured on the ball are neither correlated nor convertible.

  The term “compression” is also known herein as “ATTI compression” or “PGA compression” and refers to points obtained from a compression tester (Compression Tester, ATTI Engineering Company, Union city, New Jersey), and It is well known in the art as a scale for determining the relative compression of an object. Compression is a material property (ie, on-ball property) measured on the golf ball structure, not the material itself.

  The term “coefficient of restitution” or “COR” for a golf ball is used herein as the ratio of the ball's rebound speed to the initial input speed when the ball is launched from an air launcher onto a rigid vertical plate. Defined. The faster the golf ball rebounds, the higher the COR of the ball and the longer the distance achieved in play will usually be. The initial speed is from about 50 ft / s to about 200 ft / s, and unless otherwise noted is usually understood to be 125 ft / s. Golf balls have different COR for different initial velocities.

  The term “about” is to be understood herein to refer to all such numbers or all numbers in the range, as used in the context of a number, a greater number, or a range of numbers. . Since these ranges are continuous, any value between the minimum and maximum is included.

Detailed Description of the Invention

  The golf ball core of the present invention may be solid, liquid-filled or gas-filled and may have a single piece structure, a two-piece structure or a multi-piece structure. The core may comprise a center and an outer core layer. The outer core layer may be an integral solid, a wound layer, a separate layer that is molded or wound. When comprising two or more wound layers, each is chemically, physically or mechanically different from each other. The pincushion layer is formed from yarns of various sizes, including, but not limited to, natural rubber, polyether urea (DuPont Lyca.TM.), polyester urea, polyester block copolymer (DuPont). Hytel ™, polyethylene, polyamide, polyketone, poly (p-phenylene terephthalamide) (Kevlar ™ from DuPont), polyisoprene, and the like. The pincushion layer can be wound with various tensions to achieve different hardnesses. Suitable liquid materials that can be utilized for the liquid-filled core include aqueous solutions, liquids, gels, rubber-based gels, foams, hot melts, pastes, colloidal suspensions, reactive liquid systems, or combinations thereof. . Examples of liquid substances are salt in water, corn syrup, glycol, oil, clay, barite, gelatin gel, hydrogel, methylcellulose gel, styrene-butadiene-styrene rubber in paraffin or naphthalene oil, wax, silicate gel, agar gel, Peroxide cured polyester resin, epoxy resin, peroxide cured liquid polybutadiene rubber, reactive polyurethane or polyurea, silicone and polyester, SAE 10 oil, SAE 30 oil, methanol, ethanol, ammonia, glycerin, and carbonized tetrachloride is there.

  Solid cores are manufactured from suitable core materials known to those skilled in the art, including thermosetting plastics and thermoplastics such as natural rubber, polybutadiene, polyisoprene, styrene butadiene di and styrene propylene diene rubbers, ionomers. Resins, polyamides, polyesters, polyurethanes, polyureas, AtoFina Chemicals Inc. Pebax ™ from E. I. Includes Hytrel ™ from Du Pont de Nemours and Company and Kraton ™ from Shell Chemical Company. The core material can also be manufactured from a castable material. Suitable cast suitable materials include polyurethane, polyurea, epoxy, silicone, interpenetrating polymer networks, and the like. In addition, suitable core materials include reaction injection mold (RIM) polyurethane or polyurea, preferably a nucleated version, in which a gas such as nitrogen is passed into the sealed mold. Before being poured into the former, the reaction mixture is stirred to form a layer. Those skilled in the art will appreciate that other elastomers can be employed as the core material without departing from the scope and spirit of the invention.

  A preferred formulation for the solid core includes a base rubber, a crosslinker, and a free radical initiator. The base rubber is typically natural or synthetic rubber. A preferred base rubber is about 40% to about 100% cis-1,4 content polybutadiene, has a Mooney viscosity of at least about 35, a molecular weight of at least about 150,000, and even less than about 4 Of polydispersity. Examples of preferred polybutadiene rubbers include BUNA ™ CB22 and CB23 from Bayer, Ubepol ™ 360L and 150L from Ube Industries, and Cariflex ™ BCP820 and BCP824 from Shel Chemical. A blend of two or more such polybutadienes is preferred for the solid core. In one embodiment, a Mooney viscosity cobalt or nickel catalyzed polybutadiene of about 50 to about 150 is mixed with a Mooney viscosity neodymium catalyzed polybutadiene of about 30 to about 100. The weight ratio of the two polybutadienes can range from about 5:95 to about 95: 5. The polybutadiene may also be mixed with other elastomers known in the art as natural rubber, polyisoprene rubber, and / or styrene-butadiene rubber to modify the properties of the core.

  Suitable crosslinking agents for polybutadiene based solid cores include metal salts of unsaturated fatty acids having from 3 to 8 carbon atoms, such as monoacrylates, diacrylates, monomethacrylates, and dimethacrylates. The metal can be magnesium, calcium, zinc, aluminum, sodium, lithium, or nickel. Preferred crosslinkers include zinc diacrylate, zinc dimethacrylate and blends thereof. Zinc diacrylate is preferable in terms of increasing the initial velocity of the golf ball, but the present invention is not limited to this. The crosslinker is preferably present in an amount of at least about 15 parts, more preferably from about 15 phr to about 40 phr, relative to 100 parts by weight of the base polymer (“phr”). In the manufacturing process, it is beneficial to pre-blend some crosslinking agent to the base rubber in a masterbatch before adding other components.

  A free radical initiator is used to promote the crosslinking action between the base rubber and the crosslinking agent. Preferred free radical initiators include thermal initiators such as peroxide initiators and UV, visible, infrared, microwave, electron beam, X-ray and γ-ray radiation. And an optical initiator that is responsive to such an energy source. Peroxide initiators are well known in the art and may be any known peroxide and blends thereof that are heated to decompose during the cure cycle. Suitable peroxide initiators include organic peroxide compounds such as dicumyl peroxide, di-t-butyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, α, α- Bis (t-butylperoxy) diisopropyl benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane, and the like, and blends thereof are included. Commercially available examples include, but are not limited to, Varox (TM) 231XL and DCP-R from AtoFina, Perkadox (TM) BC and 14 from Akzo Nobel, Elastochem (TM) DCP from Rhein Chemie -70 is included. In these pure forms, the initiator is present in an amount of at least about 0.25 pph relative to the base polymer, preferably between about 0.5 pph and about 2.5 pph. One skilled in the art will readily understand that the amount is adjusted depending on the activity and concentration of the initiator.

  In the polybutadiene-based solid core of the present invention, it is preferable to improve the softness and resilience of the core by mixing a plasticizer, specifically, a halogenated organic sulfur compound such as a halogenated thiophenol or a metal salt thereof. . Halogenated thiophenol, preferably pentachlorothiophenol (PCTP) or ZnPCTP, partially functions as a cis-trans catalyst to convert polybutadiene cis-1,4 bonds to trans-1,4 bonds. The production of soft and fast cores using halogenated organosulfur compounds such as PCTP and ZnPCTP in golf balls is disclosed in US patent application 09 / 951,963, the entire contents of which are hereby incorporated herein by reference. include. PCTP is available from Struktol Company, USA under Struktol ™, and ZnPCTP is available from eChinaChem. The halogenated organosulfur compound is present in an amount of at least about 0.1 pph relative to the base rubber, more preferably in an amount between about 0.1 pph and about 2 pph. Alternatively, the utilization of the halogenated thiophenol compound is at least about 2 pph, preferably between about 2.3 pph and about 5 pph.

  The solid core may also include a filler to adjust the hardness, strength, modulus, weight, density and / or specific gravity of the core. Preferred fillers include metal or alloy powders, metal oxides and salts, ceramics, particulates, carbonaceous materials, polymeric materials, glass microspheres and blends thereof. These fillers may be monolithic or perforated, filled, unfilled, surface treated, or non-surface treated. Specific fillers for the core include tungsten powder, tungsten carbide, zinc oxide, tin oxide, tungsten oxide, barium sulfate, zinc sulfate, barium carbonate, calcium carbonate, zinc carbonate, silica and clay arrays, regrind (typical Includes a recycled core material ground to about 30 mesh particles) and high Mooney viscosity rubber liglind. Certain fillers, such as zinc oxide, are also added as coagents for the crosslinking reaction of other core components.

  Other additional additives for golf balls are well known in the art and are mixed into the core to achieve their special purpose and desired effect. Such additives include antioxidants that prevent premature crosslinking or optional molecular breakage of rubber compounds, accelerators that accelerate the polymerization reaction, processing-promoting oils that affect fluid or mixing properties, such as zinc stearate. Activators, blowing agents, cis-trans catalysts, adhesives, coupling agents, lubricants, free radical stabilizers, radical scavengers, scorch (early vulcanization) inhibitors, and blends thereof are included.

  The diameter of the single piece core of the present invention is preferably less than about 1.64 inches, its specific gravity is less than about 1.4 g / cc, the compressibility is less than about 100, and the amount of deflection at 100 kg is Greater than about 1.5 mm, the coefficient of restitution (COR) is at least about 0.78, and the hardness decreases from the periphery toward the center. More preferably, the hardness around the core is at least about 5 Shore C greater than the hardness of the center. Two-piece (dual) cores or multi-cores have different compositions and properties in the center and at least one outer core layer. The center is between about 15 phr and about 40 phr at the ZDA level, contains at least ligrind or filler, and optionally blends a plasticizer such as ZnPCTP. The center diameter is preferably from about 0.5 inch to about 1.6 inch, its compressibility is from about 10 to about 100, and its deflection at 100 Kg is greater than about 1.5 mm. The ZDA amount of the outer core layer is between about 25 phr and about 55 phr, and the outer core layer contains at least one of ligrind, balata or filler and optionally blends a plasticizer. The material hardness of the outer core layer is at least about 60 Shore C. The core comprising the center and outer core layers has a diameter of less than about 1.64 inches, a compressibility of less than about 100, a deflection at 100 Kg of greater than about 1.5 mm, and a COR of at least about 0.00. 78. In one embodiment, the core diameter is greater than about 1.62 inches. Solid cores can be made from the base formulations disclosed herein using conventional process and techniques such as compression molding.

  In order to prevent or minimize moisture, typically water vapor, from entering the core, a barrier layer is disposed between the core and the cover, preferably directly around the core. The barrier layer has an MVTR that is smaller than the MVTR of the cover, and the value is preferably less than about 0.95 grams · mm / (square m · day). The barrier layer of the present invention includes a thin and soft rubber layer, and optionally includes microparticles dispersed in the rubber material. These particles are preferably hydrophobic and form a tortuous (random and non-linear) path across the barrier layer to reduce its MVTR. The microparticles of the present invention refer to particles of a size on the order of hundreds of microns or smaller, including nanoparticles of a size from a few nanometers to a size smaller than about 1 micron. Suitable microparticles may or may not be colored, fibers, whiskers, and flake metals (which may or may not be leafing) such as aluminum flakes, iron oxide flakes, copper flakes, bronze flakes, etc., or Includes combinations of two or more thereof. Leafing metal flakes are suitable for use in this invention. Preferred metal flakes are aluminum flakes, more preferably aluminum oxide flakes. Preferably, microparticles having a size of about 4 microns to about 335 microns, more preferably a size of about 5 to about 50 microns, and most preferably a size of about 8 microns to about 32 microns are used, and the flake aspect ratio is at least about 25, at most about 30,000, preferably about 100 to about 20,000, more preferably about 100 to about 10,000. The amount of microparticles included in the barrier layer is at least about 10 parts, preferably from about 50 phr to about 250 phr, more preferably from about 70 phr and about 125 phr, per 100 parts by weight rubber material (“phr”). Between. The barrier layer may include a single layer or a plurality of sublayers.

  Suitable rubber materials for the barrier layer include, but are not limited to, synthetic or natural rubber such as polyolefins, styrene polymers, single site catalyst polymers, acrylic resins, and the like. Polyolefins and copolymers or blends thereof include balata, polyethylene, polyethylene chloride, polypropylene, polybutylene, butyl based rubber, isoprene rubber, trans polyisoprene, neoprene, ethylene-propylene rubber, ethylene-butylene rubber, and ethylene-propylene rubber. (Unconjugated diene) terpolymers are included. Styrene polymers include polystyrene and copolymers thereof, such as styrene-butadiene copolymers, poly (styrene-co-maleic anhydride), acrylonitrile-butylene-styrene copolymers, styrene-olefin block copolymers (eg, Kraton ™ from Shell Chemical). And poly (styrene sulfonate). Styrene-olefin block copolymers are disclosed in U.S. Pat. Nos. 4,501,842 and 6,190,816. The entire disclosure of these patents is hereby incorporated herein by reference. Single site catalyst polymers include homopolymers and copolymers such as implantable or non-implantable metallocene-catalyzed polyolefins. A compatible additive may be added to the blend. The compatible additive material is often a block copolymer, where each block has an affinity for only one of the blend components to be compatible. The compatible additive is believed to relate between the phase separated regions in the polymer blend across the boundary. This is used to bond multiple regions together to improve the structural integrity and mechanical properties of the compatibilized material. Optionally, these thermoplastic rubbers or blends thereof are mixed with a crosslinking agent to produce a thermoset rubber material. Suitable cross-linking agents include the polymeric polyals disclosed herein, in particular polyolefin polyols such as hydrogenated polybutadiene polyols (eg, Plytail ™ H and Plytail ™ available from Mitsubishi Kasei, Tokyo, Japan). HA, Kraton ™ L-2203, available from Kraton Polymer, Houston, TX). The amount of crosslinking agent is at least about 10 parts, more preferably at least about 20 phr, per 100 parts by weight of the rubber material. Other additives in the barrier layer include, but are not limited to, catalysts such as tertiary amines, and coupling agents such as silane, thereby binding the filler into the polymer structure. The coupling agent also serves to adhere the barrier layer to a substrate, such as a golf ball core or outer core layer, or to a layer such as a cover or intermediate layer that is produced by direct contact of the barrier layer.

  Due to the presence of microparticles such as aluminum flakes, the specific gravity of the barrier layer can be made larger than the specific gravity of the core, and as a result, the moment of inertia of the golf ball can be increased. The particle / binder weight ratio (“P / B”) of the barrier layer is from about 0.5 to about 2.5, preferably from about 1 to about 2. The specific gravity of the barrier layer is preferably from about 1 g / cc to about 1.5 g / cc, more preferably from about 1.2 g / cc to about 1.35 g / cc. The specific gravity difference between the barrier layer and the core can be greater than about 0.1 g / cc. The diameter of the core can be about 1.5 inches or greater, preferably greater than about 1.55 inches, and more preferably from about 1.62 inches to about 1.65 inches. The thickness of the barrier layer can be less than about 0.2 inches, but is preferably less than about 0.02 inches, more preferably from about 0.001 inches to about 0.01 inches, and most preferably about 0. 0.002 inches to about 0.007 inches. The barrier layer preferably has a sword hardness of between about 5 and about 20. The pencil hardness of the barrier layer is preferably between about 5B and about F.

  The barrier layer of the present invention is preferably disposed around or embedded within any portion where it is desired to reduce MVTR. Such portions include, but are not limited to, the core, the center within the core, the outer core layer of the core, the pincushion layer, the intermediate layer between the core and the cover, and the inner cover layer of the cover. Two or more barrier layers of the same or different composition may be used in the golf ball. This is the case when there are moisture absorption problems in two or more parts. Beneficially, each barrier layer protects a predetermined portion of the golf ball so that even if water vapor passes through the outer barrier layer, the inner barrier layer protects the inner layer. The barrier layer is disposed adjacent to the golf ball portion and covers the outer surface of the portion and substantially encapsulates the portion. Optionally, the barrier layer may be secured to the part using an adhesive or a coupling agent. Alternatively, the reaction itself creates a direct chemical bond between the barrier layer and its part. The barrier layer is preferably adjacent to the underlying golf ball portion, more preferably continuous. When the liquid core is employed, the water vapor barrier layer also serves to prevent water vapor from exiting from the liquid core to the outside air.

  The barrier layer can be manufactured in a number of ways. For example, the barrier layer formulation is preformed into a semi-cured shell. Specifically, the amount of the barrier layer is placed in a compression molding machine and molded with sufficient pressure, temperature, and time to produce a semi-cured, semi-rigid shell half. The shell halves are placed around the core or subassembly and the desired size is obtained by a second compression molding. In the shrink wrap method, a thin sheet stock of a barrier material is strongly pressed by vacuum suction to the molding cavity walls of the upper and lower platens of the compression molding press. The core or subassembly is inserted into the molding cavity in an arrangement between the sheet stock. The press closes the compression molder and cures the barrier layer. In an injection molding process, a mixed stock of barrier material is fed to an injection molding barrel and screw and injected through a nozzle into a molding cavity, surrounding a core or subassembly. Heat and pressure are applied to the molder to cure the barrier layer.

  A more preferred method of producing the barrier layer of this invention is spraying, in which a solid formulation of the barrier layer is dispersed in a non-aqueous solvent system, and this dispersion is sprayed onto a golf ball precursor, such as a core, Then, it is dried. Suitable solvents for dispersing the binder rubber and particles include, but are not limited to, aromatic hydrocarbons such as xylene (CAS # 1330-20-7) and toluene (CAS # 108-88-3); ketones such as Methyl ethyl ketone (MEK, CAS # 110-43-0), methyl isobutyl (MIBK, CAS # 108-10-1), methyl n-amyl ketone (MAK, CAS # 110-43-0) and diisobutyl ketone (DIBK, CAS #) 108-83-8); acetates such as n-butyl acetate (CAS # 123-86-4) and ethyl acetate (CAS # 141-78-6); alcohols such as n-amyl alcohol (CAS # 71-41). 0); ester; or a mixture thereof. To facilitate processing, the rubber material is first dispersed in a solvent to produce a relatively high viscosity (about 20000 cps to about 50000 cps) and relatively high solids (at least about 30%) intermediate product. Generate. The rubber intermediate is then dispersed with the particles in more solvent to produce a sprayable dispersion. This preferably has a viscosity of about 300 cps to about 1500 cps, more preferably a viscosity of about 500 cps to about 1000 cps, and most preferably a viscosity of about 700 cps to about 900 cps. The solvent-borne sprayable dispersion has a solids content of at least about 10%, more preferably at least about 15%, and most preferably from about 15% to about 40% solids.

  A golf ball coater system well known to those skilled in the art is typically utilized to set up a machine that produces a barrier layer by spraying. The coater line plays the role of rotating the core and delivers the core to the coating station. At the court station, a top spray gun and a bottom spray gun are set up to spray the upper and lower hemispheres of the core, respectively. Both spray guns are stationary and are positioned approximately 45 ° from the core equator. The sprayable dispersion is guided into a compression pot, which supplies the dispersion to the spray gun. Sequentially, the coater line is activated to move and rotate the core, and the spray gun starts spraying the dispersion on the core. The parameter ranges for each part of the coater system are detailed in the following example.

  Those skilled in the art will appreciate adjusting the various parts and parameters of the coater system to achieve the desired result. They are further aware of other suitable manufacturing techniques for depositing the dispersions of this invention, including dipping, vacuum deposition, reactive injection molding, and others. After depositing the dispersion, the resulting barrier layer is in a semi-cured dry state at ambient temperature within about 5 to about 10 minutes. Preferably, the core with the barrier layer is dried, eg, in a convection oven at a temperature of about 180 ° F. (about 82 ° C.) to about 250 ° F. (about 121 ° C.) Allow to dry for a period of about 10 minutes to about 60 minutes. The dry weight of the aria layer depends on the solid formulation of the dispersion and the size of the underlying core. Preferably, the dry weight of the barrier layer is at least about 0.3 grams per golf ball. After drying, before the cover is applied, an optional surface treatment such as plasma, corona, silane immersion, or a combination thereof is performed on the barrier layer.

  The golf ball cover of the present invention is preferably strong, has high cutting resistance, and is selected from ordinary materials used as golf balls according to desired performance. The cover may include one or more layers, for example, an outer core layer and one or more inner cover layers. The inner cover layer may be a pincushion layer or a hoop stress layer. Suitable cover materials include: non-ionomer acid copolymers such as E.I. I. An ethylene (female) acrylic acid copolymer and terpolymer having an acid content of about 2% to about 50%, available as Nucrel ™ from Du Pont de Nemours and Company and available as Escar ™ from ExxonMobile; Anionic and cationic ionomers such as E. I. Available from the Du Pont de Nemours and Company as Surlyn (TM) and from ExxonMobile as Iotek (TM), partially or completely by about 1% to about 100% or more depending on the organic or inorganic cation Hydrated acid copolymers; thermoplastic or thermosetting (sulfurized) synthetic or natural golf such as polyolefins and copolymers or blends thereof, polystyrene and copolymers thereof, and polymers produced by single site catalysts such as metallocene; thermoplastic or Thermosetting polyurethanes; thermoplastic or thermosetting polyureas; aliphatic or aromatic thermoplastics such as polyesters (EI Du Pont de Nemours and Company) Hytel ™ and Lomod ™ from General Electric Company, polycarbonate, polyacetal; polyimide, polyetherketone, polyamideimide, block copolymer (Kraton ™ from Shell Chemical, and co-polyetheramide) (Pebax ™ from AtoFina); vinyl resins such as polyvinyl alcohol copolymers and PVDC; polyamides such as poly (hexamethylene adipamide) and others prepared from diamines, fatty acids, dibasic acids and amino acids; acrylic resins Synthetic or natural sulfurized rubbers such as balata; and blends and alloys such as polycarbonate and acrylonitrile-butylene-styrene blends , Blends of polycarbonate and polyurethane, and blends of polyvinyl chloride with acrylonitrile-butylene-styrene or ethylene vinyl acetate.

  Preferably, the golf ball cover includes a polyurethane or polyurea formulation comprising a reaction product generated from polyal, isocyanate and optionally a curing agent. The polyal is preferably integrated into one or more soft segments of the reaction product and is substantially absent from the hard segments. Suitable polyals such as polyols and polyamides are organic, modified organic, saturated, aliphatic, alicyclic, unsaturated, aralipatic, aromatic, substituted, unsubstituted, or ionomer, Those having 2 and more reactive hydrogen groups per molecule, such as primary or secondary hydrogen groups or amine groups. The isocyanate-reactive hydroxy and / or amine groups may be end groups or side groups of the main chain of the oligomer or polymer, and in the case of secondary amine groups, they may be embedded in the main chain.

  Any isocyanate available to those skilled in the art can be suitably used in this invention. Isocyanates are organic, modified organic, saturated, aliphatic, cycloaliphatic, unsaturated, aralipatic, aromatic, substituted, unsubstituted diisocyanate or polyisocyanate monomers that are free of two or more It may be a reactive isocyanate (“NCO”) group; its isomer; its modified derivative; its duplex; its triple; or its isocyanurate. Isocyanates are also optional isocyanate-terminated multimeric additives, oligomers, polymers, prepolymers, low-free monomer prepolymers, quasi-prepolymers, and modified polyisocyanates derived from the aforementioned isocyanates and polyisocyanates. Good. Low free monomer prepolymer refers to a prepolymer having a level of free isocyanate monomer of less than 0.5 weight percent. Curing agents are monomeric, oligomeric or polymeric compounds used for chain extension and / or crosslinking in the cover formulation. Curing agents suitable for this invention include polyals and epoxies, and preferably include hydroxy curing agents, amine curing agents, and amino alcohol curing agents having a molecular weight of about 50 to about 5000.

  In order to achieve the best light stability, the reactants and curing agents, such as polyar (s), isocyanate (s), etc., contained in the polyurethane or polyurea formulation are substantially saturated. Blocked secondary diamines with a high level of blockade of stearic acid, such as ClearLink ™ 1000 (4,4′-bis (sec-butylamino) -dicyclohexylmethane) from Dorf Chemical Chemical LLC It can be used beneficially.

  Various additives may optionally be included in the cover layer formulation of the present invention in sufficient amounts to achieve individual purposes and effects. For example, a catalyst such as dibutyltin dilaurate (Dabco ™ T-12) is added in an amount from about 0.001% to about 5% by weight of the total formulation to react between the curing agent and the prepolymer. Can be promoted. A UV absorber, a light stabilizer (preferably a blocked amine light stabilizer) and an antioxidant are used to prevent yellowing of the cover and surface cracks due to optical deterioration. Other additives include, but are not limited to, reaction accelerators, fillers, viscosity building materials, mold release agents, plasticizers, compatibilizers, coupling agents, dispersants, colorants including pigments and dyes, optical Bleaching agents, surfactants, lubricants, stabilizers, metals, processing aids or oils, foaming agents, freezing point hardeners, and any other modifiers known to those skilled in the art are included. Dispersants may be cationic, anionic, non-ionic, and include those known as other leveling agents, emulsifiers, antifoaming agents, wetting agents, surfactants, and the like. The pigments may be fluorescent, autofluorescent, luminescent, or chemiluminescent, and include white pigments such as titanium oxide and zinc oxide. Properties such as density, specific gravity, flexural modulus, elongation modulus, strength, moment of inertia, hardness, wear resistance, climate resistance, volume, weight, etc. are adjusted using the filler. The filler is preferably in the form of nanoscale or microscale powders, fibers, filaments, flakes, whiskers, wires, tubes, or particles in order to achieve uniform dispersion.

  The flexural modulus of the cover layer is preferably at least about 2000 psi, its material hardness is between about 25 Shore D and about 65 Shore D, and the hardness measured on the ball surface is less than about 80 Shore D. In one embodiment, the cover layer has a Shore D hardness of about 30 to about 60 and a flexural modulus of about 10,000 psi to about 80000 psi. A thin cover layer with a thickness of about 0.01 inches to about 0.04 inches is preferred by athletes with high swing speeds, but a thickness of greater than 0.04 inches to about 0.08 inches, more preferably A relatively thick cover layer with a thickness of about 0.05 inches to about 0.07 inches is preferred by moderate swing speed athletes. The golf ball of the present invention has a large PBD core with great energy to provide distance from the tee, with greater spin, feel and improved play characteristics on the green side, which is beneficial to the latter player This is due to the relatively thick thermosetting polyurethane or polyurea cover, and solves the water absorption problem normally unavoidable with a PBD core golf ball with a normal urethane cover. In the preferred embodiment, the cover thickness is less than about 0.03 inches.

  Any method known to those skilled in the art can be used to produce the cover layer of this invention. The one-shot method is a method in which an isocyanate, a polyether polyether and a curing agent are mixed at the same time, and is practical, but the resulting mixture is non-uniform and difficult to control. The prepolymer method described above is most preferred because it results in a more uniform mixture, resulting in a more consistent polymer blend. The prepolymer can react with a diol or secondary diamine to produce a thermoplastic material, and can react with a triol, tetraol, primary diamine, triamine, tetramine to produce a thermosetting material. Other suitable methods for producing the layers include reaction injection molding (“RIM”), liquid injection molding (“LIM”), injection compression molding, pre-reacting the components to produce an injection moldable thermoplastic polyurethane. Next, a method of injection molding and combinations thereof are included. For example, RIM / compression molding, injection / compression molding, progressive compression molding, and the like. The thermoplastic blend can be cast, injection moldable, sprayable, or applied in a laminated form, or applied by other known techniques. Castable reactive liquid materials such as polyurea, polyurethane, and polyurethane / polyurea composites can provide very thin layers such as outer cover layers, which are required for golf balls. Other techniques include spraying, dipping, spin coating, or flow coating methods.

  Optionally an intermediate layer can be placed between the core and the cover, preferably between the core and the barrier layer. The intermediate layer can be part of the core as the outer core layer and can also be part of the cover as the inner cover layer. The intermediate layer of the golf ball comprises a non-ionomer acid polymer or its ionomer derivatives, polyamides, polyolefins, polyurethanes, polyureas, epoxies, polyethers, polyesters, polyether esters, such as Hytel ™ from DiPont, polyether amides For example, Pebax ™ from AtoFina, nylon, metallocene catalyst polymer, styrene block copolymer, eg Kraton ™ from Shell Chemical, acrylonitrile-butadiene-styrene copolymer (“ABS”), polyvinyl chloride, polyvinyl alcohol copolymer, Polycarbonate, polyesteramide, polyamide, polyimide, polyetherketone, polyamideimide, silicone, fat Metal salts, and combinations thereof. For example, polycarbonate and acrylonitrile-butadiene-styrene blends, polycarbonate and polyurethane blends. Two or more of these materials may be blended together to produce an intermediate layer.

  The intermediate layer can be filled with a filler for enhancing the elastic modulus or a filler for modifying the specific gravity to achieve preferable physical and mechanical properties. The modulus of the interlayer formulation can be from about 1000 psi to about 150,000 psi, the material hardness can be from about 20 Shore C to about 80 Shore D, and the thickness can be from about 0.005 inches to about 0.6 inches. It may be. The interlayer formulation may be applied as a liquid, powder, dispersion, lacquer, paste, gel, melt, or solid shell half. The intermediate layer may be generated around the core or inside the cover, the generation being sheet stock or vacuum shrink wrap, compression molding, injection molding, vacuum deposition, RIM, lamination, casting, spraying, dipping, powder By coat or any other means of deposition. Preferably, these methods are used in combination. For example, injection / compression molding, RIM / compression molding, preform / compression molding, injection molding / polishing, injection / progressive compression molding, co-injection molding, or simplified casting of a single block material.

  The resulting golf ball includes a core, a barrier layer, an optional intermediate layer, and a cover, as described above, preferably having a COR greater than about 0.79, a compressibility less than about 110, and a moment of inertia. Is less than about 84 g · square cm, and the amount of deflection at 100 kg is greater than about 1.5 mm. The overall diameter of the golf ball is preferably at least about 1.68 inches, more preferably from about 1.68 inches to 1.76 inches. In a preferred embodiment, a polyurethane or polyurea cover is placed directly around the barrier layer and they are continuous with one another. Due to its function, the coupling agent used in the barrier layer forms a direct bond with the components of the cover, thus improving the adhesion between the two layers. At least 60% of the outermost surface of the golf ball is covered by about 250 to about 450 dimples of the same or different size and shape. A preferred dimple pattern is a catenary curve, and preferred lift and drag characteristics of the golf ball of the present invention are disclosed in pending US patent application Ser. Nos. 09 / 989,191 and 10 / 096,852, respectively. I will take the contents here.

（１）Ｅ３０Ｂはある種のアルミニウムベースのリーフィングフレークであり、平均粒子サイズは約１３ミクロンであり、オハイオ州ペインスビルのＥＣＫＡＲＴ Ａｍｅｒｉｃａから入手できる。
（２）ＦＢ１９０１Ｘはテキサス州ヒューストンのＳｈｅｌｌ ＣｈｅｍｉｃａｌからのＫｒａｔｏｎ（商標）ゴムである。
（３）Ｐｏｌｙｔａｉｌ（商標）Ｈは、日本国、東京のＭｉｔｓｕｂｉｓｈｉ Ｋａｓｅｉからの架橋剤である。
（４）この配合物はさらに２．５部の第３アミン触媒（ルイジアナ州バトンルージュのＡｌｂｅｍａｒｌｅからのＡｒｍｅｅｎ（商標）ＤＭ１２Ｄ）および０．７部のカップリング剤（ウェストバージニア州サウスチャールストンのＣｒｏｍｐｔｏｎ Ｃｏｒｐｏｒａｔｉｏｎ−ＯＳｉ ＳｐｅｃｉａｌｉｔｉｅｓからのＳｉｌｑｕｅｓｔ（商標）Ａ−１１００）を含む。 The barrier layer of this invention and its application to a golf ball will be further described in the following non-limiting examples. Examples of barrier layer formulations are available from PPG Industries, Pittsburgh, Pennsylvania and are shown in Table 1 below.

(1) E30B is a type of aluminum-based leafing flake with an average particle size of about 13 microns and is available from ECKART America, Painsville, Ohio.
(2) FB1901X is Kraton ™ rubber from Shell Chemical, Houston, Texas.
(3) Polytail ™ H is a cross-linking agent from Mitsubishi Kasei, Tokyo, Japan.
(4) This formulation further contained 2.5 parts tertiary amine catalyst (Armeen ™ DM12D from Albemarle, Baton Rouge, LA) and 0.7 parts coupling agent (Crompton Corporation, South Charleston, WV). -Silquest ™ A-1100 from OSi Specialties).

  To produce Formulation 02-005-108A, an intermediate was first formed with 1 gallon of Kraton ™ FG1901X at about 33% solids in a solvent blended with 75% toluene and 25% MIBK. To facilitate the processing. Using a Cowles stirrer, 900 grams of Kraton ™ FG1901X resin (bead form) was slowly mixed into a solvent blend of 1350 grams of toluene and 450 grams of MIBK in a 1 gallon container, followed by high speed stirring. To dissolve. As the flammable solvent blend becomes hot due to the shearing action of the Cowles blade, as a precautionary measure, for example, by a water jacket or air cooling, to lower the solvent temperature below about 140 ° F. (about 60 ° C.) Control. The viscosity of the Kraton ™ intermediate was about 28000 cps to about 35000 cps at about 24 ° C. Also, 615.2 grams of Eckart ™ E30B leafing aluminum pigment with a solids content of about 65% contained 400 grams of leafing flakes, which was converted to 640 grams of Aromatic 100 (CAS # 64742) using a Cowles stirrer. -95-6) and 100 grams of MIBK solvent blend was slowly and thoroughly mixed in another container of 1 gallon. Mixing was typically carried out with agitation in the middle of 15 minutes until no agglomerates or agglomerated flakes were visible through the container sidewall. Thereafter, 1200 grams of Kraton ™ intermediate was slowly mixed in with intermediate stirring for the next 15 minutes. As a result, P / B of the compound 02-005-108A was 1.0.

配合物０２−００５−８１Ａを生成するために、４００グラムのビーズ状のＫｒａｔｏｎ（商標）１９０１Ｘを２０００グラムのトルエンに高速なＣｏｗｌｅｓの攪拌の下で１ガロンのコンテナ中で混入・溶解して、まず、固体量が約１６．７％のＫｒａｔｏｎ（商標）ＦＧ１９０１Ｘの中間物を生成した。また、Ｐｏｌｙｔａｉｌ（商標）Ｈの固形量約１０．８％の中間物が、３００グラムのＰｏｌｙｔａｉｌ（商標）Ｈを５リットルのフラスコ中で２４７６．５グラムのトルエンに攪拌させながら溶解させて、生成された。フラスコは９５°Ｆ（約３５°Ｃ）に加熱され、その後１３０°Ｆ（約５４°Ｃ）に加熱され３時間経過した。Ｐｏｌｙｔａｉｌ（商標）Ｈを室内温度まで冷却する前に、１３０°Ｆ（約５４°Ｃ）でさらに２時間攪拌し、冷却後、５ミクロンバッグで濾過されて１ガロンコンテナに入れられた。その後、４６１．４グラムのＥｓｋａｒｔ（商標）Ｅ３０Ｂのリーフィングアルミニウム顔料を、特別の１ガロンコンテナ中で、６６３グラムのＫｒａｔｏｎ（商標）の中間物および２７７．７グラムのＰｏｌｙｔａｉｌ（商標）の中間物を混入した。中間的なＣｏｗｌｅｓの攪拌を約３０分行い、リーフィングアルミニウムアグロメレート（集塊）を溶媒樹脂ブレンド中に十分に分散させた。この後、３．７５グラムのＡｒｍｅｅｎ（商標）ＤＭ１２Ｄおよび１．０５グラムのＳｉｌｑｕｅｓｔ（商標）Ａ−１１００をゆっくりと添加した。約３０秒で、粘度が著しく上昇した。最後に、１３５０グラムのトルエンを加えて０２−００５−８１Ａの配合物を生成した。そのＰ／Ｂは約２であり、固形量は約１６％であった。 To form a barrier layer on the core, a gallon sized container containing formulation 2-005-108A is first placed on the paint shaker for about 7 minutes to ensure a sprayable dispersion is uniform. Place in sealed pressure pot. Preferably, the pressure pot has a stirring function so as to maintain the uniformity of dispersion. Viscosity measurements for the 2-005-108A formulation were from about 600 cps to about 850 cps. This dispersion did not need to be further diluted prior to deposition and was used at ambient temperature. The specific spray gun used was an air operated spray gun, Brinks ™ Model 95AR, available from ITW Industries Finishing, Glendale Heights, Ill., A spray nozzle 68PB, a fluid nozzle 68SS (2.8 mm orifice diameter) and a needle stem. Combined with 768. Alternatively, the same spray gun can be used in combination with spray nozzle 67PB, fluid nozzle 67SS (2.2 mm orifice diameter) and needle stem 767. The various parameters of the pressure pot, coater line, top spray gun, and bottom spray gun used to prepare Group 1-3 golf ball precursors are shown in Table II below.

To produce formulation 02-005-81A, 400 grams of beaded Kraton ™ 1901X was mixed and dissolved in 2000 grams of toluene in a 1 gallon container under high speed Cowles stirring. First, an intermediate of Kraton ™ FG1901X with a solids content of about 16.7% was produced. Also, an intermediate of about 10.8% solids of Polytail ™ H was formed by dissolving 300 grams of Polytail ™ H in 2476.5 grams of toluene in a 5 liter flask with stirring. It was done. The flask was heated to 95 ° F. (about 35 ° C.) and then heated to 130 ° F. (about 54 ° C.) for 3 hours. Prior to cooling Polytail ™ H to room temperature, it was stirred at 130 ° F. (about 54 ° C.) for an additional 2 hours, after cooling, filtered through a 5 micron bag into a 1 gallon container. Then 461.4 grams of Eskart ™ E30B leafing aluminum pigment, in a special 1 gallon container, 663 grams of Kraton ™ intermediate and 277.7 grams of Polytail ™ intermediate. It was mixed. Intermediate Cowles stirring was performed for about 30 minutes to fully disperse the leafing aluminum agglomerates (agglomerates) in the solvent resin blend. Following this, 3.75 grams of Armeen ™ DM12D and 1.05 grams of Silquest ™ A-1100 were added slowly. In about 30 seconds, the viscosity increased significantly. Finally, 1350 grams of toluene was added to produce a formulation of 02-005-81A. The P / B was about 2 and the solid content was about 16%.

１具体例において、２ピースゴルフボールは、コア、カバー、これらコアおよびカバーの間に配されたこの発明のバリア層を含む。コアは、ムーニー粘度が約３５より大きいポリブタジエン、開始剤、および約１５ｐｈｒまたはそれ以上のレベルのＺＤＡから製造される。オプションとして、コアはＺｎＰＣＴＰを含む。コアの直径は約１．６４インチ未満であり、その比重は約１．４ｇ／ｃｃ未満であり、圧縮率は約１００未満であり、１００Ｋｇ時の撓み量は約１．５ｍｍより大きく、ＣＯＲは約０．７８より大きい。コアの外側は内側より硬く、周囲の硬度はセンタの硬度より少なくとも約５ショアＤ大きい。バリア層は、Ｐ／Ｂが約１から約２でバインダ中に分散させた粒子から製造される。好ましくは、粒子は、アルミニウムの、より好ましくは酸化アルミニウムの、リーフィングフレークであり、バインダはＳｈｅｌｌ ＣｈｅｍｉｃａｌからのＫｒａｔｏｎ（商標）のようなスチレンゴムを含む。バリア層の厚さは約０．０２インチより薄く、そのＭＶＴＲはＤｕＰｏｎｔによるＳｕｒｌｙｎ（商標）より小さい。カバーは熱可塑性または熱硬化性ポリウレタンまたはポリ尿素から製造され、その材料硬度は約２５ショアＤから約６５ショアＤであり、曲げ弾性率は約２０００ｐｓｉより大きい。好ましくは、カバーは、バリア層に入れられたカップリング剤によりバリア層に直接に接着する。生成されたゴルフボールは約２５０個から約４５０個のディンプルに覆われ、その圧縮率は約１１０より小さく、１００Ｋｇ時の撓み量は約１．５ｍｍより大きく、慣性モーメントは約８４ｇ・平方ｃｍより小さく、反発係数（ＣＯＲ）は約０．７９より大きい。 To test the deposition of the barrier layer, five groups of golf ball precursors were produced. The core group contained 12 polybutadiene-based cores with a diameter of about 1.55 inches. Each of Groups 1, 2, and 3 are about 0.0035 inches, about 0.0045 inches, and about 0.0069 inches in thickness, respectively, and are encapsulated with a barrier layer made of the formulation 02-005-81A. And 12 precursors with a core as a core group. The control group included 12 precursors with the core as a core group encapsulated in a mantle layer of Surlyn ™ ionomer about 0.035 inches thick. The 02-005-81A formulation achieved an MVTR of less than about 0.65 grams · mm / (square m · day). Three consecutive cycles of all five groups in a humidity box at about 100% humidity, about 100 ° F. (about 38 ° C.) to examine weight changes and concomitant compressibility changes due to moisture absorption Arranged in. The results after each cycle are shown in Table III below. This table shows that barrier layers of varying thickness are effective in suppressing weight and compressibility increases due to the absorption of water vapor in PBD based golf balls. The barrier layer achieves a reduction in core moisture absorption in an amount of at least about 30%, preferably in an amount of at least about 50%, more preferably in excess of about 60% compared to a core without it. . A thin barrier layer is more water vapor impermeable than a relatively thick ionomer layer, and moisture absorption is reduced by at least about 20%, and preferably by at least about 40%. The effect of suppressing the increase in compressibility by the barrier layer of the present invention is in the range of about 20% to about 60% when compared to the core without it.

In one embodiment, a two-piece golf ball includes a core, a cover, and a barrier layer of the present invention disposed between the core and the cover. The core is made from polybutadiene having a Mooney viscosity greater than about 35, an initiator, and ZDA at a level of about 15 phr or higher. Optionally, the core comprises ZnPCTP. The core diameter is less than about 1.64 inches, its specific gravity is less than about 1.4 g / cc, the compression rate is less than about 100, the amount of deflection at 100 kg is greater than about 1.5 mm, and the COR is Greater than about 0.78. The outside of the core is harder than the inside and the ambient hardness is at least about 5 Shore D greater than the hardness of the center. The barrier layer is made from particles dispersed in a binder with a P / B of about 1 to about 2. Preferably, the particles are aluminum, more preferably aluminum oxide leafing flakes, and the binder comprises a styrene rubber, such as Kraton ™ from Shell Chemical. The thickness of the barrier layer is less than about 0.02 inches, and its MVTR is smaller than Surlyn ™ by DuPont. The cover is made from a thermoplastic or thermoset polyurethane or polyurea, the material hardness is from about 25 Shore D to about 65 Shore D, and the flexural modulus is greater than about 2000 psi. Preferably, the cover adheres directly to the barrier layer by a coupling agent contained in the barrier layer. The generated golf ball is covered with about 250 to about 450 dimples, the compression ratio is less than about 110, the amount of deflection at 100 kg is greater than about 1.5 mm, and the moment of inertia is about 84 g · square cm. Small and the coefficient of restitution (COR) is greater than about 0.79.

  In other embodiments, a three-piece golf ball includes a dual core, a cover, and a barrier layer disposed between the dual core and the cover. The dual core is generated from a center and an outer core layer disposed around the center. The center is made from polybutadiene having a Mooney viscosity greater than about 35, an initiator, and ZDA at a level of about 15 phr to about 40. The center further includes a filler such as ligrind or tungsten metal powder. The center has a diameter of about 0.5 inch to about 1.6 inch, a compression ratio of about 10 to about 100, and a deflection amount at 100 kg is larger than about 1.5 mm. The outer core layer is made from polybutadiene having a Mooney viscosity greater than about 35, an initiator, and ZDA at a level of about 25 phr to about 55 phr. The outer core layer further includes a filler such as liglind, polyisoprene such as balata, or tungsten metal powder. Optionally, the core, outer core layer, or both may comprise ZnPCTP. The resulting dual core diameter is less than about 1.64 inches, the compressibility is less than about 100, the amount of deflection at 100 Kg is greater than about 1.5 mm, the ambient hardness is greater than about 60 Shore C, COR is greater than about 0.78. The barrier layer is made from particles dispersed in a binder with a P / B of about 1 to about 2. Preferably, the particles are aluminum, more preferably aluminum oxide leafing flakes, and the binder comprises a styrene rubber, such as Kraton ™ from Shell Chemical. The thickness of the barrier layer is less than about 0.02 inches, and its MVTR is smaller than Surlyn ™ by DuPont. The cover is made from a thermoplastic or thermoset polyurethane or polyurea, the material hardness is from about 25 Shore D to about 65 Shore D, and the flexural modulus is greater than about 2000 psi. Preferably, the cover adheres directly to the barrier layer by a coupling agent contained in the barrier layer. The three-piece golf ball is covered with about 250 to about 450 dimples, the compression ratio is less than about 110, the amount of deflection at 100 kg is greater than about 1.5 mm, and the moment of inertia is less than about 84 g · square cm. The coefficient of restitution (COR) is greater than about 0.79.

  The contents of the patents and patent applications referred to in the above description are hereby expressly incorporated herein by reference.

  The technical scope of the invention described and claimed herein is not limited by the specific embodiments disclosed herein. This is because these examples are only intended to illustrate many aspects of the invention. Equivalent embodiments and modifications obvious to those skilled in the art are intended to be included in the technical scope of the present invention. Furthermore, it can be easily understood that the various features of the present invention can be employed singly or in combination. The center further includes a filler such as riglind or tungsten metal powder. Such modifications and combinations are within the scope of the appended claims.

Claims (47)

In a golf ball comprising a core, a barrier layer surrounding the core, and a cover surrounding the barrier layer,
The barrier layer has a lower water vapor transmission rate than the cover;
The above-mentioned barrier layer is made of a thermoplastic or thermosetting compound in which microparticles are dispersed in a binder made of synthetic rubber, natural rubber, polyolefin, styrene polymer, or single-site catalyst polymer. ball.   The binder includes a styrene polymer, which is a styrene-butadiene copolymer, poly (styrene-co-maleic anhydride), acrylonitrile-butylene-styrene copolymer, styrene-olefin block copolymer, or poly (styrene sulfone). The golf ball of claim 1, further comprising:   The golf ball of claim 2, wherein the styrene polymer comprises at least one styrene-olefin block copolymer.   The golf ball according to claim 1, wherein the microparticles are fibers, whiskers, metal flakes, mica particles, or nanoparticles.   The golf ball according to claim 4, wherein the metal flakes include aluminum flakes, iron oxide flakes, copper flakes, or bronze flakes.   The golf ball according to claim 5, wherein the aluminum flakes include aluminum oxide flakes.   The golf ball of claim 1, wherein the microparticles have a particle size of about 4 microns to about 335 microns.   The golf ball of claim 1, wherein the microparticles are present in an amount of about 50 to about 250 parts by weight per 100 parts by weight of the binder.   The golf ball of claim 1, wherein the particle to binder weight ratio of the blend is about 1 to about 2.   The golf ball according to claim 1, wherein the binder is thermosetting and further contains a crosslinking agent.   The golf ball according to claim 10, wherein the crosslinking agent includes a polyolefin polyol, and the polyolefin polyol includes a hydrogenated polybutadiene polyol.   The golf ball of claim 11, wherein the cross-linking agent is present in an amount of at least about 10 parts by weight per 100 parts by weight of the binder.   The golf ball of claim 11, wherein the crosslinking agent is present in an amount of at least about 20 parts by weight per 100 parts by weight of the binder.   The golf ball of claim 1, wherein the formulation further comprises a catalyst or a coupling agent.   The golf ball according to claim 14, wherein the barrier layer is directly bonded to the cover by the coupling agent.   The golf ball of claim 1, wherein the barrier layer has a thickness of about 0.001 inch to about 0.01 inch.   The golf ball of claim 1, wherein the barrier layer has a thickness of about 0.002 inches to about 0.007 inches.   The golf ball of claim 1, wherein the barrier layer has a water vapor transmission rate less than about 0.95 grams · mm / (square meters · day).   The golf ball of claim 1, wherein the barrier layer has a water vapor transmission rate less than about 0.65 grams · mm / (square meters · day).   The golf ball of claim 1, wherein the barrier layer has a Sward hardness of about 5 to about 20.   The golf ball of claim 1, wherein the barrier layer has a pencil hardness of about 5B to about F.   The golf ball of claim 1, wherein the specific gravity of the vapor barrier layer is from about 1 g / cc to about 1.5 g / cc.   The golf ball of claim 1, wherein the specific gravity of the barrier layer is at least about 0.1 g / cc greater than the specific gravity of the core.   The golf ball of claim 1, wherein the formulation is dispersed in a non-aqueous solvent system comprising an aromatic hydrocarbon, ketone, acetate, alcohol, or ester.   The golf ball of claim 24, wherein the solvent-carrying dispersion includes a solids content of at least about 15%.   The golf ball of claim 24, wherein the solvent-carrying dispersion includes a solids content of at least about 30%.   The golf ball of claim 24, wherein the solvent-carrying dispersion has a viscosity of about 300 cps to about 1500 cps.   The golf ball of claim 24, wherein the solvent-carrying dispersion has a viscosity of about 500 cps to about 1000 cps.   The golf ball of claim 24, wherein the solvent-carrying dispersion has a viscosity of about 700 cps to about 900 cps.   The golf ball of claim 1, wherein the barrier layer is applied using spraying or dipping. In a golf ball comprising a core, a barrier layer surrounding the core, and a cover surrounding the barrier layer,
The barrier layer has a lower water vapor transmission rate than the cover;
The golf ball according to claim 1, wherein the barrier layer includes aluminum flakes, and the aluminum flakes include aluminum oxide. In a golf ball comprising a core, a barrier layer surrounding the core, and a cover surrounding the barrier layer,
The barrier layer has a lower water vapor transmission rate than the cover;
The golf ball according to claim 1, wherein the barrier layer includes means for forming a hydrophobic winding path across the barrier layer. A core having a diameter of at least about 1.62 inches;
A barrier layer that wraps around the core and is thinner than about 0.02 inches;
A cover thinner than about 0.03 inches that encloses the barrier layer;
The golf ball according to claim 1, wherein the barrier layer has a water vapor transmission rate smaller than that of the cover.   34. The golf ball of claim 33, wherein the binder comprises a thermoplastic or thermosetting compound in which microparticles are dispersed in the binder.   35. The golf ball of claim 34, wherein the microparticles include aluminum flakes including aluminum oxide, and the binder includes at least one styrene polymer.   35. A golf ball according to claim 34, wherein the formulation further comprises a cross-linking agent, a catalyst or a coupling agent.   35. The golf ball of claim 34, wherein the formulation is dispersed in a non-aqueous solvent system comprising an aromatic hydrocarbon, ketone, acetate, alcohol, or ester.   35. The golf ball of claim 34, wherein the weight ratio of the formulation to particles is about 0.5 to about 2.5.   The golf ball of claim 1, wherein the barrier layer has a water vapor transmission rate less than about 0.95 grams · mm / (square meters · day).   The golf ball of claim 1, wherein the barrier layer has a thickness of about 0.002 cm to about 0.007 inch. The core is
A diameter of about 1.62 inches to about 1.64 inches;
A compression ratio of less than about 100,
A deflection amount at 100 kg larger than about 1.5 mm;
A coefficient of restitution greater than about 0.78;
34. The golf ball of claim 33, having a specific gravity of less than about 1.4 g / cc. The core is
Polybutadiene having a Mooney viscosity greater than about 35;
A crosslinking agent in an amount greater than about 15 parts by weight per 100 parts by weight of the polybutadiene;
The golf ball of claim 33, comprising an optional plasticizer. The core is
A center having a diameter of about 0.5 inches to about 1.6 inches and a compressibility of about 10 to about 100, with a deflection of 100 kg A quantity larger than about 1.5 mm;
34. A golf ball according to claim 33, further comprising an outer core layer surrounding the center. The center
Polybutadiene having a Mooney viscosity greater than about 35;
A crosslinking agent in an amount of about 15 parts to about 40 parts by weight with respect to 100 parts by weight of the polybutadiene;
Wriglin or filler,
44. The golf ball of claim 43, comprising an optional plasticizer. The outer core layer is
Polybutadiene having a Mooney viscosity greater than about 35;
A crosslinking agent in an amount of about 25 parts by weight to about 55 parts by weight with respect to 100 parts by weight of the polybutadiene;
Ligrind, polyisoprene or filler,
With an optional plasticizer,
44. The golf ball of claim 43, wherein the outer core layer has a material hardness greater than about 60 Shore C. The cover has an outermost surface occupied by about 250 to about 450 dimples; and
Having a blend of thermoplastic polyurethane, thermosetting polyurethane, thermoplastic polyurea, or thermosetting polyurea;
34. The golf ball of claim 33, wherein the formulation has a material hardness of about 25 Shore D to about 65 Shore D and a flexural modulus of at least about 2000 psi. A compression ratio less than about 110;
A coefficient of restitution greater than about 0.79;
34. A golf ball according to claim 33, having a moment of inertia less than about 84 g · square cm and a deflection at 00 kg greater than about 1.5 mm.