US20030069085A1 - Golf ball with vapor barrier layer and method of making same - Google Patents

Golf ball with vapor barrier layer and method of making same Download PDF

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Publication number
US20030069085A1
US20030069085A1 US10/103,414 US10341402A US2003069085A1 US 20030069085 A1 US20030069085 A1 US 20030069085A1 US 10341402 A US10341402 A US 10341402A US 2003069085 A1 US2003069085 A1 US 2003069085A1
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United States
Prior art keywords
golf ball
moisture vapor
barrier layer
vapor barrier
rubber
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US10/103,414
Inventor
Matthew Hogge
Mitchell Lutz
Michael Sullivan
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Acushnet Co
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Acushnet Co
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Publication date
Priority claimed from US09/973,342 external-priority patent/US6632147B2/en
Priority to US10/103,414 priority Critical patent/US20030069085A1/en
Application filed by Acushnet Co filed Critical Acushnet Co
Assigned to ACUSHNET COMPANY reassignment ACUSHNET COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOGGE, MATTHEW F., LUTZ, MITCHELL E., SULLIVAN, MICHAEL J.
Publication of US20030069085A1 publication Critical patent/US20030069085A1/en
Priority to US10/754,781 priority patent/US6932720B2/en
Priority to US10/755,638 priority patent/US7357733B2/en
Priority to US11/083,453 priority patent/US7182702B2/en
Priority to US11/350,989 priority patent/US20060128505A1/en
Priority to US11/560,926 priority patent/US7951015B2/en
Priority to US13/084,044 priority patent/US8251839B2/en
Priority to US13/567,148 priority patent/US8454455B2/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04Polysulfides
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003Golf balls
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003Golf balls
    • A63B37/0004Surface depressions or protrusions
    • A63B37/0006Arrangement or layout of dimples
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/12Special coverings, i.e. outer layer material
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003Golf balls
    • A63B37/0004Surface depressions or protrusions
    • A63B37/002Specified dimple diameter
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003Golf balls
    • A63B37/0023Covers
    • A63B37/0029Physical properties
    • A63B37/0031Hardness
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003Golf balls
    • A63B37/0023Covers
    • A63B37/0029Physical properties
    • A63B37/0033Thickness
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003Golf balls
    • A63B37/007Characteristics of the ball as a whole
    • A63B37/0077Physical properties
    • A63B37/0093Moisture vapour transmission rate [MVTR]

Definitions

  • the present invention relates to a novel structure for a golf ball, and more particularly to a golf ball with a moisture vapor barrier layer.
  • Solid core golf balls are well known in the art.
  • the core is made from polybutadiene rubber material, which provides the primary source of resiliency for the golf ball.
  • U.S. Pat. Nos. 3,241,834 and 3,313,545 disclose the early work in polybutadiene chemistry. It is also known in the art that increasing the cross-link density of polybutadiene can increase the resiliency of the core.
  • the core is typically protected by a cover from repeated impacts from golf clubs.
  • the golf ball may comprise additional layers, which can be an outer core or an inner cover layer. One or more of these additional layers may be a wound layer of stretched elastic windings to increase the ball's resiliency.
  • a known drawback of polybutadiene cores cross-linked with peroxide and/or zinc diacrylate is that this material is adversely affected by moisture. Water moisture vapor reduces the resiliency of the cores and degrades its properties. A polybutadiene core will absorb water and loose its resilience. Thus, these cores must be covered quickly to maintain optimum ball properties.
  • the cover is typically made from ionomer resins, balata, and urethane, among other materials.
  • the ionomer covers, particularly the harder ionomers, offer some protection against the penetration of water vapor. However, it is more difficult to control or impart spin to balls with hard covers.
  • Conventional urethane covers while providing better ball control, offer less resistance to water vapor than ionomer covers.
  • Prolonged exposure to high humidity and elevated temperature may be sufficient to allow water vapor to invade the cores of some commercially available golf balls. For example at 110° F. and 90% humidity for a sixty day period, significant amounts of moisture enter the cores and reduce the initial velocity of the balls by 1.8 ft/s to 4.0 ft/s or greater.
  • the change in compression may vary from 5 PGA to about 10 PGA or greater.
  • the absorbed water vapor also reduces the coefficient of restitution (CoR) of the ball.
  • U.S. Pat. No. 5,820,488 discloses a golf ball with a solid inner core, an outer core and a water vapor barrier layer disposed therebetween.
  • the water vapor barrier layer preferably has a water vapor transmission rate lower than that of the cover layer.
  • the water vapor barrier layer can be a polyvinylidene chloride (PVDC) layer. It can also be formed by an in situ reaction between a barrier-forming material and the outer surface of the core. Alternatively, the water vapor barrier layer can be a vermiculite layer.
  • PVDC polyvinylidene chloride
  • 5,885,172 and 6,132,324 disclose, among other things, a golf ball with a polybutadiene or wound core with an ionomer resin inner cover and a relatively soft outer cover.
  • the hard ionomer inner cover offers some resistance to water vapor penetration and the soft outer cover provides the desirable ball control.
  • U.S. Pat. No. 5,875,891 discloses an impermeable packaging for golf balls.
  • the impermeable packaging acts as a moisture barrier limiting moisture absorption by golf balls during storage, but not during use.
  • the moisture vapor barrier layer disclosed in the prior patents can be rigid and makes the ball stiffer. Furthermore, producing a rigid layer may cause significant production obstacles.
  • less rigid polymers such as butyl rubber and other rubbers, are known to have low permeability to air, gases and moisture.
  • Butyl rubber is widely used as sealant for rooftops, as inner liner in tubeless tires, and as lining for chemical tanks, among other uses.
  • butyl rubber's usage has been limited to practice balls or driving range balls due to its slow initial velocity and low CoR, as discussed in U.S. Pat. Nos. 5,209,485 and 4,995,613.
  • butyl rubber is also used as the outermost cover layer or a part of the cover due to its durability, as disclosed, in U.S. Pat. Nos. 5,873,796 and 5,882,567, among others.
  • the moisture vapor barrier advantage of butyl rubber has not heretofore been utilized in the golf ball art to make a better performing golf ball.
  • the present invention is directed to a golf ball comprising a layer of moisture vapor barrier with a moisture vapor transmission rate preferably lower than that of the cover.
  • the moisture vapor barrier layer comprises butyl rubber.
  • the butyl rubber may also be a halogenated butyl rubber such as bromobutyl rubber or chlorobutyl rubber.
  • the butyl rubber may also be a sulfonated butyl rubber.
  • the butyl rubber may be blended with other polymers, such as double bond-vulcanizable rubber, ethylene propylene diene monomer rubber and vinylidene chloride.
  • the present invention is also directed to a golf ball comprising a moisture vapor barrier layer, which comprises copolymer of isobutylene and p-methylstyrene or polyisobutylene.
  • the moisture vapor barrier layer is placed on to a core subassembly and cured by infrared radiation (IR).
  • IR-curable moisture vapor barrier materials include, but not limited to, butyl rubber, polysulfide rubber and single-pack castable polymers, among others.
  • an outer layer of the golf ball may comprise a polymer that has a cured temperature greater than the softening temperature or melting temperature of the encased subassembly. Such outer layer may be cured by IR.
  • the outer layer may be a cover, an intermediate layer or a moisture vapor barrier layer.
  • the present invention is also directed to a golf ball comprising a butyl rubber moisture vapor barrier and a relatively soft cover.
  • the soft cover has a Shore D of less than 65 or between about 30 and about 60, and more preferably between about 35 and about 50, and most preferably about 40 and about 45.
  • the cover preferably has a thickness of between about 0.010 inch to about 0.050 inch, and more preferably about 0.030 inch.
  • the cover preferably comprises a thermoset polymer.
  • FIG. 1 is a front view of a dimpled golf ball in accordance to the present invention.
  • FIG. 2 is a cross-sectional view of the golf ball in FIG. 1 showing a solid core surrounded by a thin moisture vapor barrier layer and a cover;
  • FIG. 3 is a cross-sectional view of another golf ball in accordance to the present invention showing a solid core with multiple wound layers surrounded by a thin moisture vapor barrier layer.
  • reference number 10 broadly designates a golf ball in accordance to the present invention.
  • Golf ball 10 preferably has a solid core 12 , an intermediate layer 14 and a cover 16 .
  • Solid core 12 may comprise a single spherical element, or it may comprise a spherical element with one or more intermediate layers surrounding the spherical element.
  • Solid core 12 can be made from any suitable core materials including thermoset plastics, such as natural rubber, polybutadiene (PBD), polyisoprene, styrene-butadiene or styrene-propylene-diene rubber, and thermoplastics such as ionomer resins, polyamides, polyesters, or a thermoplastic elastomer.
  • thermoplastic elastomers include Pebax®, which is believed to comprise polyether amide copolymers, Hytrel®, which is believed to comprise polyether ester copolymers, thermoplastic urethane, and Kraton®, which is believed to comprise styrenic block copolymers elastomers.
  • the core materials can also be formed from a castable material. Suitable castable materials include those comprising a urethane, polyurea, epoxy, silicone, IPN's, etc.
  • suitable core materials may also include a reaction injection molded polyurethane or polyurea, including those versions referred to as nucleated, where a gas, typically nitrogen, is incorporated via intensive agitation or mixing into at least one component of the polyurethane, typically, the pre-polymer, prior to component injection into a closed mold where essentially full reaction takes place resulting in a cured polymer having reduced specific gravity.
  • a gas typically nitrogen
  • RIM reaction injection molded
  • the core may have a liquid center.
  • Cover 16 is preferably tough, cut-resistant, and selected from conventional materials used as golf ball covers based on the desired performance characteristics.
  • the cover may comprise one or more layers.
  • Suitable cover materials include ionomer resins, such as Surlyn® available from DuPont, blends of ionomer resins, thermoplastic or thermoset urethane, acrylic acid, methacrylic acid, thermoplastic rubber polymers consisting of block copolymers in which the elastomeric midblock of the molecule is an unsaturated rubber or a saturated olefin rubber, e.g., Kraton® rubbers available from Shell Chemical Co., polyethylene, and synthetic or natural vulcanized rubber such as balata.
  • ionomer resins such as Surlyn® available from DuPont, blends of ionomer resins, thermoplastic or thermoset urethane, acrylic acid, methacrylic acid, thermoplastic rubber polymers consisting of block copolymers in which the elastomeric midblock of
  • core 12 is made from a polybutadiene rubber material and cover 16 is made from a composition comprising a thermoset or thermoplastic urethane or a composition comprising an ionomer resin.
  • intermediate layer 14 comprises a moisture vapor barrier layer preferably disposed around core 12 .
  • moisture vapor barrier layer 14 has a moisture vapor transmission rate that is lower than that of the cover, and more preferably less than the moisture vapor transmission rate of an ionomer resin such as Surlyn® which is in the range of about 0.45 to about 0.95 grams ⁇ mm/m 2 ⁇ day.
  • the moisture vapor transmission rate of ionomer resin is less than 0.6 grams ⁇ mm/m 2 ⁇ day as reported in “Permeability and other Film Properties of Plastics and Elastomer” published by the Plastic Design Library (1995).
  • the moisture vapor transmission rate is defined as the mass of moisture vapor that diffuses into a material of a given thickness per unit area per unit time.
  • the preferred standards of measuring the moisture vapor transmission rate include ASTM F1249-90 entitled “Standard Test Method for Water Vapor Transmission Rate Through Plastic Film and Sheeting Using a Modulated Infrared Sensor,” and ASTM F372-94 entitled “Standard Test Method for Water Vapor Transmission Rate of Flexible Barrier Materials Using an Infrared Detection Technique,” among others.
  • a preferred polymer for the moisture vapor barrier layer is butyl rubber.
  • Butyl rubber (IIR) is an elastomeric copolymer of isobutylene and isoprene. Detailed discussions of butyl rubber are provided in U.S. Pat. Nos. 3,642,728, 2,356,128 and 3,099,644. The disclosures of these references are incorporated herein by reference in their entireties.
  • Butyl rubber is an amorphous, non-polar polymer with good oxidative and thermal stability, good permanent flexibility and high moisture and gas resistance.
  • butyl rubber includes copolymers of about 70% to 99.5% by weight of an isoolefin, which has about 4 to 7 carbon atoms, e.g., isobutylene, and about 0.5% to 30% by weight of a conjugated multiolefin, which has about 4 to 14 carbon atoms, e.g., isoprene.
  • the resulting copolymer contains about 85% to about 99.8% by weight of combined isoolefin and 0.2% to 15% of combined multiolefin.
  • Commercially available butyl rubbers such as those manufactured by ExxonMobil Chemical Company, typically have about 1 to 2.5 mole percent of isoprene.
  • butyl rubbers generally have molecular weight of about 20,000 to about 500,000. Suitable butyl rubber is also available from United Coatings under the tradename ElastronTM 858.
  • Elastrom 858 is a butyl rubber coating applied as a solution in a volatile hydrocarbon solvent, which is typically sprayed or dipped on to an object or a surface, and contains lead peroxide as a crosslinking agent.
  • Halogenated butyl rubbers are also available in halogenated form.
  • Halogenated butyl rubbers may be prepared by halogenating butyl rubber in a solution containing inert C3-C5 hydrocarbon solvent, such as pentane, hexane or heptane, and contacting this solution with a halogen gas for a predetermined amount of time, whereby halogenated butyl rubber and a hydrogen halide are formed.
  • the halogenated butyl rubber copolymer may contain up to one halogen atom per double bond.
  • Halogenated butyl rubbers or halobutyl rubbers include bromobutyl rubber, which may contain up to 3% reactive bromine, and chlorobutyl rubber, which may contain up to 3% reactive chlorine.
  • Halogenated butyl rubbers are also available from ExxonMobil Chemical.
  • Butyl rubbers and halogenated rubbers advantageously have low permeability to air, gases and moisture. For example, as reported by the manufacturer the permeability of nitrogen in butyl rubber is more than one order of magnitude less than that in neoprene, styrene butadiene rubber, natural rubber and nitrile butadiene rubber.
  • butyl rubber is also available in sulfonated form, such as those disclosed in the '728 patent and in U.S. Pat. No. 4,229,337.
  • butyl rubber having a viscosity average molecular weight in the range of about 5,000 to 85,000 and a mole percent unsaturation of about 3% to about 4% may be sulfonated with a sulfonating agent comprising a sulfur trioxide (SO 3 ) donor in combination with a Lewis base containing oxygen, nitrogen or phosphorus.
  • SO 3 donor includes compound containing available SO 3 , such as chlorosulfonic acid, fluorosulfonic acid, sulfuric acid and oleum.
  • the moisture vapor transmission rate of butyl rubber is in the range of about 0.001 to about 0.100 grams ⁇ mm/m 2 ⁇ day.
  • Suitable moisture vapor barrier polymers include the elastomers that combine the low permeability of butyl rubbers with the environmental and aging resistance of ethylene propylene diene monomer rubbers (EPDM), commercially available as ExxproTM from ExxonMobil Chemical. More specifically, these elastomers are brominated polymers derived from a copolymer of isobutylene (IB) and p-methylstyrene (PMS). Bromination selectively occurs on the PMS methyl group to provide a reactive benzylic bromine functionality.
  • Another suitable moisture vapor barrier polymer is copolymer of isobulyline and isoprene with a styrene block copolymer branching agent to improve manufacturing processability.
  • polyisobutylene is a homopolymer, which is produced by cationic polymerization methods.
  • Commercially available grades of polyisobutylene under the tradename VistanexTM also from ExxonMobil Chemical, are highly paraffinic hydrocarbon polymers composed on long straight chain molecules containing only chain-end olefinic bonds.
  • An advantage of such elastomer is the combination of low permeability and chemical inertness to resist moisture vapor encroachment, and chemical or oxidative attacks.
  • Polyisobutylene is available as a viscous liquid or semi-solids, and can be dissolved in certain hydrocarbon solvents.
  • halogenated butyl rubber can be blended with a second rubber, preferably a double bond-vulcanizable rubber, in a specific mixing ratio in a two-step kneading process and then cured to form a rubber blend that has low air/vapor permeability and high adhesion to diene rubbers.
  • a second rubber preferably a double bond-vulcanizable rubber
  • a clear advantage of this rubber blend is that it provides enhanced adherence to a polybutadiene core or subassembly to provide an enhanced moisture/water vapor barrier layer.
  • This rubber blend is discussed in U.S. Pat. No. 6,342,567 B2. The '567 patent is hereby incorporated herein by reference.
  • moisture vapor barrier polymers include thermoplastic elastomer blends that may be dynamically vulcanized and comprise a butyl rubber or a halogenated butyl rubber, such as those discussed in U.S. Pat. Nos. 6,062,283, 6,334,919 B1 and 6,346,571 B1. These references are incorporated herein by reference.
  • butyl rubber may be blended with a vinylidene chloride polymer, i.e., saran, as disclosed in U.S. Pat. No. 4,239,799. The '799 patent is also incorporated herein by reference.
  • Butyl rubbers can be cured by a number of curing agents.
  • Preferred curing agents for golf ball usage include sulphur for butyl rubber, and a peroxide curing agent, preferably zinc oxide, for halogenated butyl rubbers.
  • Other suitable curing agents may include antimony oxide, lead oxide or lead peroxide.
  • Lead based curing agents may be used when appropriate safety precautions are implemented.
  • Butyl rubbers are commercially available in various grades from viscous liquid to solids with varying the degree of unsaturation and molecular weights. Latex grades are also available.
  • Butyl rubber and halogenated rubber can be processed by milling, calendering, extruding, injection molding and compression molding, among other techniques. These processing techniques can produce a semi-cured sheets or half-shelves of the moisture vapor barrier material, which can be wrapped around a core or a core subassembly. The moisture vapor barrier can be fully cured by exposure to heat at elevated temperatures typically in the range of about 250° F. to 2000° F.
  • any number of fillers, additives, fibers and flakes such as mica, micaceous ion oxide, metal, ceramic, graphite, aluminum or more preferably leafing aluminum, can be incorporated into the moisture vapor barrier layer to create a physical barrier, i.e., a more tortuous path, against moisture vapor encroachment.
  • IR infrared radiation
  • U.S. Pat. No. 6,174,388 B1 discloses that IR can be used effectively to heat and cure the surface of a polymeric object while leaving the other portions of the object unchanged.
  • U.S. Pat. Nos. 5,677,362 and 5,672,393 disclose that IR heating can be used in conjunction with ultraviolet heating to cure polymers effectively. The disclosure of the patents are incorporated by reference in their entireties.
  • moisture vapor barrier polymers which have cured or cross-linking temperatures that are higher than the softening temperature or the melting temperature of the materials encased therein, can be now employed as the moisture vapor barrier layer and/or other outer layers.
  • another suitable IR-cured water vapor barrier material is polysulfide rubber including those disclosed in U.S. Pat. Nos. 4,263,078 and 4,165,425, among others. These references are incorporated herein by reference.
  • the polysulfide rubber is cured with lower alkyl tin oxide, such as di-n-butyl tin oxide, and used in hot applied processes as disclosed in the '425 patent.
  • This particular polysulfide rubber is thiol terminated and cured with the lower alkyl tin oxide at temperatures between 100° C. and 300° C. to become a solid thermoplastic elastomer that can be softened by heating and then cast or injection molded into a water vapor barrier layer.
  • This polysulfide compound is preferably cured by IR.
  • Another suitable IR-curable polysulfide rubber is based on thiol terminated liquid polysulfide polymer cured with zinc oxide and a sulfur containing compound selected from 2-mercaptobenzothiazol, zinc lower alkyl dithiocarbamate and alkyl thiuram polysulfides at temperatures from about 200° F. to about 390° F.
  • Agents which improve the flowing properties of the composition, such as copolymers of styrene and alkylenes, organic or inorganic reinforcing fibrous materials, phenolic resins, coumarone-indene resins, antioxidants, heat stabilizers, polyalkylene polymers, factice, terpene resins, terpene resins esters, benzothiazyl disulfide or diphenyl guanidine, can also be added to the composition.
  • this polysulfide rubber possesses a good ability to wet the substrate and forms good bonds with such substrate when cooled and, therefore, is a preferred sealant for the golf ball core.
  • This polysulfide compound is also preferably cured by IR.
  • Moisture vapor barrier layer comprising polysulfide rubber is fully disclosed in co-pending patent application entitled “Golf Ball With Vapor Barrier Layer and Method for Making Same” filed on the same day as the present application and assigned to the same assignee. The disclosure of this co-pending patent application is incorporated herein by reference.
  • suitable IR-cured water vapor barrier polymers include single-pack castable polymers.
  • a preferred single-pack polymer uses uretdiones or blocked isocyanates to form a single-pack urethane component.
  • the single-pack blocked isocyanate system which preferably comprises isocyanate combined with an amine or poloyl, is advantageously stable at room temperature.
  • the application of heat, such as infrared radiation causes the isocyanate to become unblocked or to react to form a urethane. No mixing or dynamically controlling the ratios of the components is required.
  • Uretdione castable materials can be pre-formulated as a single-pack system without premature reaction.
  • the mixed single-pack material can be directly injected or poured into a mold, avoiding metering and mixing of multiple components. Parts can be made utilizing viscous or solid materials that previously could not be used with traditional two-pack systems.
  • uretdiones and blocked isocyanates when combined with suitable reactive components can be milled into rubber stock for use with other manufacturing techniques, discussed above.
  • a non-limiting example of a single-pack system in accordance to the present invention is as follows. Finely ground uretdione is dispersed in a liquid polyol or polyamine in combination with a tin catalyst and cyclic amidine catalyst. A slurry is created. The slurry mixture is poured into a suitable golf ball mold to make the required part, e.g., core, intermediate layer or cover. The mold is then heated to reach the predetermined deblocking temperature of about 150-180° C., and the reaction is allowed sufficient time to complete. The cured component then can be removed from the mold for further processing, if necessary.
  • the single-pack moisture vapor barrier layer utilizes blocked isocyanates that volatilize when de-blocking occurs, such as diethylmaleonate (DEM) or methyl ethyl ketoxime (MEKO) blocked hexamethylene diisocyanate cyclic trimer.
  • DEM diethylmaleonate
  • MEKO methyl ethyl ketoxime
  • the preferred hardeners are uretdiones or a blocked isocyanates, where the blocking agent remains in the component as a solid once cast, such as DMP or triazole blocked isocyanates.
  • the structures of the preferred blocking agents are:
  • the Shore D hardness values for the core and moisture vapor barrier sub-assemblies have been measured less than about 60 and more specifically in the range of about 5-50.
  • the moisture barrier sub-assemblies may have Shore D hardness value of greater than 50, when more rigid materials, such as stiff ionomer with a Shore D hardness of greater than 55 are used in conjunction with the moisture vapor barrier layer 14 .
  • a golf ball in accordance to the present invention comprises a solid or multiple-layer solid polybutadiene core 12 having an outer diameter of greater than about 1.50 inches, more preferably 1.550 inches and most preferably about 1.580 inches.
  • Moisture vapor barrier layer 14 has a thickness preferably in the range of about 0.001 inch to about 0.100 inch, more preferably in range of about 0.010 inch to about 0.050 inch and cover 16 is a urethane cover with sufficient thickness to produce a 1.680 inch diameter golf ball.
  • the moisture vapor barrier layer is a thin layer of suitable butyl rubber polymers discussed above, preferably less than 0.050 inch, more preferable less than 0.030 inch and most preferably less than 0.010 inch. It is also preferable that the butyl rubber moisture vapor barrier layer would not significantly and negatively affect the coefficient of restitution of the golf ball.
  • the polybutadiene core 12 and the thin butyl rubber moisture vapor barrier layer 14 are covered by a relatively soft polymer cover having a thickness from about 0.010 to about 0.050 inch, more preferably about 0.030 inch and has a Shore D of less than 65 or from about 30 to about 60, more preferably from about 35 to about 50 and even more preferably about 40 to about 45.
  • cover polymers include thermoset urethanes and polyurethanes, thermoset urethane ionomers and thermoset urethane epoxies.
  • golf ball 20 may have multiple layer core 12 a , 12 b and 12 c , surrounded by intermediate layer 14 and dimpled cover 16 .
  • Core layers 12 b and 12 c may be an integral solid layer or discrete layers molded on each other.
  • both outer core layers 12 b and 12 c could be wound layers, or one of these two layers may be a wound layer, and the innermost core 12 a may be liquid-filled.

Abstract

A golf ball with at least one moisture vapor barrier layer is disclosed. In accordance to one aspect of the invention, the moisture vapor barrier layer may comprise butyl rubber. The butyl rubber may also be a halogenated butyl rubber such as bromobutyl rubber or chlorobutyl rubber. The butyl rubber may also be a sulfonated butyl rubber. The butyl rubber may be blended with other polymers. In accordance to another aspect of the invention, the moisture vapor barrier layer is placed on to a core subassembly and cured by infrared radiation (IR). IR-curable moisture vapor barrier materials include, but not limited to, butyl rubber, polysulfide rubber and single-pack castable polymers, among others. In accordance to another aspect of the invention, an outer layer of the golf ball may comprise a polymer that has a cured temperature greater than the softening temperature or melting temperature of the encased subassembly. Such outer layer may be cured by IR. The outer layer may be a cover, an intermediate layer or a moisture vapor barrier layer.

Description

    STATEMENT OF RELATED PATENT APPLICATION
  • This non-provisional, utility patent application is a continuation-in-part of a co-pending patent application Ser. No. 09/973,342, entitled “Golf Ball With Vapor Barrier Layer and Method of Making Same”, filed on Oct. 9, 2001. The parent application is hereby incorporated by reference in its entirety.[0001]
  • FIELD OF THE INVENTION
  • The present invention relates to a novel structure for a golf ball, and more particularly to a golf ball with a moisture vapor barrier layer. [0002]
  • BACKGROUND OF THE INVENTION
  • Solid core golf balls are well known in the art. Typically, the core is made from polybutadiene rubber material, which provides the primary source of resiliency for the golf ball. U.S. Pat. Nos. 3,241,834 and 3,313,545 disclose the early work in polybutadiene chemistry. It is also known in the art that increasing the cross-link density of polybutadiene can increase the resiliency of the core. The core is typically protected by a cover from repeated impacts from golf clubs. The golf ball may comprise additional layers, which can be an outer core or an inner cover layer. One or more of these additional layers may be a wound layer of stretched elastic windings to increase the ball's resiliency. [0003]
  • A known drawback of polybutadiene cores cross-linked with peroxide and/or zinc diacrylate is that this material is adversely affected by moisture. Water moisture vapor reduces the resiliency of the cores and degrades its properties. A polybutadiene core will absorb water and loose its resilience. Thus, these cores must be covered quickly to maintain optimum ball properties. The cover is typically made from ionomer resins, balata, and urethane, among other materials. The ionomer covers, particularly the harder ionomers, offer some protection against the penetration of water vapor. However, it is more difficult to control or impart spin to balls with hard covers. Conventional urethane covers, on the other hand, while providing better ball control, offer less resistance to water vapor than ionomer covers. [0004]
  • Prolonged exposure to high humidity and elevated temperature may be sufficient to allow water vapor to invade the cores of some commercially available golf balls. For example at 110° F. and 90% humidity for a sixty day period, significant amounts of moisture enter the cores and reduce the initial velocity of the balls by 1.8 ft/s to 4.0 ft/s or greater. The change in compression may vary from 5 PGA to about 10 PGA or greater. The absorbed water vapor also reduces the coefficient of restitution (CoR) of the ball. [0005]
  • Several prior patents have addressed the water vapor absorption problem. U.S. Pat. No. 5,820,488 discloses a golf ball with a solid inner core, an outer core and a water vapor barrier layer disposed therebetween. The water vapor barrier layer preferably has a water vapor transmission rate lower than that of the cover layer. The water vapor barrier layer can be a polyvinylidene chloride (PVDC) layer. It can also be formed by an in situ reaction between a barrier-forming material and the outer surface of the core. Alternatively, the water vapor barrier layer can be a vermiculite layer. U.S. Pat. Nos. 5,885,172 and 6,132,324 disclose, among other things, a golf ball with a polybutadiene or wound core with an ionomer resin inner cover and a relatively soft outer cover. The hard ionomer inner cover offers some resistance to water vapor penetration and the soft outer cover provides the desirable ball control. Additionally, U.S. Pat. No. 5,875,891 discloses an impermeable packaging for golf balls. The impermeable packaging acts as a moisture barrier limiting moisture absorption by golf balls during storage, but not during use. [0006]
  • The moisture vapor barrier layer disclosed in the prior patents can be rigid and makes the ball stiffer. Furthermore, producing a rigid layer may cause significant production obstacles. On the other hand, less rigid polymers, such as butyl rubber and other rubbers, are known to have low permeability to air, gases and moisture. Butyl rubber is widely used as sealant for rooftops, as inner liner in tubeless tires, and as lining for chemical tanks, among other uses. In the golf ball art, butyl rubber's usage has been limited to practice balls or driving range balls due to its slow initial velocity and low CoR, as discussed in U.S. Pat. Nos. 5,209,485 and 4,995,613. Butyl rubber is also used as the outermost cover layer or a part of the cover due to its durability, as disclosed, in U.S. Pat. Nos. 5,873,796 and 5,882,567, among others. However, the moisture vapor barrier advantage of butyl rubber has not heretofore been utilized in the golf ball art to make a better performing golf ball. [0007]
  • Also, high-temperature curing of certain polymeric materials to form the water vapor barrier layer or other outer layers on the golf ball is difficult to accomplish, since such curing or crosslinking heats the entire golf ball subassembly. This heating method may degrade the untargeted components or layers within the subassembly. Additionally, this curing method limits suitable outer layer materials to materials having a cured temperature that is lower than the softening temperature or lower melting temperature of the inner layers or core. [0008]
  • Hence, there remains a need for a golf ball with an improved water vapor barrier layer and improved methods for applying a water vapor barrier layer on to the core of the golf ball. [0009]
  • SUMMARY OF THE INVENTION
  • The present invention is directed to a golf ball comprising a layer of moisture vapor barrier with a moisture vapor transmission rate preferably lower than that of the cover. Preferably, the moisture vapor barrier layer comprises butyl rubber. The butyl rubber may also be a halogenated butyl rubber such as bromobutyl rubber or chlorobutyl rubber. The butyl rubber may also be a sulfonated butyl rubber. The butyl rubber may be blended with other polymers, such as double bond-vulcanizable rubber, ethylene propylene diene monomer rubber and vinylidene chloride. [0010]
  • The present invention is also directed to a golf ball comprising a moisture vapor barrier layer, which comprises copolymer of isobutylene and p-methylstyrene or polyisobutylene. [0011]
  • In accordance to another aspect of the invention, the moisture vapor barrier layer is placed on to a core subassembly and cured by infrared radiation (IR). IR-curable moisture vapor barrier materials include, but not limited to, butyl rubber, polysulfide rubber and single-pack castable polymers, among others. [0012]
  • In accordance to another aspect of the invention, an outer layer of the golf ball may comprise a polymer that has a cured temperature greater than the softening temperature or melting temperature of the encased subassembly. Such outer layer may be cured by IR. The outer layer may be a cover, an intermediate layer or a moisture vapor barrier layer. [0013]
  • The present invention is also directed to a golf ball comprising a butyl rubber moisture vapor barrier and a relatively soft cover. Preferably, the soft cover has a Shore D of less than 65 or between about 30 and about 60, and more preferably between about 35 and about 50, and most preferably about 40 and about 45. The cover preferably has a thickness of between about 0.010 inch to about 0.050 inch, and more preferably about 0.030 inch. The cover preferably comprises a thermoset polymer.[0014]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • In the accompanying drawings which form a part of the specification and are to be read in conjunction therewith and in which like reference numerals are used to indicate like parts in the various views: [0015]
  • FIG. 1 is a front view of a dimpled golf ball in accordance to the present invention; [0016]
  • FIG. 2 is a cross-sectional view of the golf ball in FIG. 1 showing a solid core surrounded by a thin moisture vapor barrier layer and a cover; and [0017]
  • FIG. 3 is a cross-sectional view of another golf ball in accordance to the present invention showing a solid core with multiple wound layers surrounded by a thin moisture vapor barrier layer.[0018]
  • DETAILED DESCRIPTION OF THE INVENTION
  • As shown generally in FIGS. 1 and 2, where like numbers designate like parts, [0019] reference number 10 broadly designates a golf ball in accordance to the present invention. Golf ball 10 preferably has a solid core 12, an intermediate layer 14 and a cover 16. Solid core 12 may comprise a single spherical element, or it may comprise a spherical element with one or more intermediate layers surrounding the spherical element. Solid core 12 can be made from any suitable core materials including thermoset plastics, such as natural rubber, polybutadiene (PBD), polyisoprene, styrene-butadiene or styrene-propylene-diene rubber, and thermoplastics such as ionomer resins, polyamides, polyesters, or a thermoplastic elastomer. Suitable thermoplastic elastomers include Pebax®, which is believed to comprise polyether amide copolymers, Hytrel®, which is believed to comprise polyether ester copolymers, thermoplastic urethane, and Kraton®, which is believed to comprise styrenic block copolymers elastomers. These products are commercially available from Elf-Atochem, E. I. Du Pont de Nemours and Company, various manufacturers, and Shell Chemical Company, respectively. The core materials can also be formed from a castable material. Suitable castable materials include those comprising a urethane, polyurea, epoxy, silicone, IPN's, etc.
  • Additionally, suitable core materials may also include a reaction injection molded polyurethane or polyurea, including those versions referred to as nucleated, where a gas, typically nitrogen, is incorporated via intensive agitation or mixing into at least one component of the polyurethane, typically, the pre-polymer, prior to component injection into a closed mold where essentially full reaction takes place resulting in a cured polymer having reduced specific gravity. These materials are referred to as reaction injection molded (RIM) materials. Alternatively, the core may have a liquid center. [0020]
  • [0021] Cover 16 is preferably tough, cut-resistant, and selected from conventional materials used as golf ball covers based on the desired performance characteristics. The cover may comprise one or more layers. Suitable cover materials include ionomer resins, such as Surlyn® available from DuPont, blends of ionomer resins, thermoplastic or thermoset urethane, acrylic acid, methacrylic acid, thermoplastic rubber polymers consisting of block copolymers in which the elastomeric midblock of the molecule is an unsaturated rubber or a saturated olefin rubber, e.g., Kraton® rubbers available from Shell Chemical Co., polyethylene, and synthetic or natural vulcanized rubber such as balata.
  • Additionally, other suitable core and cover materials are disclosed in U.S. Pat. No. 5,919,100 and international publications WO 00/23519 and WO 01/29129. These disclosures are incorporated by reference in their entirety. Preferably, [0022] core 12 is made from a polybutadiene rubber material and cover 16 is made from a composition comprising a thermoset or thermoplastic urethane or a composition comprising an ionomer resin.
  • To prevent or minimize the penetration of moisture, typically water vapor, into [0023] core 12 of golf ball 10, intermediate layer 14 comprises a moisture vapor barrier layer preferably disposed around core 12. Preferably, moisture vapor barrier layer 14 has a moisture vapor transmission rate that is lower than that of the cover, and more preferably less than the moisture vapor transmission rate of an ionomer resin such as Surlyn® which is in the range of about 0.45 to about 0.95 grams·mm/m2·day. Typically, the moisture vapor transmission rate of ionomer resin is less than 0.6 grams·mm/m2·day as reported in “Permeability and other Film Properties of Plastics and Elastomer” published by the Plastic Design Library (1995). The moisture vapor transmission rate is defined as the mass of moisture vapor that diffuses into a material of a given thickness per unit area per unit time. The preferred standards of measuring the moisture vapor transmission rate include ASTM F1249-90 entitled “Standard Test Method for Water Vapor Transmission Rate Through Plastic Film and Sheeting Using a Modulated Infrared Sensor,” and ASTM F372-94 entitled “Standard Test Method for Water Vapor Transmission Rate of Flexible Barrier Materials Using an Infrared Detection Technique,” among others.
  • A preferred polymer for the moisture vapor barrier layer is butyl rubber. Butyl rubber (IIR) is an elastomeric copolymer of isobutylene and isoprene. Detailed discussions of butyl rubber are provided in U.S. Pat. Nos. 3,642,728, 2,356,128 and 3,099,644. The disclosures of these references are incorporated herein by reference in their entireties. Butyl rubber is an amorphous, non-polar polymer with good oxidative and thermal stability, good permanent flexibility and high moisture and gas resistance. Generally, butyl rubber includes copolymers of about 70% to 99.5% by weight of an isoolefin, which has about 4 to 7 carbon atoms, e.g., isobutylene, and about 0.5% to 30% by weight of a conjugated multiolefin, which has about 4 to 14 carbon atoms, e.g., isoprene. The resulting copolymer contains about 85% to about 99.8% by weight of combined isoolefin and 0.2% to 15% of combined multiolefin. Commercially available butyl rubbers, such as those manufactured by ExxonMobil Chemical Company, typically have about 1 to 2.5 mole percent of isoprene. Butyl rubbers generally have molecular weight of about 20,000 to about 500,000. Suitable butyl rubber is also available from United Coatings under the tradename Elastron™ 858. Elastrom 858 is a butyl rubber coating applied as a solution in a volatile hydrocarbon solvent, which is typically sprayed or dipped on to an object or a surface, and contains lead peroxide as a crosslinking agent. [0024]
  • Butyl rubbers are also available in halogenated form. Halogenated butyl rubbers may be prepared by halogenating butyl rubber in a solution containing inert C3-C5 hydrocarbon solvent, such as pentane, hexane or heptane, and contacting this solution with a halogen gas for a predetermined amount of time, whereby halogenated butyl rubber and a hydrogen halide are formed. The halogenated butyl rubber copolymer may contain up to one halogen atom per double bond. Halogenated butyl rubbers or halobutyl rubbers include bromobutyl rubber, which may contain up to 3% reactive bromine, and chlorobutyl rubber, which may contain up to 3% reactive chlorine. Halogenated butyl rubbers are also available from ExxonMobil Chemical. Butyl rubbers and halogenated rubbers advantageously have low permeability to air, gases and moisture. For example, as reported by the manufacturer the permeability of nitrogen in butyl rubber is more than one order of magnitude less than that in neoprene, styrene butadiene rubber, natural rubber and nitrile butadiene rubber. [0025]
  • Butyl rubber is also available in sulfonated form, such as those disclosed in the '728 patent and in U.S. Pat. No. 4,229,337. Generally, butyl rubber having a viscosity average molecular weight in the range of about 5,000 to 85,000 and a mole percent unsaturation of about 3% to about 4% may be sulfonated with a sulfonating agent comprising a sulfur trioxide (SO[0026] 3) donor in combination with a Lewis base containing oxygen, nitrogen or phosphorus. The Lewis base serves as a complexing agent for the SO3 donor. SO3 donor includes compound containing available SO3, such as chlorosulfonic acid, fluorosulfonic acid, sulfuric acid and oleum.
  • Typically, the moisture vapor transmission rate of butyl rubber is in the range of about 0.001 to about 0.100 grams·mm/m[0027] 2·day.
  • Other suitable moisture vapor barrier polymers include the elastomers that combine the low permeability of butyl rubbers with the environmental and aging resistance of ethylene propylene diene monomer rubbers (EPDM), commercially available as Exxpro™ from ExxonMobil Chemical. More specifically, these elastomers are brominated polymers derived from a copolymer of isobutylene (IB) and p-methylstyrene (PMS). Bromination selectively occurs on the PMS methyl group to provide a reactive benzylic bromine functionality. Another suitable moisture vapor barrier polymer is copolymer of isobulyline and isoprene with a styrene block copolymer branching agent to improve manufacturing processability. [0028]
  • Another suitable moisture vapor barrier polymer is polyisobutylene. Polyisobutylene is a homopolymer, which is produced by cationic polymerization methods. Commercially available grades of polyisobutylene, under the tradename Vistanex™ also from ExxonMobil Chemical, are highly paraffinic hydrocarbon polymers composed on long straight chain molecules containing only chain-end olefinic bonds. An advantage of such elastomer is the combination of low permeability and chemical inertness to resist moisture vapor encroachment, and chemical or oxidative attacks. Polyisobutylene is available as a viscous liquid or semi-solids, and can be dissolved in certain hydrocarbon solvents. [0029]
  • In accordance to another aspect of the invention, halogenated butyl rubber can be blended with a second rubber, preferably a double bond-vulcanizable rubber, in a specific mixing ratio in a two-step kneading process and then cured to form a rubber blend that has low air/vapor permeability and high adhesion to diene rubbers. A clear advantage of this rubber blend is that it provides enhanced adherence to a polybutadiene core or subassembly to provide an enhanced moisture/water vapor barrier layer. This rubber blend is discussed in U.S. Pat. No. 6,342,567 B2. The '567 patent is hereby incorporated herein by reference. Alternatively, a brominated isobutylene/p-methylstyrene, discussed above, can be used in place of the halogenated rubber. Other moisture vapor barrier polymers include thermoplastic elastomer blends that may be dynamically vulcanized and comprise a butyl rubber or a halogenated butyl rubber, such as those discussed in U.S. Pat. Nos. 6,062,283, 6,334,919 B1 and 6,346,571 B1. These references are incorporated herein by reference. Alternatively, butyl rubber may be blended with a vinylidene chloride polymer, i.e., saran, as disclosed in U.S. Pat. No. 4,239,799. The '799 patent is also incorporated herein by reference. [0030]
  • Butyl rubbers can be cured by a number of curing agents. Preferred curing agents for golf ball usage include sulphur for butyl rubber, and a peroxide curing agent, preferably zinc oxide, for halogenated butyl rubbers. Other suitable curing agents may include antimony oxide, lead oxide or lead peroxide. Lead based curing agents may be used when appropriate safety precautions are implemented. Butyl rubbers are commercially available in various grades from viscous liquid to solids with varying the degree of unsaturation and molecular weights. Latex grades are also available. [0031]
  • Butyl rubber and halogenated rubber can be processed by milling, calendering, extruding, injection molding and compression molding, among other techniques. These processing techniques can produce a semi-cured sheets or half-shelves of the moisture vapor barrier material, which can be wrapped around a core or a core subassembly. The moisture vapor barrier can be fully cured by exposure to heat at elevated temperatures typically in the range of about 250° F. to 2000° F. [0032]
  • Additionally, any number of fillers, additives, fibers and flakes, such as mica, micaceous ion oxide, metal, ceramic, graphite, aluminum or more preferably leafing aluminum, can be incorporated into the moisture vapor barrier layer to create a physical barrier, i.e., a more tortuous path, against moisture vapor encroachment. [0033]
  • In accordance to another aspect of the invention. The curing of the moisture vapor barrier material on to the core or the core subassembly is preferably accomplished by infrared radiation (IR). IR advantageously heats the moisture vapor material, e.g., butyl rubber, locally without penetrating the underlying golf ball core and/or other encased layers. Hence, the predetermined properties of the core and/or of the encased layers would not be affected by the heating/curing of the moisture vapor barrier layer. U.S. Pat. No. 6,174,388 B1 discloses that IR can be used effectively to heat and cure the surface of a polymeric object while leaving the other portions of the object unchanged. U.S. Pat. Nos. 5,677,362 and 5,672,393 disclose that IR heating can be used in conjunction with ultraviolet heating to cure polymers effectively. The disclosure of the patents are incorporated by reference in their entireties. [0034]
  • Another advantage of using IR as the curing technique is that suitable moisture vapor barrier polymers, which have cured or cross-linking temperatures that are higher than the softening temperature or the melting temperature of the materials encased therein, can be now employed as the moisture vapor barrier layer and/or other outer layers. [0035]
  • In accordance to another aspect of the present invention, another suitable IR-cured water vapor barrier material is polysulfide rubber including those disclosed in U.S. Pat. Nos. 4,263,078 and 4,165,425, among others. These references are incorporated herein by reference. In one example, the polysulfide rubber is cured with lower alkyl tin oxide, such as di-n-butyl tin oxide, and used in hot applied processes as disclosed in the '425 patent. This particular polysulfide rubber is thiol terminated and cured with the lower alkyl tin oxide at temperatures between 100° C. and 300° C. to become a solid thermoplastic elastomer that can be softened by heating and then cast or injection molded into a water vapor barrier layer. This polysulfide compound is preferably cured by IR. [0036]
  • Another suitable IR-curable polysulfide rubber is based on thiol terminated liquid polysulfide polymer cured with zinc oxide and a sulfur containing compound selected from 2-mercaptobenzothiazol, zinc lower alkyl dithiocarbamate and alkyl thiuram polysulfides at temperatures from about 200° F. to about 390° F. Agents, which improve the flowing properties of the composition, such as copolymers of styrene and alkylenes, organic or inorganic reinforcing fibrous materials, phenolic resins, coumarone-indene resins, antioxidants, heat stabilizers, polyalkylene polymers, factice, terpene resins, terpene resins esters, benzothiazyl disulfide or diphenyl guanidine, can also be added to the composition. Advantageously, this polysulfide rubber possesses a good ability to wet the substrate and forms good bonds with such substrate when cooled and, therefore, is a preferred sealant for the golf ball core. This polysulfide compound is also preferably cured by IR. [0037]
  • Moisture vapor barrier layer comprising polysulfide rubber is fully disclosed in co-pending patent application entitled “Golf Ball With Vapor Barrier Layer and Method for Making Same” filed on the same day as the present application and assigned to the same assignee. The disclosure of this co-pending patent application is incorporated herein by reference. [0038]
  • In accordance to another aspect of the present invention, suitable IR-cured water vapor barrier polymers include single-pack castable polymers. A preferred single-pack polymer uses uretdiones or blocked isocyanates to form a single-pack urethane component. The single-pack blocked isocyanate system, which preferably comprises isocyanate combined with an amine or poloyl, is advantageously stable at room temperature. The application of heat, such as infrared radiation, causes the isocyanate to become unblocked or to react to form a urethane. No mixing or dynamically controlling the ratios of the components is required. [0039]
  • Uretdione castable materials can be pre-formulated as a single-pack system without premature reaction. The mixed single-pack material can be directly injected or poured into a mold, avoiding metering and mixing of multiple components. Parts can be made utilizing viscous or solid materials that previously could not be used with traditional two-pack systems. Advantageously, uretdiones and blocked isocyanates when combined with suitable reactive components can be milled into rubber stock for use with other manufacturing techniques, discussed above. [0040]
  • A non-limiting example of a single-pack system in accordance to the present invention is as follows. Finely ground uretdione is dispersed in a liquid polyol or polyamine in combination with a tin catalyst and cyclic amidine catalyst. A slurry is created. The slurry mixture is poured into a suitable golf ball mold to make the required part, e.g., core, intermediate layer or cover. The mold is then heated to reach the predetermined deblocking temperature of about 150-180° C., and the reaction is allowed sufficient time to complete. The cured component then can be removed from the mold for further processing, if necessary. [0041]
  • In another example, 3,5 dimethylpyrazole (DMP) blocked-IPDI is used in place of the uretdione in the above example. The mold is then heated to the deblocking temperature of about 140-160° C., and the reaction is allowed sufficient time to complete. In another non-limiting example, the single-pack moisture vapor barrier layer utilizes blocked isocyanates that volatilize when de-blocking occurs, such as diethylmaleonate (DEM) or methyl ethyl ketoxime (MEKO) blocked hexamethylene diisocyanate cyclic trimer. Such an example could be sprayed or dipped onto the golf ball core, subassembly or the like and then followed with an IR cure. [0042]
  • Non-limiting chemical structures of the single-pack system are shown below: [0043]
  • Formation of uretdiones: [0044]
    Figure US20030069085A1-20030410-C00001
  • Preferred chemical structure of polyuretdione cross-linker: [0045]
    Figure US20030069085A1-20030410-C00002
  • The preferred hardeners are uretdiones or a blocked isocyanates, where the blocking agent remains in the component as a solid once cast, such as DMP or triazole blocked isocyanates. The structures of the preferred blocking agents are: [0046]
    Figure US20030069085A1-20030410-C00003
  • Single-pack castable water vapor barrier material is fully disclosed in parent application Ser. No. 09/973,342, which has been incorporated by referenced. [0047]
  • In accordance to one aspect of the invention, the Shore D hardness values for the core and moisture vapor barrier sub-assemblies have been measured less than about 60 and more specifically in the range of about 5-50. Alternatively, according to other aspects of the invention, the moisture barrier sub-assemblies may have Shore D hardness value of greater than 50, when more rigid materials, such as stiff ionomer with a Shore D hardness of greater than 55 are used in conjunction with the moisture [0048] vapor barrier layer 14.
  • Preferably, a golf ball in accordance to the present invention comprises a solid or multiple-layer [0049] solid polybutadiene core 12 having an outer diameter of greater than about 1.50 inches, more preferably 1.550 inches and most preferably about 1.580 inches. Moisture vapor barrier layer 14 has a thickness preferably in the range of about 0.001 inch to about 0.100 inch, more preferably in range of about 0.010 inch to about 0.050 inch and cover 16 is a urethane cover with sufficient thickness to produce a 1.680 inch diameter golf ball.
  • More preferably, the moisture vapor barrier layer is a thin layer of suitable butyl rubber polymers discussed above, preferably less than 0.050 inch, more preferable less than 0.030 inch and most preferably less than 0.010 inch. It is also preferable that the butyl rubber moisture vapor barrier layer would not significantly and negatively affect the coefficient of restitution of the golf ball. Preferably, the [0050] polybutadiene core 12 and the thin butyl rubber moisture vapor barrier layer 14 are covered by a relatively soft polymer cover having a thickness from about 0.010 to about 0.050 inch, more preferably about 0.030 inch and has a Shore D of less than 65 or from about 30 to about 60, more preferably from about 35 to about 50 and even more preferably about 40 to about 45. Such a cover is fully disclosed in U.S. Pat. Nos. 5,885,172 and 6,132,324. The disclosures of these two patents are incorporated herein by reference in their entireties. Preferred cover polymers include thermoset urethanes and polyurethanes, thermoset urethane ionomers and thermoset urethane epoxies.
  • In accordance to yet another aspect of the invention, as shown in FIG. 3 [0051] golf ball 20 may have multiple layer core 12 a, 12 b and 12 c, surrounded by intermediate layer 14 and dimpled cover 16. Core layers 12 b and 12 c may be an integral solid layer or discrete layers molded on each other. Alternatively, both outer core layers 12 b and 12 c could be wound layers, or one of these two layers may be a wound layer, and the innermost core 12 a may be liquid-filled.
  • While various descriptions of the present invention are described above, it is understood that the various features of the present invention can be used singly or in combination thereof. Therefore, this invention is not to be limited to the specifically preferred embodiments depicted therein. [0052]

Claims (60)

What is claimed is:
1. A golf ball comprising a core, a moisture vapor barrier layer and a cover, wherein the moisture barrier layer has a moisture vapor transmission rate that is lower than that of the cover and wherein the moisture vapor barrier layer comprises butyl rubber.
2. The golf ball of claim 1, wherein the butyl rubber comprises a halogenated butyl rubber.
3. The golf ball of claim 2, wherein the halogenated butyl rubber is a bromobutyl rubber.
4. The golf ball of claim 2, wherein the halogenated butyl rubber is a chlorobutyl rubber.
5. The golf ball of claim 1, wherein the butyl rubber is a sulfonated butyl rubber.
6. The golf ball of claim 2, wherein the halogenated butyl rubber is blended with a double bond-vulcanizable rubber.
7. The golf ball of claim 6, wherein the core comprises a diene rubber.
8. The golf ball of claim 7, wherein the core comprises a polybutadiene rubber.
9. The golf ball of claim 1, wherein the moisture vapor transmission rate of the moisture vapor barrier layer is less than the moisture vapor transmission rate of ionomer resin.
10. The golf ball of claim 1, wherein the moisture vapor transmission rate of the moisture vapor barrier layer is less than about 0.6 grams·mM/m2·day.
11. The golf ball of claim 1, wherein the moisture barrier layer comprises filler.
12. The golf ball of claim 11, wherein the filler is selected from a group consisting of aluminum, mica, micaceous iron oxide, metal, ceramic and graphite.
13. The golf ball of claim 1, wherein the butyl rubber is blended with ethylene propylene diene monomer rubber.
14. The golf ball of claim 1, wherein the butyl rubber is blended with vinylidene chloride polymer.
15. A golf ball comprising a core, a moisture vapor barrier layer and a cover, wherein the moisture barrier layer has a moisture vapor transmission rate that is lower than that of the cover and wherein the moisture vapor barrier comprises a brominated polymer, wherein the brominated polymer comprises a copolymer of isobutylene and p-methylstyrene.
16. The golf ball of claim 15, wherein the brominated polymer is blended with a double bond-vulcanizable rubber.
17. The golf ball of claim 16, wherein the core comprises a diene rubber.
18. The golf ball of claim 17, wherein the core comprises a polybutadiene rubber.
19. The golf ball of claim 15, wherein the moisture vapor transmission rate of the moisture vapor barrier layer is lower than the moisture vapor transmission rate of ionomer resin.
20. The golf ball of claim 1, wherein the moisture vapor transmission rate of the moisture vapor barrier layer is less than about 0.6 grams·mm/m2·day.
21. The golf ball of claim 1, wherein the moisture barrier layer comprises filler.
22. The golf ball of claim 21, wherein the filler is selected from a group consisting of aluminum, mica, micaceous iron oxide, metal, ceramic and graphite.
23. A golf ball comprising a core, a moisture vapor barrier layer and a cover, wherein the moisture barrier layer has a moisture vapor transmission rate that is lower than that of the cover and wherein the moisture vapor barrier comprises polyisobutylene.
24. A golf ball comprising a core subassembly, an outer layer encasing the core subassembly, wherein the outer layer comprises a polymer having a crosslinking temperature that is higher than the softening temperature of a portion of the core subassembly.
25. The golf ball of claim 24, wherein the crosslinking temperature is higher than the melting temperature of a portion of the core subassembly.
26. The golf ball of claim 24, wherein the core subassembly comprises a core.
27. The golf ball of claim 26, wherein the core subassembly further comprises at least an intermediate layer encasing the core.
28. The golf ball of claim 24, wherein the outer layer is a cover layer.
29. The golf ball of claim 24, wherein the outer layer is an intermediate layer.
30. The golf ball of claim 24, wherein the outer layer is a moisture vapor barrier layer.
31. The golf ball of claim 24, wherein the outer layer is cured by infrared radiation.
32. A golf ball comprising a core and a moisture vapor barrier layer and a cover, wherein the moisture barrier layer has a moisture vapor transmission rate that is lower than that of the cover and wherein the moisture vapor barrier layer is cured by infrared radiation.
33. The golf ball of claim 32, wherein the moisture vapor barrier layer comprises butyl rubber.
34. The golf ball of claim 33, wherein the butyl rubber is a halogenated butyl rubber.
35. The golf ball of claim 33, wherein the butyl rubber is a sulfonated butyl rubber.
36. The golf ball of claim 32, wherein the moisture vapor barrier layer comprises polysulfide rubber.
37. The golf ball of claim 32, wherein the moisture vapor barrier layer comprises a single-pack castable polymer.
38. The golf ball of claim 37, wherein the single-pack castable isocyanate comprises uretdione moiety.
39. The golf ball of claim 38, wherein the isocyanate is blended with an amine or polyol.
40. The golf ball of claim 37, wherein the single-pack castable isocyanate comprises blocked isocyanate.
41. The golf ball of claim 40, wherein the isocyanate is blended with an amine or polyol.
42. The golf ball of claim 37, wherein the single-pack castable polymer comprises 3,5 dimethylpyrazole (DMP) blocked-IPDI.
43. The golf ball of claim 1, wherein the cover has a Shore D hardness of less than about 65.
44. The golf ball of claim 43, wherein the cover has a Shore D hardness between about 30 and about 60.
45. The golf ball of claim 44, wherein the cover has a Shore D hardness between about 35 and about 50.
46. The golf ball of claim 45, wherein the cover has a Shore D hardness between about 40 and about 45.
47. The golf ball of claim 1, wherein the cover has a thickness between about 0.010 inch to about 0.050 inch.
48. The golf ball of claim 47, wherein the cover has a thickness of about 0.030.
49. The golf ball of claim 1, wherein the cover comprises a thermoset polymer.
50. The golf ball of claim 49, wherein the thermoset polymer is thermoset polyrrethane.
51. The golf ball of claim 49, wherein the thermoset polymer is thermoset polyurethane ionomer.
52. The golf ball of claim 49, wherein the thermoset polymer is thermoset polyurethane epoxy.
53. The golf ball of claim 1, wherein the cover comprises thermoplastic polyurethane.
54. The golf ball of claim 1, wherein the core comprises polybutadiene.
55. The golf ball of claim 1, wherein the core comprises a polymer, wherein the polymer is selected from a group consisting of natural rubber, polyisoprene, styrene-butadiene rubber, styrene-propylene-diene rubber, ionomer resin, polyamide, polyester, polyether amide copolymer, polyether ester copolymer, thermoplastic urethane, styrenic block copolymers elastomer, urethane, polyurea, epoxy, silicone, IPN, reaction injection molded polyurethane, and reaction injection molded polyurea.
56. The golf ball of claim 1, wherein the moisture vapor barrier layer is formed by spraying.
57. The golf ball of claim 1, wherein the moisture vapor barrier layer is formed by dipping.
58. The golf ball of claim 1, wherein the moisture vapor barrier layer is formed by casting.
59. The golf ball of claim 1, wherein the moisture vapor barrier layer is formed by compression molding.
60. The golf ball of claim 1, wherein the moisture vapor barrier layer is formed by injection molding.
US10/103,414 2001-10-09 2002-03-21 Golf ball with vapor barrier layer and method of making same Abandoned US20030069085A1 (en)

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US10/754,781 US6932720B2 (en) 2001-10-09 2004-01-09 Golf ball with vapor barrier layer and method of making same
US10/755,638 US7357733B2 (en) 2001-10-09 2004-01-12 Golf ball with vapor barrier layer and method of making same
US11/083,453 US7182702B2 (en) 2001-10-09 2005-03-18 Golf ball with vapor barrier layer and method of making same
US11/350,989 US20060128505A1 (en) 2001-10-09 2006-02-09 Golf ball layers having improved barrier properties
US11/560,926 US7951015B2 (en) 2001-10-09 2006-11-17 Multilayer golf ball containing at least three core layers, at least one intermediate barrier layer, and at least one cover layer
US13/084,044 US8251839B2 (en) 2001-10-09 2011-04-11 Multilayer golf ball containing at least three core layers, at least one intermediate barrier layer, and at least one cover layer
US13/567,148 US8454455B2 (en) 2001-10-09 2012-08-06 Multilayer golf ball containing at least three core layers, at least one intermediate barrier layer, and at least one cover layer

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030209840A1 (en) * 2002-05-08 2003-11-13 Hogge Matthew F. Infrared heating method for creating cure gradients in golf balls and golf ball cores
US20040048688A1 (en) * 2001-10-09 2004-03-11 Hogge Matthew F. Golf ball with vapor barrier layer and method of making same
US20060083863A1 (en) * 2004-10-18 2006-04-20 Christopher Cavallaro Golf ball having sprayed layer of liquid polybutadiene
US20060122011A1 (en) * 2002-05-08 2006-06-08 Hogge Matthew F Infrared heating method for creating cure gradients in golf balls and golf ball cores
US20070129510A1 (en) * 2005-12-06 2007-06-07 Acushnet Company Golf ball layer compositions formed from oxirane functional endcapped polymers
US20100248862A1 (en) * 2009-03-30 2010-09-30 Sullivan Michael J Golf ball having moisture barrier layers made from polyolefin compositions
US20130217516A1 (en) * 2011-12-16 2013-08-22 Bridgestone Sports Co., Ltd. Golf ball
US8920264B2 (en) 2010-07-21 2014-12-30 Nike, Inc. Golf ball and method of manufacturing a golf ball
US9033824B2 (en) 2011-12-16 2015-05-19 Bridgestone Sports Co., Ltd. Golf ball
US9050500B2 (en) 2011-12-16 2015-06-09 Bridgestone Sports Co., Ltd. Golf ball
US9427629B1 (en) 2015-03-25 2016-08-30 Acushnet Company Golf ball incorporating a thin moisture barrier layer
USD823956S1 (en) * 2017-05-19 2018-07-24 Nexen Corporation Golf ball
US10046205B1 (en) * 2017-03-23 2018-08-14 Acushnet Company Golf ball incorporating thin thermoformed pre-form(s) having low normalized moisture vapor transmission rate
USD831138S1 (en) * 2017-03-21 2018-10-16 Foremost Golf Mfg., Ltd. Golf ball
US10150009B2 (en) 2017-03-23 2018-12-11 Acushnet Company Golf ball incorporating thin moisture barrier film having low normalized moisture vapor transmission rate
USD868912S1 (en) * 2017-05-09 2019-12-03 Volvik, Inc. Golf ball
US10752806B2 (en) 2014-06-18 2020-08-25 Ppg Industries Ohio, Inc. Elastic gas barrier coating compositions
US11819739B2 (en) 2021-07-12 2023-11-21 Acushnet Company Golf ball and method of making same

Families Citing this family (89)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8066928B2 (en) * 2001-01-24 2011-11-29 Acushnet Company Method of providing a moisture vapor barrier layer to a core of a golf ball
US20080315469A1 (en) * 2007-06-22 2008-12-25 Hogge Matthew F Method of providing a moisture vapor barrier layer to a core of a golf ball
US20060211518A1 (en) * 2001-06-26 2006-09-21 Sullivan Michael J Multi-Layer Golf Balls Comprising Ionomers with a Percent Neutralization Gradient
US20060128505A1 (en) * 2001-10-09 2006-06-15 Sullivan Michael J Golf ball layers having improved barrier properties
US7951015B2 (en) * 2001-10-09 2011-05-31 Acushnet Company Multilayer golf ball containing at least three core layers, at least one intermediate barrier layer, and at least one cover layer
US20030069085A1 (en) * 2001-10-09 2003-04-10 Hogge Matthew F. Golf ball with vapor barrier layer and method of making same
US20100304895A1 (en) * 2001-11-28 2010-12-02 Brian Comeau Multi-layer golf balls having moisture barrier layers based on polyalkenamer compositions
US20070155542A1 (en) * 2002-05-08 2007-07-05 Sullivan Michael J Gold ball having a foamed layer created by infrared radiation
US7238122B2 (en) * 2002-08-27 2007-07-03 Acushnet Company Ormocer composites for golf ball components
US8152653B2 (en) 2004-05-07 2012-04-10 Acushnet Company Thick inner cover multi-layer golf ball
US20080153629A1 (en) * 2004-05-07 2008-06-26 Sullivan Michael J Thick Outer Cover Layer Golf Ball
US7537530B2 (en) * 2007-07-03 2009-05-26 Acushnet Company Golf ball with negative hardness gradient core
US7537529B2 (en) * 2007-07-03 2009-05-26 Acushnet Company Golf ball with negative hardness gradient core
US7261647B2 (en) * 2005-02-18 2007-08-28 Acushnet Company Nano-particulate compositions for decreasing the water vapor transmission rate of golf ball layers
US7636339B2 (en) * 2005-08-10 2009-12-22 Cisco Technology, Inc. Method and system for automatic configuration of virtual talk groups based on location of media sources
US7744489B2 (en) * 2007-07-03 2010-06-29 Acushnet Company Multi-layer core golf ball having opposing hardness gradient with steep gradient outer core layer
US10029150B2 (en) 2007-07-03 2018-07-24 Acushnet Company Golf ball having medium positive gradient quotient and low trans content
US10252115B2 (en) 2007-07-03 2019-04-09 Acushnet Company Golf ball incorporating positive hardness gradient thermoset polyurethane outer cover layer
US9238160B2 (en) 2007-07-03 2016-01-19 Acushnet Company Method of making color golf ball and resulting color golf ball
US9320944B2 (en) 2007-07-03 2016-04-26 Acushnet Company Multi-layer cover dual core golf ball having a high acid casing and low gradient center
US8500575B2 (en) 2007-07-03 2013-08-06 Acushnet Company Golf ball comprising a core layer having a hardness gradient and trans gradient
US7744490B2 (en) 2007-07-03 2010-06-29 Acushnet Company Golf ball core with soft outer transition volume and negative hardness gradient
US8313395B2 (en) * 2007-07-03 2012-11-20 Acushnet Company Multilayer core golf ball having hardness gradient within and between each core layer
US7429221B1 (en) 2007-07-03 2008-09-30 Acushnet Company Negative hardness gradient outer core layer for dual core golf ball
US8021248B2 (en) 2007-07-03 2011-09-20 Acushnet Company Multilayer core golf ball having hardness gradient within and between each core layer
US8317637B2 (en) * 2007-07-03 2012-11-27 Acushnet Company Multilayer core golf ball having hardness gradient within and between each core layer
US8152655B2 (en) 2007-07-03 2012-04-10 Acushnet Company Multi-piece golf ball comprising low hardness gradient core
US9480881B2 (en) 2007-07-03 2016-11-01 Acushnet Company Golf ball single layer core having a gradient quotient
US9289653B2 (en) 2007-07-03 2016-03-22 Acushnet Company Golf ball with single layer core having specific regions of varying hardness
US7410429B1 (en) 2007-07-03 2008-08-12 Acushnet Company Negative hardness gradient inner core for dual core golf ball
US7815526B2 (en) * 2007-11-14 2010-10-19 Acushnet Company Dual core golf ball having negative-hardness-gradient thermoplastic inner core and steep positive-hardness-gradient thermoset outer core layer
US10112081B2 (en) 2007-07-03 2018-10-30 Acushnet Company Golf ball incorporating positive hardness gradient thermoset polyurethane outer cover layer
US7678312B2 (en) * 2007-07-03 2010-03-16 Acushnet Company Method of treating rubber composition with cure inhibitor to create soft skin in golf ball core
US7909709B2 (en) * 2007-07-03 2011-03-22 Acushnet Company Multi-layer core golf ball having opposing hardness gradient with steep gradient inner core layer
US9480882B2 (en) 2007-07-03 2016-11-01 Acushnet Company Golf ball multilayer core having a gradient quotient
US8821316B2 (en) 2007-07-03 2014-09-02 Acushnet Company Negative hardness gradient cores made of polyalkenamer rubber for golf balls
US7963863B2 (en) * 2007-07-03 2011-06-21 Acushnet Company Golf ball with negative hardness gradient core
US9511264B2 (en) 2007-07-03 2016-12-06 Acushnet Company Multilayer core golf ball having hardness gradient within and between each core layer
US8137214B2 (en) 2007-07-03 2012-03-20 Acushnet Company Dual-core comprising negative gradient center and positive gradient outer core layer
US8313394B2 (en) * 2007-07-03 2012-11-20 Acushnet Company Multilayer core golf ball having hardness gradient within and between each core layer
US7819760B2 (en) * 2007-07-03 2010-10-26 Acushnet Company Golf ball layer having reduced surface hardness and method of making same
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US20090008831A1 (en) * 2007-07-03 2009-01-08 Bulpett David A Negative Hardness Gradient Core Produced from a Low, Time-Based Cure Cycle Index
US9056227B2 (en) 2007-07-03 2015-06-16 Acushnet Company Golf ball comprising a core having a shallow hardness gradient
US20090008832A1 (en) * 2007-07-03 2009-01-08 Bulpett David A Negative Hardness Gradient Core Produced from a Low, Temperature-Based Cure Cycle Index
US9199134B2 (en) 2007-07-03 2015-12-01 Acushnet Company Method of making color golf ball and resulting color golf ball
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US8025594B2 (en) 2009-06-26 2011-09-27 Acushnet Company Golf ball with single layer core having specific regions of varying hardness
US9795836B2 (en) 2007-07-03 2017-10-24 Acushnet Company Golf balls comprising medium hardness gradient core
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US9072944B2 (en) 2007-11-14 2015-07-07 Acushnet Copany Dual core golf ball having a shallow “positive hardness gradient” thermoplastic inner core and a steep “positive hardness gradient” thermoset outer core layer
US9873026B2 (en) 2007-11-14 2018-01-23 Acushnet Company Thermoplastic dual core having positive hardness gradient inner and outer core layers
US9999809B2 (en) 2007-11-14 2018-06-19 Acushnet Company Dual core having thermoplastic inner core, thermoset outer core layer, and positive hardness gradient
US8740725B2 (en) 2007-11-14 2014-06-03 Acushnet Company Dual core golf ball having positive-hardness-gradient thermoplastic inner core and shallow negative-hardness-gradient outer core layer
US9675846B2 (en) 2007-11-14 2017-06-13 Acushnet Company Dual core golf ball having positive-hardness-gradient thermoplastic inner core and positive-hardness-gradient thermoset outer core layer
US9789367B2 (en) 2007-11-14 2017-10-17 Acushnet Company Thermoplastic dual core having a negative gradient inner core and a positive gradient outer core
US9566475B2 (en) 2007-11-14 2017-02-14 Acushnet Company Golf ball having a thermoplastic positive hardness gradient inner core layer and a thermostat shallow positive hardness gradient outer core layer
US7942761B2 (en) * 2007-11-14 2011-05-17 Acushnet Company Dual core golf ball having negative-hardness-gradient thermoplastic inner core and shallow negative-hardness-gradient outer core layer
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US9352194B2 (en) 2007-11-14 2016-05-31 Acushnet Company Dual core golf ball having a shallow “positive hardness gradient” thermoplastic inner core and a steep “positive hardness gradient” thermoset outer core layer
US9433828B2 (en) 2007-11-14 2016-09-06 Acushnet Company Dual core golf ball having negative-hardness-gradient thermoplastic inner core and steep positive-hardness-gradient thermoset outer core layer
US9149689B2 (en) 2007-11-14 2015-10-06 Acushnet Company Dual core golf ball having positive-hardness-gradient thermoplastic inner core and positive-hardness-gradient thermoset outer core layer
US7762910B2 (en) * 2007-11-14 2010-07-27 Acushnet Company Dual core golf ball having negative-hardness-gradient thermoplastic inner core and steep negative-hardness-gradient outer core layer
US8764585B2 (en) 2007-11-14 2014-07-01 Acushnet Company Dual core golf ball having a shallow “positive hardness gradient” thermoplastic inner core and a steep “positive hardness gradient” thermoset outer core layer
US9433829B2 (en) 2007-11-14 2016-09-06 Acushnet Company Dual core golf ball having positive-hardness-gradient thermoplastic inner core and positive-hardness-gradient thermoset outer core layer
US9649538B2 (en) 2013-08-05 2017-05-16 Acushnet Company Multi-layer core golf ball
US9643060B2 (en) 2008-01-10 2017-05-09 Acushnet Company Multi-layer core golf ball
US9717957B2 (en) 2013-08-05 2017-08-01 Acushnet Company Multi-layer core golf ball
US8475297B2 (en) 2011-02-23 2013-07-02 Nike, Inc. Golf ball with carbon dioxide absorbents
US8480516B2 (en) 2011-02-23 2013-07-09 Nike, Inc. Methods for encouraging use of greenhouse gas reducing golf balls
US8915799B2 (en) * 2011-10-06 2014-12-23 Acushnet Company Variable moment of inertia golf ball
US9592425B2 (en) 2012-04-20 2017-03-14 Acushnet Company Multi-layer core golf ball
US9649539B2 (en) 2012-04-20 2017-05-16 Acushnet Company Multi-layer core golf ball
US9643061B2 (en) 2013-08-05 2017-05-09 Acushnet Company Multi-layer core golf ball
US9737764B2 (en) 2013-08-05 2017-08-22 Acushnet Company Multi-layer core golf ball
US9393462B2 (en) 2014-06-30 2016-07-19 Acushnet Company Golf ball with thin moisture vapor barrier layer
USD813326S1 (en) * 2017-01-27 2018-03-20 Callaway Golf Company Golf ball
USD811498S1 (en) * 2017-03-20 2018-02-27 Callaway Golf Company Golf ball
USD811499S1 (en) * 2017-03-24 2018-02-27 Callaway Golf Company Golf ball

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2426916A (en) * 1944-07-25 1947-09-02 Stoner Mudge Inc Process for producing polysulfide rubber of low water permeability
US4955966A (en) * 1987-06-11 1990-09-11 Asics Corporation Rubber composition and golf ball comprising it
US5461135A (en) * 1994-09-23 1995-10-24 Olin Corporation Polyisocyanates containing uretidione and allophanate groups, a process for their production, and their use in one and two component coating compositions
US5521272A (en) * 1993-09-03 1996-05-28 Olin Corporation Isocyanate-crosslinked coatings having reduced yellowing
US5692974A (en) * 1995-06-07 1997-12-02 Acushnet Company Golf ball covers
US5885172A (en) * 1997-05-27 1999-03-23 Acushnet Company Multilayer golf ball with a thin thermoset outer layer
US6245862B1 (en) * 1997-03-13 2001-06-12 Acushnet Company Golf balls comprising sulfonated or phosphonated ionomers
US6287216B1 (en) * 1999-12-03 2001-09-11 Acushnet Company Wound golf ball and method of making same
US20010034398A1 (en) * 2000-03-27 2001-10-25 Takashi Ohira Aqueous coating composition for golf ball and golf ball using the same

Family Cites Families (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2356128A (en) * 1939-10-20 1944-08-22 Jasco Inc Mixed olefinic polymerization process and product
US3099644A (en) * 1959-10-06 1963-07-30 Exxon Research Engineering Co Continuous chlorination and bromination of butyl rubber
US3313545A (en) * 1963-09-12 1967-04-11 Pcr Patent Dev Corp Unitary molded golf ball
US3241834A (en) * 1965-08-25 1966-03-22 Wham O Mfg Company Highly resilient polybutadiene ball
US3502338A (en) * 1967-08-10 1970-03-24 Abbott Lab Golf ball made from a vulcanized elastomer composition
US3642728A (en) * 1968-10-07 1972-02-15 Exxon Research Engineering Co Sulfonated polymers
US3989568A (en) * 1974-11-21 1976-11-02 Acushnet Company Polyurethane covered golf balls
US4123061A (en) * 1976-05-20 1978-10-31 Acushnet Company Ball and process and composition of matter for production thereof
US4141559A (en) * 1976-12-27 1979-02-27 Uniroyal, Inc. Two-piece solid golf ball
US4209485A (en) * 1977-05-03 1980-06-24 Greenspan Donald J Method of making a valve apparatus
US4250273A (en) * 1977-06-13 1981-02-10 The Firestone Tire & Rubber Company Thermoplastic elastomer blends
US4239799A (en) * 1977-12-09 1980-12-16 W. R. Grace & Co. Blends of butyl rubber and polymers of vinylidene chloride
US4165425A (en) * 1978-06-08 1979-08-21 Thiokol Corporation Alkyl tin oxide cured polysulfide rubbers in hot melt applications
US4263078A (en) * 1978-06-08 1981-04-21 Thiokol Corporation Method of making an article comprising polysulfide rubbers
US4265976A (en) * 1978-09-19 1981-05-05 Celanese Corporation Radiation-curable coated article having moisture barrier propetes
JPS5545735A (en) * 1978-09-26 1980-03-31 Osaka Soda Co Ltd Halogen-containing polymer vulcanizing composition
US4229337A (en) * 1978-10-02 1980-10-21 Exxon Research & Engineering Co. Aromatic amide plasticizer for ionic polymers
US4356676A (en) * 1981-09-21 1982-11-02 Norton Company Sealant strip
JPS62137075A (en) * 1984-10-30 1987-06-19 住友ゴム工業株式会社 Multipiece solid golf ball
US4593062A (en) * 1984-12-10 1986-06-03 Exxon Research & Engineering Co. Dynamically cured thermoplastic olefin polymers
US5162445A (en) * 1988-05-27 1992-11-10 Exxon Chemical Patents Inc. Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof
US6013727A (en) * 1988-05-27 2000-01-11 Exxon Chemical Patents, Inc. Thermoplastic blend containing engineering resin
US4995613A (en) * 1988-12-15 1991-02-26 Spin-Alizer Corporation Process for manufacturing practice golf ball
KR920006255B1 (en) * 1990-06-01 1992-08-01 일야실업 주식회사 Three piece solid golf ball
DE69108806T2 (en) 1990-07-20 1995-09-21 Acushnet Co Golf ball made of polyurethane.
US5873796A (en) * 1990-12-10 1999-02-23 Acushnet Company Multi-layer golf ball comprising a cover of ionomer blends
DE4306155A1 (en) * 1993-02-27 1994-09-01 Hoechst Ag Transparent, non-sealable oriented polyolefin multilayer film, process for its production and its use
US5984806A (en) * 1997-01-13 1999-11-16 Spalding Sports Worldwide, Inc. Perimeter weighted golf ball with visible weighting
US5779562A (en) * 1993-06-01 1998-07-14 Melvin; Terrence Multi-core, multi-cover golf ball
CA2116399C (en) * 1993-07-29 2004-04-20 Michael J. Sullivan Golf ball and method for making same
EP0643002B1 (en) * 1993-09-06 1997-10-29 Focke & Co. (GmbH & Co.) Manipulator with telescopic portion
JPH0884788A (en) * 1994-09-20 1996-04-02 Sumitomo Rubber Ind Ltd Thread-wound golf ball
US6079465A (en) * 1995-01-23 2000-06-27 The Yokohama Rubber Co., Ltd. Polymer composition for tire and pneumatic tire using same
US5981654A (en) * 1997-05-23 1999-11-09 Acushnet Company Golf ball forming compositions comprising polyamide
EP0815146B1 (en) 1995-03-20 2001-06-20 Dymax Corporation Encapsulation formulation, method, and apparatus
JP2791943B2 (en) * 1995-04-04 1998-08-27 ブリヂストンスポーツ株式会社 Thread wound golf ball
GB2316880B (en) * 1995-06-07 1999-03-31 Acushnet Co Urethane golf ball covers using epoxy curing agents
US5965669A (en) * 1995-06-07 1999-10-12 Acushnet Company Multi-layer golf ball and composition
JP2787011B2 (en) * 1995-06-28 1998-08-13 ブリヂストンスポーツ株式会社 Thread wound golf ball
US5506014A (en) * 1995-09-01 1996-04-09 Eastman Chemical Company Pet copolyesters containing succinic and naphthalenedicarboxylic acid moieties having improved barrier properties
US5882567A (en) * 1996-02-16 1999-03-16 Acushnet Company Method of making a golf ball having multiple layers
US5919100A (en) * 1996-03-11 1999-07-06 Acushnet Company Fluid or liquid filled non-wound golf ball
DE69737185T2 (en) * 1996-05-29 2007-11-08 The Yokohama Rubber Co., Ltd. METHOD FOR PRODUCING AIR TIRES USING LOW-PERMEABLE THERMOPLASTIC ELASTOMER COMPOSITION IN A GAS PERFORATED LAYER
EP0819732B1 (en) * 1996-07-15 2005-06-15 Sumitomo Rubber Industries Ltd. Rubber composition
JP3125722B2 (en) * 1996-10-28 2001-01-22 ブリヂストンスポーツ株式会社 Multilayer solid golf ball
JPH10127821A (en) * 1996-11-06 1998-05-19 Sumitomo Rubber Ind Ltd Multi-piece solid golf ball
US6001930A (en) * 1997-03-13 1999-12-14 Acushnet Company Golf ball forming compositions comprising polyamide blended with sulfonated or phosphonated polymers
US5875891A (en) * 1997-05-09 1999-03-02 Taylor Made Golf Company, Inc. Packaging for golf balls
US6045460A (en) * 1997-05-29 2000-04-04 Bridgestone Sports Co., Ltd. Multi-piece solid golf ball
US6232389B1 (en) * 1997-06-09 2001-05-15 Inmat, Llc Barrier coating of an elastomer and a dispersed layered filler in a liquid carrier and coated articles
JP3909127B2 (en) * 1997-09-18 2007-04-25 ブリヂストンスポーツ株式会社 Golf ball
BR9806292A (en) * 1997-10-03 2001-09-18 Kimberly Clark Co Highly improved elastic composite materials made of thermoplastic triblock elastomers
JP4038625B2 (en) * 1997-12-17 2008-01-30 ブリヂストンスポーツ株式会社 Solid golf ball and method for producing solid golf ball
JPH11253580A (en) * 1998-03-16 1999-09-21 Bridgestone Sports Co Ltd Multi-piece solid golf ball
GB9905914D0 (en) * 1998-03-16 1999-05-05 Bridgestone Sports Co Ltd Multi-piece solid golf ball
JP3221390B2 (en) * 1998-03-16 2001-10-22 ブリヂストンスポーツ株式会社 Multi-piece solid golf ball
DE19813270A1 (en) * 1998-03-25 1999-09-30 Hoechst Diafoil Gmbh Polyester film with high oxygen barrier and improved adhesion to metal layers, process for their production and their use
US6653382B1 (en) 1999-10-21 2003-11-25 E. I. Du Pont De Nemours And Company Highly-neutralized ethylene copolymers and their use in golf balls
CA2342763A1 (en) 1998-10-21 2000-04-27 E.I. Du Pont De Nemours And Company Highly-resilient thermoplastic elastomer compositions
US6113505A (en) * 1998-12-22 2000-09-05 Acushnet Company Wound golf ball with multi-ply thread
US6030296A (en) * 1999-02-26 2000-02-29 Acushnet Company Wound golf ball
US6174388B1 (en) * 1999-03-15 2001-01-16 Lockheed Martin Energy Research Corp. Rapid infrared heating of a surface
US6117024A (en) * 1999-04-20 2000-09-12 Callaway Golf Company Golf ball with polyurethane cover
US6180715B1 (en) * 1999-09-03 2001-01-30 The Dow Chemical Company Aqueous solution and dispersion of an acid salt of a polyetheramine
US6354965B1 (en) * 2000-02-02 2002-03-12 Acushnet Company Golf balls including low water activity fluid and methods for making same
US6398668B1 (en) * 2000-08-07 2002-06-04 Callaway Golf Company Golf ball with an oxygen barrier
US6479162B1 (en) * 2000-09-29 2002-11-12 Cryovac, Inc. Vinylidene chloride polymer composition and film
US20030069085A1 (en) * 2001-10-09 2003-04-10 Hogge Matthew F. Golf ball with vapor barrier layer and method of making same
US6632147B2 (en) 2001-10-09 2003-10-14 Acushnet Company Golf ball with vapor barrier layer and method of making same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2426916A (en) * 1944-07-25 1947-09-02 Stoner Mudge Inc Process for producing polysulfide rubber of low water permeability
US4955966A (en) * 1987-06-11 1990-09-11 Asics Corporation Rubber composition and golf ball comprising it
US5521272A (en) * 1993-09-03 1996-05-28 Olin Corporation Isocyanate-crosslinked coatings having reduced yellowing
US5461135A (en) * 1994-09-23 1995-10-24 Olin Corporation Polyisocyanates containing uretidione and allophanate groups, a process for their production, and their use in one and two component coating compositions
US5692974A (en) * 1995-06-07 1997-12-02 Acushnet Company Golf ball covers
US6245862B1 (en) * 1997-03-13 2001-06-12 Acushnet Company Golf balls comprising sulfonated or phosphonated ionomers
US5885172A (en) * 1997-05-27 1999-03-23 Acushnet Company Multilayer golf ball with a thin thermoset outer layer
US6287216B1 (en) * 1999-12-03 2001-09-11 Acushnet Company Wound golf ball and method of making same
US20010034398A1 (en) * 2000-03-27 2001-10-25 Takashi Ohira Aqueous coating composition for golf ball and golf ball using the same

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040048688A1 (en) * 2001-10-09 2004-03-11 Hogge Matthew F. Golf ball with vapor barrier layer and method of making same
US7004854B2 (en) 2001-10-09 2006-02-28 Acushnet Company Golf ball with vapor barrier layer and method of making same
US20060122011A1 (en) * 2002-05-08 2006-06-08 Hogge Matthew F Infrared heating method for creating cure gradients in golf balls and golf ball cores
US7670542B2 (en) * 2002-05-08 2010-03-02 Acushnet Company Infrared heating method for creating cure gradients in golf balls and golf ball cores
US20030209840A1 (en) * 2002-05-08 2003-11-13 Hogge Matthew F. Infrared heating method for creating cure gradients in golf balls and golf ball cores
US20060083863A1 (en) * 2004-10-18 2006-04-20 Christopher Cavallaro Golf ball having sprayed layer of liquid polybutadiene
US20070129510A1 (en) * 2005-12-06 2007-06-07 Acushnet Company Golf ball layer compositions formed from oxirane functional endcapped polymers
US7517943B2 (en) 2005-12-06 2009-04-14 Acushnet Company Golf ball layer compositions formed from oxirane functional endcapped polymers
US20100248862A1 (en) * 2009-03-30 2010-09-30 Sullivan Michael J Golf ball having moisture barrier layers made from polyolefin compositions
US8303436B2 (en) 2009-03-30 2012-11-06 Acushnet Company Golf ball having moisture barrier layers made from polyolefin compositions
US8920264B2 (en) 2010-07-21 2014-12-30 Nike, Inc. Golf ball and method of manufacturing a golf ball
US20130217516A1 (en) * 2011-12-16 2013-08-22 Bridgestone Sports Co., Ltd. Golf ball
US9033824B2 (en) 2011-12-16 2015-05-19 Bridgestone Sports Co., Ltd. Golf ball
US9050500B2 (en) 2011-12-16 2015-06-09 Bridgestone Sports Co., Ltd. Golf ball
US10752806B2 (en) 2014-06-18 2020-08-25 Ppg Industries Ohio, Inc. Elastic gas barrier coating compositions
US9427629B1 (en) 2015-03-25 2016-08-30 Acushnet Company Golf ball incorporating a thin moisture barrier layer
USD831138S1 (en) * 2017-03-21 2018-10-16 Foremost Golf Mfg., Ltd. Golf ball
US10046205B1 (en) * 2017-03-23 2018-08-14 Acushnet Company Golf ball incorporating thin thermoformed pre-form(s) having low normalized moisture vapor transmission rate
US10150009B2 (en) 2017-03-23 2018-12-11 Acushnet Company Golf ball incorporating thin moisture barrier film having low normalized moisture vapor transmission rate
USD868912S1 (en) * 2017-05-09 2019-12-03 Volvik, Inc. Golf ball
USD823956S1 (en) * 2017-05-19 2018-07-24 Nexen Corporation Golf ball
US11819739B2 (en) 2021-07-12 2023-11-21 Acushnet Company Golf ball and method of making same

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US7182702B2 (en) 2007-02-27
US6932720B2 (en) 2005-08-23
US20040142769A1 (en) 2004-07-22
US20050164810A1 (en) 2005-07-28
US20040185963A1 (en) 2004-09-23

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