JP5044369B2 - Multilayer golf ball comprising at least three core layers, at least one intermediate barrier layer, and at least one cover layer - Google Patents

Description

  The present invention relates to a multi-layer golf ball having varying hardness over at least three layers of a core.

  This non-provisional patent application is a continuation-in-part of pending US patent application 11 / 083,453 filed March 18, 2005, which is filed January 9, 2004, US patent application 10 / 754,781. This is a continuation of what is currently patented as US Pat. No. 6,932,720, which is a continuation of US patent application 10 / 103,414, now abandoned on March 21, 2002. This is a partial continuation of what was filed on October 9, 2001 and is currently patented as US Pat. No. 6,632,147. The contents of these parent applications and patents are incorporated herein by reference.

  Solid core golf balls are known in the art. Generally, the core is made of a polybutadiene rubber material, which provides the primary source of golf ball resilience. US Pat. Nos. 3,241,834 (Patent Document 1) and 3,313,545 (Patent Document 2) disclose early work on polybutadiene chemistry. It is also known in the art that increasing the crosslink density of the polybutadiene increases the resilience of the core. The core is typically protected by a cover from repeated impacts by the golf club. The golf ball may include an additional layer that can be an outer core or an inner cover layer. One or more of these additional layers may be wound layers of stretched elastic windings to increase the resilience of the ball.

  A known disadvantage of polybutadiene cores crosslinked with peroxides and / or zinc diacrylate is that the material is adversely affected by moisture. Water vapor reduces the resilience of the core and degrades its properties. The polybutadiene core absorbs moisture and loses its resilience. Therefore, these cores must be covered quickly in order to maintain optimal ball characteristics. The cover is generally made of ionomer resin, balata and urethane, or other materials. Ionomer covers, especially hard ionomers, provide some protection against water vapor ingress. However, it is quite difficult to control or give the spin of a ball with a hard cover. Ordinary urethane covers, on the other hand, provide good ball control but are less water vapor resistant than ionomer covers.

  When exposed to high humidity and elevated temperatures for a long period of time, water vapor enters the core of commercially available golf balls. For example, for 60 days at 43.3 ° C. (110 ° F.) and 90% humidity, a significant amount of moisture enters the core and the initial velocity of the ball is 0.54 m (1.8 ft) / s to 1.2 m ( Decelerate at 4.0 ft) / s or higher. The change in compression varies from 5 PGA to about 10 PGA or more. The absorbed moisture also reduces the coefficient of restitution (CoR) of the ball.

  Several prior patents address this moisture absorption problem. US Pat. No. 5,820,488 discloses a golf ball having 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 the water vapor transmission rate 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 the 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 describe, for example, polybutadiene or wound with an ionomer resin inner cover and a relatively soft outer cover. A golf ball having an attached core is disclosed. The hard ionomer inner cover provides some resistance to water vapor penetration and the soft outer cover provides the desired ball control. It is also desirable to minimize the moisture barrier layer so that other properties of the ball are not affected. In addition, US Pat. No. 5,875,891 discloses an impervious packing for golf balls. This impermeable packing acts as a moisture barrier that limits moisture absorption by the golf ball during storage.

  The water vapor barrier layer disclosed in the prior patents is often hard and hardens the ball. Furthermore, manufacturing a hard layer is a manufacturing obstacle. On the other hand, less rigid polymers, such as butyl rubber and other rubbers, are known to have low permeability to air, gas, and water vapor. Butyl rubber is widely used as a sealant for roofs, inner liners for tubeless tires, and linings for chemical tanks. In the golf ball industry, the use of scattered rubber has been limited to practice balls, or practice field balls, due to their low initial speed and low CoR. This is discussed in U.S. Pat. Nos. 5,209,485 (Patent Document 7) and 4,995,613 (Patent Document 8). Butyl rubber is also used for the innermost cover layer, i.e. part of the cover, due to its durability, which is described in U.S. Pat. Nos. 5,873,796 and 5,882. No. 567 (Patent Document 10) and others. However, until now, it has not been possible to make golf balls of higher performance by using the advantages of butyl rubber as a water vapor barrier for golf balls.

  It is also difficult to form a water vapor barrier layer or other outer layer on a golf ball by curing a predetermined polymer material at a high temperature. This is because such curing or crosslinking heats the entire golf ball subassembly. The heating method degrades unintended parts in the subassembly. In addition, this curing method constrains the appropriate outer layer material to a material that has a lower curing temperature than the softening temperature or lower melting temperature of the inner layer or core.

Accordingly, there remains a need for golf balls that have an improved water vapor barrier layer and that change the hardness within the core of the golf ball.
US Pat. No. 3,241,834 U.S. Pat. No. 3,313,545 US Pat. No. 5,820,488 US Pat. No. 5,885,172 US Pat. No. 6,132,324 US Pat. No. 5,875,891 US Pat. No. 5,209,485 US Pat. No. 4,995,613 US Pat. No. 5,873,796 US Pat. No. 5,882,567

  This is the same as in the claims and description.

  The present invention is directed to a multi-layer golf ball having at least three core layers, at least one cover layer, and at least one intermediate layer between the core and the cover layer that serves as a vapor barrier layer. As employed herein, a golf ball subassembly has at least an inner core and may further include one or more outer core layers, an intermediate layer, and an outer cover. An optional layer subassembly is the layer plus all the inner layers below the layer.

  As generally shown in FIGS. 1 and 2, like numerals represent like parts and reference numeral 10 generally represents a golf ball according to the present invention. The golf ball 10 preferably has a solid core 12, a mid layer 14 and a cover 16. The solid core 12 has one innermost spherical element and may have at least two additional core layers surrounding the spherical element. The solid core 12 can be made from any suitable core material, such as thermosetting plastics such as natural rubber, polybutadiene (PBD), polyisoprene, styrene-butadiene or styrene-propylene-diene rubber, and thermoplastics. For example, ionomer resins, polyamides, polyesters, or thermoplastic elastomers. Suitable thermoplastic elastomers may include Pebax ™, which is believed to have a polyetheramide copolymer, Hytrel ™, which is believed to have a polyetherester copolymer, a thermoplastic urethane, and a styrene block copolymer elastomer. Kraton (TM), which are listed in Elf-Atochem, E.I. I. Du Pont de Nemours and Co. , Various manufacturers, and Shell Chemical Co. Each of which is commercially available. The core material can also be formed from a castable material. Suitable castable materials include urethane, polyurea, epoxy, silicone, IPN and the like.

  In addition, suitable core materials also include at least one component of the polyurethane, generally a pre-press, prior to injecting the component into a closed mold that results in a complete reaction and a cured polymer having a reduced specific gravity. Examples include polyurethanes or polyureas that are reaction injection molded, including those versions called nucleation, in which a gas, typically nitrogen, is bubbled into the polymer. These materials are referred to as reaction injection molding (RIM) materials.

  For example, when the core 12 includes multiple layers, as in FIG. 3, it is preferred that the multiple layers have a gradient in physical / mechanical properties, such as hardness, from the outermost to the innermost layer. Or increase from the outermost to the innermost layer. The characteristic gradient will be described in more detail below.

  The cover 16 is preferably strong and cut resistant and is selected from conventional materials used as golf ball covers based on the desired performance characteristics. The cover may include one or more layers. Suitable cover materials include ionomer resins such as Surlyn ™ commercially available from DuPont, blends of ionomer resins, thermoplastic or thermoset urethanes, acrylic acid, methacrylic acid, and an elastic central block of molecules that are unsaturated. Mention may be made of rubber or saturated olefin rubbers, for example thermoplastic rubber polymers consisting of block copolymers such as Kraton ™ rubber commercially available from Shell Chemical, polyethylene and synthetic or natural vulcanizates such as balata.

  In addition, other suitable cover and core materials are disclosed in US Pat. No. 5,919,100 and International Publication Nos. WO00 / 23519 and WO01 / 29129. These disclosures are incorporated by reference in their entirety. Preferably, the core 12 is made of a polybutadiene rubber material and the cover 16 is made of a composition comprising a thermosetting or thermoplastic urethane or a composition comprising an ionomer resin.

In order to prevent or minimize the ingress of moisture, generally water vapor, into the golf ball core 12, the intermediate layer 14 is preferably a water vapor barrier layer disposed directly around the core 12. Preferably, the water vapor barrier layer 14 has a water vapor transmission rate that is lower than the water vapor transmission rate of the cover, more preferably from about 0.45 to about 0.95 g · mm / m 2 of an ionomer resin, such as Surlyn ™. -It has a water vapor transmission rate lower than the water vapor transmission rate in the day range. Typically, the ionomer resin has a water vapor transmission rate of less than 0.6 g · mm / m ² · day, as reported in “Permeability and pptger Film Properties of Plastic Elastmer” published by Plastic Design Library (1995). Has been. The water vapor transmission rate is defined as the mass of water vapor that diffuses into a given thickness of material per unit area per unit time. Preferred criteria for measuring water vapor permeability, ASTM F1249-90 "Standard Test Method for Water Vapor Transmission Rate Through Plastic Film and Sheeting Using a Modulated Infrared Sensor" and ASTM F372-99 "Standard Test Method for Water Vapor Transmission Rate of FlexibleBarrier Materials Using an Infrared Detection Technique ”.

  A preferred polymer for the water vapor barrier layer is butyl rubber. Butyl rubber (IIR) is an elastomeric copolymer of isobutylene and isoprene. A detailed discussion of butyl rubber is found in U.S. Pat. Nos. 3,642,728 and 3,099,644, the contents of which are hereby incorporated by reference. Butyl rubber is an amorphous, nonpolar polymer that has oxidation and thermal stability, good permanent flexibility, and high water vapor and gas resistance. Generally, butyl rubber is about 70% to 99.5% by weight of an isoolefin containing about 4 to 7 carbon primitives, such as isobutylene, and about 0.5% to 30% by weight of about 4%. A conjugated multiolefin containing 14 carbon atoms, for example a copolymer with isoprene. The resulting copolymer comprises from about 85% to about 99.8% by weight bound isoolefin and 0.2% to 15% by weight bound multiolefin. Commercially available butyl rubber, such as that manufactured by ExxonMobil Chemical Company, typically has about 1 to 2.5 mole percent isoprene. The molecular weight of butyl rubber is generally about 20,000 to about 500,000. A suitable butyl rubber is also available from United Coaning under the Elastron ™ trade name, which is a butyl rubber coating applied as a solution in a volatile hydrocarbon solvent and sprayed onto the object or surface. Soaked and contains lead peroxide as a crosslinker.

Butyl rubber is also available in halogenated form. Halogenated butyl rubber is obtained by contacting butyl rubber in a solution containing an inert C _{5 to} C ₇ hydrocarbon solvent, such as pentane, hexane, or heptane, with halogen gas in contact with the solution for a predetermined time. Can be prepared by halogenation. Thereby, halogenated butyl rubber and hydrogen halide are produced. The halogenated butyl rubber copolymer can contain at most one halogen atom per double bond. Halogenated butyl rubber or halobutyl rubber includes bromobutyl rubber containing no more than 3% reactive bromine and chlorobutyl rubber containing no more than 3% reactive chlorine. Halogenated butyl rubber is also available from Exxon Mobile Chemical. Butyl rubber and halogenated rubber advantageously have low permeability to air, gas, and moisture. For example, manufacturers report that the permeability of nitrogen in butyl rubber is more than an 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 and is disclosed, for example, in the “728” patent and US Pat. No. 4,229,337. In general, butyl rubber having a viscosity average molecular weight in the range of about 5000 to about 85000 and a mole percent unsaturation of about 3% to about 4% is a sulfonating agent containing a sulfur trioxide (SO ₃ ) donor, oxygen, nitrogen, or It can be sulfonated in combination with a Lewis base containing phosphorus. The Lewis base acts as a complexing agent for the SO ₃ donor. SO ₃ donors include available SO ₃ containing compounds such as chlorosulfonic acid, fluorosulfonic acid, sulfuric acid, and oleum.

Typically, the water vapor transmission rate of butyl rubber ranges from about 0.001 to about 0.100 grams / mm ² / day.

  Other suitable water vapor barrier polymers include elastomers that combine the environment and aging resistance of ethylene propylene diene monomer rubber (EPDM) with butyl rubber, which is commercially available as Exxpro ™ from Exxon Mobile Chemical. More specifically, the elastomer is a brominated polymer derived from isobutadiene (IB) and p-methylstyrene (PMS). Bromination occurs selectively on the PMS methyl group to provide a reactive benzyl bromine functional group. Another suitable water vapor barrier polymer is a copolymer of isobutylene and isoprene, with a styrene block copolymer branching agent to improve manufacturing processability.

  Another suitable water vapor barrier polymer is polyisobutylene. Polyisobutylene is a homopolymer and is produced by a cationic polymerization method. A grade of polyisobutylene, commercially available from Exxon Mobile Chemical under the trademark Vistanex, is a highly paraffinic hydrocarbon polymer synthesized into long chain molecules containing only terminal olefinic bonds. The advantages of such elastomers are a combination of low permeability that prevents water vapor penetration and chemical inertness to chemical attack. Polyisobutylene is available as a viscous liquid or semi-solid and can be dissolved in certain hydrocarbon solvents.

  According to another aspect of the invention, the halogenated butyl rubber is blended with a second rubber, preferably a double bond vulcanized rubber, in a specific mixing ratio in a two-step kneading step and then cured. Rubber blends with low air / water vapor curability and great adhesion to diene rubber may be formed. This rubber blend is clearly advantageous in that it provides an improved moisture / water vapor barrier layer with enhanced adhesion to the polybutadiene core or subassembly. This rubber blend is discussed in US Pat. No. 6,342,567B2. The contents of the '567 patent are incorporated herein by reference. Alternatively, brominated isobutylene / p-methylstyrene can be used in place of the halogenated rubber as described above. Other water vapor barrier polymers may be dynamically vulcanized and have thermoplastic elastomer blends with butyl rubber or halogenated butyl rubber, which are described, for example, in US Pat. No. 6,062,283 B1, US Pat. As discussed in US Pat. Nos. 334,919B1 and 6,346,571B1. These references are incorporated herein by reference. Alternatively, butyl rubber may be blended with a vinylidene chloride polymer or copolymer, such as Saran ™, disclosed in US Pat. No. 4,239,799. The '799 patent is also incorporated herein by reference.

  Butyl rubber can be cured with many curing agents. Preferred curatives for golf ball applications include sulfur for butyl rubber and peroxide curatives, preferably zinc oxide for halogenated butyl rubber. Other suitable curing agents may include antimony oxide, lead oxide, or lead peroxide. Zinc-based hardeners can be employed when appropriate safety markings are made. Butyl rubber is available in varying grades ranging from viscous liquids to solids with varying saturation and molecular weight. Latex grades are also available.

  Butyl rubber and halogenated butyl rubber can be processed by milling, calendering, extrusion molding, injection molding, compression molding, and other techniques. These processing techniques can produce a semi-cured sheet or shell of water vapor barrier material that can be wrapped around a core or core subassembly. The water vapor barrier can be fully cured by heating to an elevated temperature, typically in the range of about 121.1 ° C. (250 ° F.) to about 1093 ° C. (2000 ° F.).

  In addition, any type of filler, additive, fiber, and flake, such as mica, mica-like iron oxide, metal, ceramic, graphite, aluminum, or more preferably, foliate aluminum is physically incorporated into the water vapor barrier layer. Barriers, i.e. winding paths, can be created to cope with water vapor ingress.

  According to another aspect of the invention, infrared radiation (IR) is preferably used to cure the water vapor barrier material on the core or core subassembly. The IR advantageously heats the water vapor material, such as butyl rubber, partially without penetrating the underlying golf ball core and / or other encapsulated layers. Thus, the predetermined properties of the core and / or the encapsulated layer are not adversely affected by heating / curing of the water vapor barrier layer. US Pat. No. 6,174,388 B1 discloses that IR can be effectively employed to heat and cure the surface of a polymer object without changing other parts of the object. ing. U.S. Pat. Nos. 5,677,362 and 5,672,393 disclose that IR heating can be employed with ultraviolet heating to effectively cure the polymer. The disclosures of these patents are incorporated herein by reference.

  Another advantage of employing IR as a curing technique is that a suitable water vapor barrier polymer having a curing or crosslinking temperature greater than the softening or melting temperature of the encapsulated material can be employed as the water vapor barrier layer and / or other outer layer. This is the point.

  According to other aspects of the invention, other suitable water vapor barrier materials are polysulfides, which are disclosed in U.S. Pat. Nos. 4,263,078, and 4,165,425, Including others. These references are incorporated herein by reference. In one example, the polysulfide rubber is cured with a lower alkyl tin oxide, such as di-n-butyl tin oxide, and employed in a hot applied process as disclosed in the '425 patent. This specific polysulfide rubber is thiol-terminated and is cured with lower alkyl tin oxide at a temperature between about 100 ° C. and about 300 ° C. to form a solid thermoplastic elastomer that is softened by heat to form or A water vapor barrier layer can be formed by injection molding. This polysulfide compound is preferably cured by IR.

  Other suitable IR curable polysulfide rubbers are based on thiol-terminated liquid polysulfide polymers, which are composed of zinc oxide and 2-mercaptobenzothiazole, zinc lower alkyl dithiocarbamate, and alkyl thiuram polysulfide. The selected sulfur-containing compound cures at a temperature of about 93.3 ° C. (200 ° F.) to about 198.9 ° C. (390 ° F.). Agents that improve the flow properties of the composition, such as copolymers of styrene and alkylene, organic or inorganic reinforcing fiber materials, phenolic resins, coumarone indene resins, antioxidants, thermal stabilizers, polyalkylene polymers, oil rubber, A terpene resin, terpene resin ester, benzothiazole disulfide, or diphenylguanidine may be added to the composition. Advantageously, the polysulfide rubber has a good tendency to wet with the substrate upon cooling to achieve good bonding with the substrate and is therefore a preferred sealant for golf balls. This polysulfide compound is also preferably cured by IR.

  A water vapor barrier layer having a polysulfide rubber was filed on January 12, 2004 and assigned to the present applicant under the name “Golf Ball with Water Vapor Barrier Layer and Method for Producing the Same”, and as US Patent Application Publication No. 2004/0185963. This is fully disclosed in published pending US patent application 10 / 755,638. This disclosure is incorporated herein by reference.

  According to another aspect of the invention, a suitable IR cured water vapor barrier polymer is a single pack moldable polymer. Preferred single pack polymers use uretdione or blocked isocyanate to form a single pack urethane component. Preferably, a single pack blocked isocyanate system comprising an isocyanate combined with an amine or polyol is stable at room temperature. The application of heat causes the isocyanate to deblock and undergo a reaction to form the urethane. It is not necessary to mix or adjust the ratio of the components.

  The uretdione castable material can be pre-configured as a single pack system without premature reaction. The mixed single pack material can be injected or injected directly into the mold, avoiding metering or mixing of multiple components. Parts can be made by using viscous or solid materials that could not be used before in conventional two-pack systems. Advantageously, uretdione and blocked isocyanate can be kneaded into rubber stock for use in other production methods described above when combined with suitable reactive components.

  Non-limiting examples of single pack systems according to this invention are as follows. Finely ground uretdione is combined with a tin catalyst and a cyclic amidine catalyst and dispersed in a liquid polyol or polyamine to produce a slurry. This slurry mixture is poured into a suitable golf ball mold to make the necessary parts, such as the core, intermediate layer or cover. The mold is then heated to a predetermined deblocking temperature of about 150-180 ° C., and sufficient time is taken to complete the reaction. The cured component can then be removed from the mold for further processing, if necessary.

  In another example, 3,5-dimethylpyrazole (DMP) block IPDI is used instead of uretdione in the above example. The mold is then heated to a deblocking temperature of about 140 ° C. to about 160 ° C. to allow sufficient time for the reaction to complete. In another non-limiting example, a single pack of water vapor barrier layer can be used to block blocked isocyanates that volatilize when deblocking occurs, such as diethyl maleate (DEM) or methyl ethyl ketoxime (MEKO) blocked hexamethylene diisocyanate cycle. It is a mer. Such examples can be sprayed or dipped into golf balls, subassemblies, or the like, followed by IR curing.

The non-limiting chemical structure of a single pack system is shown below. The uretdione is generated as follows.

The preferred chemical structure of the polyuretdione crosslinking agent is as follows:

Preferred curing agents are uretdiones or blocked isocyanates, and the blocking agent remains in the component as a solid once cast, eg as DMP or triazole blocked isocyanate. A preferred blocking agent structure is as follows.

  Single pack castable water vapor barrier materials are fully disclosed in the parent application patent application 09 / 973,342, the contents of which are hereby incorporated by reference.

  Preferably, the golf ball according to the present invention has a solid or multi-layer solid polybutadiene core 12 having an outer diameter greater than about 1.50 inches, more preferably 1.550 inches, and most preferably about 1. 580 inches. The thickness of the water vapor barrier layer 14 is preferably in the range of about 0.001 inch to about 0.100 inch, more preferably in the range of about 0.010 inch to about 0.050 inch. It is urethane, and its thickness is sufficient to form a 1.680 inch diameter golf ball.

  More preferably, the water vapor barrier layer is a thin layer of a suitable butyl rubber polymer as described above, and its thickness is preferably less than 0.050 inch, more preferably 0.030 inch. Less than, most preferably less than 0.010 inches. The butyl rubber water vapor barrier layer preferably does not significantly or negatively affect the coefficient of restitution of the golf ball. Preferably, the polybutadiene core 12 and the thin butyl rubber water vapor barrier layer 14 are covered by a relatively soft polymer cover, which has a thickness of about 0.010 inch to about 0.127 cm (.0.17 cm). 050 inches), more preferably 0.030 inches, and the Shore D of the cover is less than 65, or from about 30 to about 60, more preferably from about 35 to about 50, Preferably from about 40 to about 45. Such covers are fully disclosed in US Pat. Nos. 5,885,172 and 6,132,324. The disclosures of these two patents are incorporated herein by reference. Preferred cover polymers include thermosetting urethanes and polyurethanes, polyureas, thermoplastic urethane ionomers and thermosetting urethane epoxies.

  As discussed above and shown in FIG. 3, the golf ball 20 may include multi-layer cores 12 a, 12 b, and 12 c that are surrounded by the mid layer 14 and the dimple cover 16. The core layers 12b and 12c may preferably be an integral solid layer or separate layers that are molded together. Alternatively, both the inner and outer layers 12b and 12c may be wound layers, or one of those layers may be a wound layer and the innermost core or center 12a is liquid filled. good.

In some embodiments in which a golf ball according to the present invention has at least three core layers (i.e., at least a center 12a, an inner core layer 12b, and an outer core layer 12c), one or more of the following features in the core layer: Exists.
Feature a:
The center advantageously has (a) a diameter of from about 0.5 inches to about 1.6 inches, and (b) a Mooney viscosity greater than about 35, (C) has a deflection of at least about 1 mm at a load of about 100 kg, and (d) the amount of diene crosslinking agent (eg, zinc diacrylate) is about 10 to about 40 parts per hundred parts of resin (phr: per hundred resin). Or (e) having some of these combinations.
Feature b:
The inner core layer advantageously has (a) an outer diameter of about 1.610 inches or less, (b) a Mooney viscosity greater than about 35, and (c) a diene crosslinker ( The amount of zinc diacrylate) is from about 15 to about 45 parts per hundred parts of resin (phr), or (d) has some of these combinations.
Feature c:
The outer core layer advantageously has (a) an outer diameter not greater than about 1.660 inches, (b) a Mooney viscosity greater than about 35, and (c) a diene crosslinker ( The amount of zinc diacrylate) is from about 15 to about 45 parts per hundred parts of resin (phr), or (d) has some of these combinations.

  In one embodiment, one or more (eg, all) of the core layers may include a sulfur compound such as zinc pentachlorochlorophenol. In one embodiment, one or more (eg, all) of the core layers may include fillers such as barium sulfate, tungsten, zinc oxide, and combinations thereof.

  In some embodiments in which the golf ball core layer achieves a hardness gradient in accordance with the present invention, the center, inner core and outer core layers each have increased hardness (center hardness <inner core hardness <outer core hardness). Hardness), for example, the center hardness may be about 50 Shore C or less, the inner core hardness may be greater than about 50 Shore C, the outer core hardness may be greater than about 65 Shore C, or a combination thereof It may be. In these golf balls, the hardness gradient of the core increases from the center to the outer core, and these golf balls are typically harder and usually increase the hitting distance more.

  In some embodiments in which the core layer of the golf ball achieves a hardness gradient in accordance with the present invention, the hardness of the center, inner core, and outer core layer is reduced respectively (center hardness> inner core hardness> outer core Hardness), for example, the center hardness may be greater than about 60 Shore C, the inner core hardness may be less than about 60 Shore C, the outer core hardness may be less than about 50 Shore C, or a combination thereof. It's okay. In these golf balls, the hardness gradient of the core decreases from the center to the outer core, and these golf balls are typically softer and generally provide a greater spin rate for better control.

  In one embodiment, the specific gravity of the center, inner core layer, and outer core layer are substantially similar (eg, in the range of about 5% of each other). In other embodiments, the specific gravity of each of the center, inner core layer, and outer core layer is significantly different from each other (eg, neither core layer is in the range of about 5% of any other layer). In other embodiments, the specific gravity of each of the center, inner core layer, and outer core layer is substantially the same for two of the at least three layers, such that the third of the at least three layers is the third. The layers are significantly different from two layers that are approximately equal.

In these multi-layer core golf balls according to the present invention, advantageously, at least one intermediate layer functioning as a barrier layer against moisture and / or oxygen is comprised of the innermost core layer and the (outermost) cover layer. It may be placed in between. Typically, in these examples, the water vapor transmission rate of the intermediate layer (s) can advantageously be better (smaller) than the Surlyn ™ number above the transmission (ie, about Less than 0.6 gram · mm / m ² · day, or less than about 0.6 gram · mm / m ² · day if the cover is less than about 0.6 gram · mm / m ² · day). In preferred embodiments, the thickness of the intermediate barrier layer is relatively uniform and may be about 0.020 inches or less.

  In one embodiment, the intermediate barrier layer comprises a thermoplastic binder and a particulate material having a low water vapor and / or oxygen permeability. Without being bound by theory, the particulate material advantageously works by forming a tortuous path through which the permeate / penetrant (eg, water vapor and / or oxygen) passes. In one preferred embodiment, the ratio of particulate material to binder material may be from about 0.8: 1.2 to about 1.2: 0.8, preferably from about 0.9: 1 to about 1.1. : 0.9, for example 1: 1. In other embodiments, the thermoplastic elastomer binder may comprise a material such as Kraton ™, while the particulate material may comprise high aspect ratio (platelet, disc, etc.) aluminum flakes. Preferably the aspect ratio is greater than 2: 1.

  In one preferred embodiment, there are at least three core layers and one intermediate barrier layer, in which case the cover may comprise a thermoset or thermoplastic polyurethane (eg polyurethane urea), having a hardness of about 25 to about 65 Shore D, and its flexural modulus is at least about 13.79 MPa (2000 psi).

  In a preferred embodiment, a golf ball according to the present invention has at least three core layers, at least one intermediate barrier layer, and at least one cover layer, in which case the resulting golf ball is advantageously One or more features of That is, Atti compression is less than about 110; COR is at least about 0.790; Deflection at about 100 kg load is at least about 1.5 mm; Cover surface has about 250 to about 450 dimples; And combinations thereof.

  Suitable materials for some of the golf balls according to the present invention can be found in US patent application 11 / 061,338, filed February 18, 2005, filed as US patent application publication 2005 / 0176523A1. The disclosure of which is incorporated herein by reference.

  In some embodiments, the core of the multi-layer golf ball is a fluid (gas or liquid) filled core, such as those described in US patent application Ser. No. 10 / 670,514 and US Pat. No. 6,632,147. The disclosure of which is incorporated herein by reference. Fluids suitable for use in the core include air, other gases, liquid solutions, liquids, gels, foams, hot melts, other fluid materials and combinations thereof depending on their specific gravity. Examples of suitable liquids are aqueous solutions such as brine, corn syrup, brine and corn syrup, glycol and water or oil. The liquid may further be a paste, a colloidal suspension such as clay, barite, water or other liquid, or a brine / glycol mixture. Examples of suitable gels are water gelatin gels, hydrogels, water / methylcellulose gels, and copolymer rubbers and paraffinic and / or naphthenic oils based on materials such as styrene-butadiene-styrene (SBS) rubber. . Examples of suitable melts are waxes and hot melts. A hot melt is a material that is solid at room temperature or approximately room temperature and becomes liquid at elevated temperatures. A high melting temperature is preferred because the liquid core is heated to a high temperature during molding of the inner core, outer core, and cover. Alternatively, the liquid may be a selectively reactive liquid system that is combined to form a solid. Examples of suitable reactive liquids are silicate gels, agar gels, peroxide cured polyester resins, two-component epoxy resins, peroxide cured liquid polybutadiene rubber compositions, reactive polyurethanes, silicones, and polyesters. Further, suitable fluids include low density liquids such as petroleum, vegetable or animal based oils, methanol, ethanol, ammonia, etc., or high density liquids such as glycerin or carbon tetrachloride.

  The core may be a thermosetting or thermoplastic material such as polyurethane, polyurea, partially or fully neutralized ionomer, thermosetting polydiene rubber such as polybutadiene, ethylene propylene diene monomer rubber, ethylene propylene rubber, natural rubber, balata. , Butyl rubber, halobutyl rubber, styrene butadiene rubber, or any styrenic block copolymer, such as styrene ethylene butadiene styrene rubber, others, metallocene or other single site catalyzed polyolefins, polyurethane copolymers, for example with silicone. However, the material must meet the above COR criteria.

  In addition to the materials described above, compositions within the scope of this invention may incorporate one or more polymers. Examples of additional polymers that are optimal for use in the present invention include, but are not limited to: That is, thermoplastic elastomer, thermosetting elastomer, synthetic rubber, thermoplastic vulcanizate, copolymeric ionomer, terpolymeric ionomer, polycarbonate, polyolefin, polyamide, copolymeric polyamide, polyester, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer Polyarylate, polyacrylate, polyphenylene ether, impact modified polyphenylene ether, high impact polystyrene, diallyl phthalate polymer, metallocene catalyzed polymer styrene-acrylonitrile (SAN) (including olefin modified SAN and acrylonitrile-styrene-acrylonitrile), Styrene-maleic anhydride (S / MA) polymer, styrene copolymer, functional styrene copolymer, government Styrene terpolymer, styrene terpolymer, cellulose polymer, liquid crystal polymer (LCP), ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), ethylene-propylene copolymer, ethylene vinyl acetate, polyurea, And polysiloxanes or these types of metallocene catalyst polymers. Polyamides suitable as additional materials for compositions within the scope of this invention include resins obtained as follows. (1) As (a) dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, or 1,4-cyclohexanedicarboxylic acid, (b) diamine such as ethylenediamine, tetraethylenediamine, pentamethylenediamine, hexamethylene Polymerization is carried out with diamine, decamethylenediamine, 1,4-cyclohexylamine or m-xylylenediamine. As (2), ring-opening polymerization of a cyclic lactam such as epsilon caprolactam or omega laurolactam is performed. As (3), an aminocarboxylic acid such as 6-aminocaproic acid, 9-aminocaproic acid, 11-aminocaproic acid or 12-aminocaproic acid is polymerized. Alternatively, as (4), a cyclic lactam is copolymerized with a dicarboxylic acid and a diamine. Specific examples of suitable polyamides are nylon 6, nylon 66, nylon 11, nylon 12, copolymer nylon, nylon MXD6 and nylon 46.

  Other preferred materials suitable for use as an additional material in the compositions within the scope of this invention are polyester elastomers sold under the trade name “SKYPEL” by SK Chemicals, Korea, or trade names from Kuraray, Japan. It is a diblock or triblock copolymer sold under the name “SEPTON” and also sold under the name “KRATON” from Kraton Polymers Group of Chester, UK. All the materials raised above significantly improve the quality of the ball layer prepared within the scope of this invention.

  Ionomers are also well suited for blending into compositions within the scope of this invention. Suitable ionomer polymers (eg, copolymers, or terpolymer type ionomers) include α-olefin / unsaturated-carboxylic acid copolymer type ionomer resins or terpolymer resins. Copolymer ionomers are obtained by neutralizing at least some of the carboxyl groups in a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms with a metal ion. Examples of suitable α-olefins include, but are not limited to, ethylene, propylene, 1-butene, and 1-hexene. Examples of suitable unsaturated carboxylic acids are, but are not limited to, acrylic, methacrylic, ethacryl, α-chloroacrylic, croton, malein, fumar, and itaconic acid. Copolymer ionomers include ionomers that vary in acid content and degree of neutralization, and neutralization is performed with monovalent or divalent cations, as discussed above.

The terpolymer ionomer is a carboxyl in a copolymer of an α-olefin, an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and an α, β-unsaturated carboxylate having 2 to 22 carbon atoms. Obtained by neutralizing at least part of the group with metal ions. Examples of suitable ionomer resins include, but are not limited to, the trade name “SURLYN” of EI DuPont de Nemours & Co., Wilmington, DE or Exxon of Irving, Texas. Including those manufactured as IOTEK.

  Silicone materials are also suitable for blending into compositions within the scope of this invention. These are monomers, oligomers, prepolymers or polymers and may or may not be accompanied by additional reinforcing fillers. One suitable type of silicone material can incorporate alkene groups containing at least two carbon atoms in their molecule. Examples of alkene groups include, but are not limited to, vinyl, allyl, butenyl, pentenyl, hexenyl and decenyl. The alkene group may be located at any position of the silicone structure, including one or both ends of the structure. The remaining (ie non-alkene) silicone-bonded organic groups of this component are independently selected from hydrocarbon or halogenated hydrocarbon groups, which do not contain aliphatic unsaturation. Non-limiting examples of these are: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and hexyl; cycloalkyl groups such as cyclohexyl and cycloheptyl; aryl groups such as phenyl, tolyl and xylyl; aralkyl groups such as benzyl And phenethyl; and halogenated alkyl groups such as 3,3,3-trifluoropropyl and chloromethyl. Another type of silicone material suitable for use in this invention is one that has hydrocarbon groups without aliphatic unsaturation. Specific examples suitable for use in preparing the compositions of this invention are the following. Trimethylsiloxy-endblocked dimethylsiloxane-methylhexenylsiloxane copolymer; dimethylhexenylsiloxy-endblocked dimethylsiloxane-methylhexenylsiloxane copolymer; trimethylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxane copolymer; trimethylsiloxy-endblocked methyl Phenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymer; dimethylvinylsiloxy-endblocked dimethylpolysiloxane; dimethylvinylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxane copolymer; dimethylvinylsiloxy-endblocked methylphenylpolysiloxane; dimethyl Vinylsiloxy-end-blocked methylpheny A and above copolymers; siloxane - methyl vinyl siloxane copolymer - dimethylsiloxane. However, at least one terminal group is dimethylhydroxysiloxy. Commercially available silicones suitable for use in the compositions of the present invention include "Silastic" from Dow Corning, Midland, Michigan, "Blensil" from GE Silicones, Waterford, New York, and Adrian, Michigan. Wacker Silicones' “Elastosil”.

  Other types of copolymers can also be added to compositions within the scope of this invention. Examples that are suitable for use within the scope of this invention include epoxy monomers, styrene-butadiene-styrene block copolymers where the polybutadiene block contains epoxy groups, styrene-isoprene-styrene, where the polyisoprene block contains epoxy It is a block copolymer. Commercially available examples of these epoxy functional copolymers are ESBS A1005, ESBS A1010, ESBS A1020, ESBS AT018, and ESBS AT019 sold by Daicel Chemical Industries of Osaka, Japan.

  Preferred examples for the slow core are polybutadiene, SBR, almost no zinc diacrylate (0-10 parts), optional dimethyl acrylate, or non-zinc salt unsaturated monomers such as trimethylolpropane triacrylate (SR sold by Sartomer) -350), containing a peroxide initiator. Other formulations of the core are disclosed in U.S. Patent Publication No. 2005-0255941A1, filed by Applicant and incorporated herein by reference. Alternatively, a sulfur formulation with non-peroxide sulfur may be employed. This is disclosed, for example, in US Pat. No. 7,041,008. Incorporated herein by reference. Alternatively, non-peroxide, sulfur vulcanized formulations can be used, such as those disclosed in pending US Patent No. 10 / 772,689. This reference is also incorporated herein by reference.

  The diameter of the core is about 0.100 inches to about 1.64 inches, and preferably about 1.00 inches to about 1.62 inches. Typical core diameters are from 0.25 inches to 1.625 inches, increasing by 0.05 inches. Conventional core sizes are 0.050 inch, 1.00 inch, 1.10 inch, 1.20 inch, 1.30 inch, 1.40 inch, 1.45 inch, 1.50 inch, 1. 55 inches, 1.57 inches, 1.58 inches, 1.59 inches, and 1.60 inches. That is, the core size plus any one or more intermediate layers is in the same size and size range as the core size described above, and may be slightly larger.

Other suitable materials for the core include, but are not limited to:
(A) Polyurethanes, eg prepared from polyols and diisocyanates or polyisocyanates, disclosed in US Pat. Nos. 5,334,673, 6,506,851 and US patent application 10 / 194,059 What has been.
(B) Polyureas such as those disclosed in US Pat. No. 5,484,870 and US patent application 10 / 228,311.
(C) A polyurethane-urea hybrid, blend or copolymer comprising urethane and / or urea segments.

  The core of the multi-layer golf ball preferably comprises a polyurethane comprising a reaction product of at least one polyisocyanate and at least one curing agent. The curing agent may include, for example, one or more diamines, one or more polyols, or combinations thereof. The polyisocyanate may be combined with one or more polyols to form a prepolymer. This is combined with at least one curing agent as described above. Thus, the polyols described herein are suitable as one or both elements of the polyurethane material. That is, it is suitable for use as a part of the prepolymer and the curing agent.

  Golf ball cores and optional layers can also be made from highly neutralized polymers ("HNP"). The acid portion of HNP is typically an ethylene-based ionomer, preferably more than about 70%, more preferably more than about 90%, and most preferably at least about 100% neutralized. HNP can also be blended with the second polymer component, and if this component contains acid groups, it can be neutralized according to conventional methods, with the organic fatty acids of this invention, or both. The second polymer component may be partially or fully neutralized, preferably ionomer copolymers and ionomer terpolymers, ionomer precursors, thermoplastics, polyamides, polycarbonates, polyesters, polyurethanes, polyureas, heat Includes plastic elastomers, polybutadiene rubber, balata, metallocene catalyzed polymers (grafted and ungrafted), single site polymers, highly crystalline acid polymers, cationic ionomers, and the like. The material hardness of the HNP polymer is typically between about 20 and about 80 Shore D, and the flexural modulus is between about 3000 psi and about 200000 psi.

  The base rubber of one or more of the core layers is typically natural rubber or synthetic rubber. A preferred base rubber is 1,4-polybutadiene having a cis structure of at least 40%. More preferably, the base rubber includes a high Mooney viscosity rubber. If desired, the core properties may be modified by mixing polybutadiene with other elastomers known in the art, such as natural rubber, polystyrene rubber and / or styrene butadiene rubber.

  The cross-linking agent is a metal salt of an unsaturated fatty acid, such as an unsaturated fatty acid of 3 to 8 carbon atoms, such as a zinc or magnesium salt of acrylic acid or methacrylic acid. Suitable crosslinking agents are metal salt diacrylates, dimethacrylates and monomethacrylates, and the metal is magnesium, calcium, zinc, aluminum, sodium, lithium or nickel. The crosslinker is present from about 15 to about 30 parts, preferably from about 19 to about 25 parts, and most preferably from about 20 to about 24 parts per 100 parts rubber. The core composition of the present invention may also include at least one organic or inorganic cis-trans catalyst to convert the polybutadiene cis-isomer to the trans-isomer.

  Initiators are known as polymerization initiators that decompose in the cure cycle. Suitable initiators are peroxide compounds such as 1,1-di- (t-butylperoxy), 3,3,5-trimethylcyclohexane, a-a bis (t-butylperoxy) diisopropylbenzene, 2,5- Dimethyl-2,5 (t-butylperoxy) hexane or di-t-butylperoxide and mixtures thereof.

  Fillers are compounds or compositions that modify core density, other properties, typically tungsten, zinc oxide, barium sulfide, silica, calcium carbonate, zinc carbonate, metals, metal oxides and salts, ligrind (Typically recycled core material ground to about 30 mesh), such as high Mooney viscosity rubber riglind.

  At least one of the outer core layers is formed from a resilient rubber base component that includes a high Mooney viscosity rubber and the crosslinker is present from about 20 to about 40 parts per 100 parts and from about 30 to about 38 parts per 100 parts. Present, most preferably about 37 parts per 100 parts. The term “parts per hundred” is parts by weight based on rubber.

  If the core is comprised of a fluid filled center, the center is manufactured first and the inner core is molded around the center. Conventional molding techniques can be employed for this process. An outer core and cover are then formed thereon, as described above. The fluid in the inner core can be a wide range of materials, such as air, aqueous solutions, liquids, gels, foams, hot melts, other fluid materials and combinations thereof. The fluid is modified to modify the ball's characteristic parameters, such as moment of inertia or spin decay rate. Examples of suitable liquids are aqueous solutions such as brine, corn syrup, brine and corn syrup, glycol and water or oil. The liquid may further be a paste, a colloidal suspension such as clay, barite, carbon black in water or other liquid, or a brine / glycol mixture. Examples of suitable gels are water gelatin gels, hydrogels, water / methylcellulose gels and copolymer rubbers based on materials such as styrene-butadiene-styrene rubber and paraffinic and / or naphthenic oils. Examples of suitable melts are waxes and hot melts. A hot melt is a material that is solid at room temperature or approximately room temperature and becomes liquid at elevated temperatures. A high melting temperature is desirable because the liquid core is heated to a high temperature during molding of the inner core, outer core and cover. Alternatively, the liquid may be a selectively reactive liquid system that is combined to form a solid. Examples of suitable reactive liquids are silicate gels, agar gels, peroxide cured polyester resins, two-component epoxy resins, peroxide cured liquid polybutadiene rubber compositions.

The “effective compression constant” is also written as “EC”, which is the displacement of a 1.50 inch diameter sphere made from any single material used for the core under a load of 100 Kg. Ratio, expressed by the formula EC = F / d. Here, F is a weight of 100 kg, and d is a deviation expressed in millimeters. When the test sphere is composed only of the inner core material, the effective compression constant of the inner core material alone is represented by EC _IC . When the test sphere is only the outer core material, the effective compression constant of the outer core material alone is expressed in EC _OC . The sum of the constants _{EC IC} and _{EC OC} of the inner core and outer core are constant EC _S. If the test sphere of the inner and outer core material, the core effective compression constant is denoted by EC _C. Core effective compression constant C _C is, when the smaller the sum EC _S constants EC _IC and EC _OC of the inner core and outer core, highly preferred core was found to be produced. It is recommended that the core effective compression constant is C _C less than about 90% of the sum EC _S of the inner and outer core constants EC _IC and EC _OC . More preferably, the core effective compression constant _CC is less than 50% of the sum EC _S of the inner core and outer core constants EC _IC and EC _OC . The ratio of inner core material to outer core material and the geometry of the inner core and outer core are selected to achieve these core effective compression constants.

  The resulting golf ball typically has a coefficient of restitution greater than about 0.7, preferably greater than about 0.75, and more preferably greater than about 0.78. Also, the Atti compression of this golf ball is typically at least about 40, preferably from about 50 to about 120, more preferably from about 60 to 100. The hardness of the golf ball cured polybutadiene material is typically at least about 15 Shore A, preferably between about 30 Shore A and 80 Shore D, and more preferably between about 50 Shore A and 60 Shore D. .

  In addition to HNP neutralized with organic fatty acids and salts thereof, the core composition may include at least one rubber material having a resilience index of at least about 40. Preferably, the elasticity index is at least about 50. Accordingly, polymers for producing resilient golf balls are suitable for this invention, including but not limited to CB23, CB22, commercially available from Bayer, Orange, Texas, and commercially available from Enichem, Italy. BR60 available and 1207G commercially available from Goodyear, Akron, Ohio.

  Further, the non-vulcanized rubber, such as polybutadiene, has a Mooney viscosity between about 40 and about 80, more preferably about 45 to about 65, most preferably about It has a Mooney viscosity between 45 and about 55. Mooney viscosity is typically measured according to ASTM-D1646.

  In yet another embodiment, the core has a reaction product comprising a cis-trans conversion catalyst, an elastic polymer component comprising polybutadiene, a free radical source, optional crosslinkers and fillers or both. Preferably, the polybutadiene reaction product is used to form at least a portion of the core of the golf ball, and the following relates to an embodiment for preparing the core. Preferably, the first dynamic stiffness measured at −50 ° C. of the reaction product is about 130 percent less than the second dynamic stiffness measured at 0 ° C. More preferably, the first dynamic stiffness is about 125 percent less than the second dynamic stiffness. Most preferably, the first dynamic stiffness is about 110 percent less than the second dynamic stiffness.

  The cis-trans conversion includes cis-trans, such as organic sulfur or metal-containing organic sulfur compounds, sulfur or metal-free substituted or unsubstituted aromatic organic compounds, inorganic sulfide compounds, aromatic organometallic compounds, or mixtures thereof. A trans-conversion catalyst is required. The cis-trans conversion catalyst component may include one or more cis-trans conversion catalysts described herein. For example, the cis-trans conversion catalyst may be a blend of an organic sulfur component and an inorganic sulfide component.

  Preferred organic sulfur components are 4,4'-diphenyl disulfide, 4,4'-ditolyl disulfide, or 2,2'-benzamide diphenyl disulfide, or blends thereof. Additional preferred organic sulfur components include, but are not limited to, pentachlorothiophenol, zinc pentachlorothiophenol, non-metal salts of pentachlorothiophenol, such as ammonia salts of pentachlorothiophenol, magnesium pentachlorothiophenol, Cobalt pentachlorothiophenol, pentafluorothiophenol, zinc pentafluorothiophenol, and blends thereof. Preferred candidates are pentachlorothiophenol (available from Struktol, Stow, Ohio), zinc pentachlorothiophenol (available from Chinachem, San Francisco, Calif.), And blends thereof. Additional examples are described in commonly assigned US patent application Ser. No. 10 / 882,130, incorporated herein by reference.

  If present, the organosulfur cis-trans conversion catalyst is preferably sufficient to produce the reaction product to contain at least about 12 percent trans-polybutadiene isomer based on total elastic polymer components. Although present in an amount, it is typically present in an amount sufficient to produce more than about 32 percent trans-polybutadiene isomer based on the total elastomeric polymer component. In other embodiments, metal-containing organic sulfur components can be used in accordance with the present invention. Suitable metal-containing organosulfur components include, but are not limited to, cadmium, copper, lead, and ruthenium analogs of diethyldithiocarbamate, diamyldithiocarbamate and dimethyldithiocarbamate or mixtures thereof. An additional suitable example can be found in US patent application Ser. No. 10 / 40,592, filed by the applicant.

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

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

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

  The PGA compression of a golf ball core or core portion prepared in accordance with the present invention is typically about 160 or less, preferably about 10 to about 150, as measured at the sphere surface. More preferably from about 15 to about 140, and most preferably from about 20 to about 120. There are various equivalent ways to measure compression. For example, 70 Atti compression (previously called “PGA compression”) is equivalent to a center hardness of 3.2 mm deflection with a 100 kg load, 36 Kgf / mm “spring constant”. In one embodiment, the deflection of the golf ball core is about 3.3 mm to 7 mm in a 130 kg-10 kg test. Various compression measurement techniques are described in J. Org. It is discussed in Datton's paper, as described above.

  Any other suitable monk discussed above can be used on the ball.

The golf ball may similarly have one or more homopolymer or copolymer inner cover materials, such as:
(A) Vinyl resins, such as those produced by polymerization of vinyl chloride, or those produced by copolymerization of vinyl chloride with vinyl acetate, acrylic esters or vinylidene chloride;
(B) using polyolefins such as polyethylene, polypropylene, polybutylene and copolymers, such as ethylene methyl acrylate, ethylene ethyl acrylate, ethylene vinyl acetate, ethylene methacrylic acid or ethylene acrylic acid or propylene acrylic acid and single site or metallocene catalysts Copolymers and homopolymers produced;
(C) polyurethanes, such as those made from polyols and diisocyanates or polyisocyanates and those disclosed in US Pat. No. 5,334,673;
(D) polyureas, such as those described in US Pat. No. 5,484,870;
(E) polyamides, such as those made from poly (hexamethylene adipamide) and other diamines and dibasic acids, and amino acids such as those made from poly (caprolactam), and polyamides and SURLYN ™, polyethylene, Blends with ethylene copolymers, ethyl-propylene-nonconjugated diene terpolymers, and the like;
(F) acrylic resins and blends of these resins with polyvinyl chloride, elastomers, and the like;
(G) thermoplastics such as urethane; olefinic thermoplastic rubbers such as blends of polyolefins with ethylene-propylene-nonconjugated diene terpolymers; block copolymers of styrene and butadiene, isoprene or ethylene-butylene rubber; or copoly (ether- Amide), for example, PEBAX ™ commercially available from ELF Atchem of Philadelphia, PA;
(H) a polyphenylene oxide resin or a blend of polyphenylene oxide and high impact polystyrene, commercially available under the trade name NORYL (TM) by General Electric Company of Pittsfield, MA;
(I) Thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / glycol modified and elastomers under the trade name HYTREL ™ by EI DuPont de Neumours & Co. of Wilmington, DE And marketed under the name LOMOD (TM) by the General Electric Company of Pittsfield, MA;
(J) Blends containing acrylonitrile butadiene styrene, polybutylene terephthalate, polyethylene terephthalate, styrene maleic anhydride, polyethylene, elastomers, and similar polycarbonates, and polyvinyl chloride with acrylonitrile butadiene styrene or ethylene vinyl acetate or other elastomers. And (k) blends of thermoplastic rubber with polyethylene, propylene, polyacetal, nylon, polyester, cellulose ester, and the like.

  Preferably, the inner cover includes the following polymer. Homopolymers or copolymers based on ethylene, propylene, butene-1 or hexane-1, which contain functional monomers such as acrylic acid and methacrylic acid and fully or partially neutralized ionomer resins and These blends, methyl acrylate, methyl methacrylate homopolymers and copolymers, imidized polymers containing amino groups, polycarbonate, reinforced polyamide, polyphenylene oxide, high impact polystyrene, polyether ketone, polysulfone, poly (phenylene sulfide), Acrylonitrile-butadiene, acrylic-styrene-acrylonitrile, poly (ethylene terephthalate), poly (butylene terephthalate), poly (ethylene vinyl alcohol), poly (Tetrafluoroethylene) and those containing functional comonomers a copolymers thereof, and blends thereof. Suitable cover compositions further include polyether or polyester thermoplastic urethanes, thermoset polyurethanes, low modulus ionomers such as ethylene copolymer ionomers containing acids, E is ethylene and X is present from about 0 to 50% by weight. It includes an E / X / Y terpolymer that is an acrylate or methacrylate-based softening comonomer and that is acrylic acid or methacrylic acid with Y present in about 5-35% by weight. Preferably, low spin rate embodiments designed to maximize flight distance include about 16-35% by weight acrylic acid or methacrylic acid, making the ionomer a high modulus ionomer. In the high spin embodiment, the inner cover layer includes an ionomer in which about 10-15% by weight of acid is present, and includes a softening comonomer. In addition, high density polyurethane ("HDPE"), low density polyurethane ("LDPE"), LLDPE, and polyolefin homopolymers and copolymers are suitable for various golf ball layers.

In one example, the outer cover is preferably a polyurethane composition comprising a reaction product of at least one isocyanate, polyol, and at least one curing agent. Any polyisocyanate available to those skilled in the art is suitable for use in accordance with the present invention. Examples of polyisocyanates include but are not limited to: 4,4′-diphenylmethane diisocyanate (“MDI”); polymer MDI; carbodiimide-modified liquid MDI; 4,4′-dicyclohexylmethane diisocyanate (“H ₁₂ MDI”) P-phenylene diisocyanate ("PPDI"); m-phenylene diisocyanate ("MPDI"); toluene diisocyanate ("TDI");3,3'-dimethyl-4,4'-biphenylene diisocyanate ("TODI"); Isophorone diisocyanate ("IPDI"); hexamethylene diisocyanate ("HDI"); naphthalene diisocyanate ("NDI"); xylene diisocyanate ("XDI"); p-tetramethylxylene diisocyanate ("p-TM") DI "); m-tetramethylxylene diisocyanate (" m-TMXDI "); ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene-1,4-diisocyanate; cyclohexyl diisocyanate; 1,6-hexamethylene-diisocyanate ( "HDI");dodecane-1,12-diisocyanate;cyclobutane-1,3-diisocyanate;cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate; 1-isocyanate-3,3,5-trimethyl-5 -Isocyanate methylcyclohexane; methylcyclohexylene diisocyanate; triisocyanate of HDI; triisocyanate of 2,4,4-trimethyl-1,6-hexane diisocyanate ("T DI "); tetracene diisocyanate; naphthalene diisocyanate; anthracene diisocyanate; and mixtures thereof; uretdione of hexamethylene diisocyanate; the isocyanurate of toluene diisocyanate. Polyisocyanates are known to those skilled in the art as having one or more isocyanate groups such as diisocyanates, triisocyanates and tetraisocyanates. Preferably, the polyisocyanate comprises MDI, PPDI, TDI, or mixtures thereof, more preferably the polyisocyanate comprises MDI. As used herein, the term “MDI” refers to 4,4′-diphenylmethane diisocyanate, polymeric MDI, carbodiimide modified liquid MDI, and mixtures thereof, and further the diisocyanate used is “low free monomer”. It should be understood by those skilled in the art that the amount of “free” monomer is a low isocyanate group, typically that the amount of free monomer group is less than about 0.1%. is there. Examples of “low free monomer” diisocyanates are, but not limited to, low free monomer MDI, low free monomer TDI, and low free monomer PPDI.

  The at least one polyisocyanate should have less than about 14% unreacted NCO groups. Preferably the at least one polyisocyanate has no more than about 7.5% NCO, more preferably less than about 7.0%.

  Any polyol available to one skilled in the art is suitable for use in accordance with the present invention. Examples of polyols include, but are not limited to, polyether polyols, hydroxy-terminated polybutadienes (including partially / fully hydrogenated derivatives), polyester polyols, polycaprolactone polyols, and polycarbonate polyols. In a preferred embodiment, the polyol comprises a polyether polyol. Examples are, but not limited to, polytetramethylene ether glycol ("PTMEG"), polyethylene propylene glycol, polyoxypropylene glycol, and mixtures thereof. The hydrocarbon chain can have saturated or unsaturated bonds and substituted or unsubstituted aromatic and cyclic groups. Preferably, the polyol of this invention comprises PTMEG.

  In another embodiment, the polyurethane material of this invention includes a polyester polyol. Suitable polyester polyols include, but are not limited to, polyethylene adipate glycol; polybutylene adipate glycol; polyethylene propylene adipate glycol; o-phthalate-1,6-hexanediol; poly (hexamethylene adipate) glycol; and mixtures thereof It is. The hydrocarbon chain can have saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups.

  In another embodiment, the polyurethane material of this invention includes a polycaprolactone polyol. Suitable polycaprolactone polyols include, but are not limited to, 1,6-hexanediol-initiated polycaprolactone, diethylene glycol initiated polycaprolactone, trimethylolpropane initiated polycaprolactone, neopentyl glycol initiated polycaprolactone, 1,4-butanediol initiated Polycaprolactone, PTMEG-initiated polycaprolactone, and mixtures thereof. The hydrocarbon chain can have saturated or unsaturated, or substituted or unsubstituted aromatic and cyclic groups.

  In yet another embodiment, the polyurethane material of this invention includes a polycarbonate polyol. Suitable polycarbonates include, but are not limited to, polyphthalate carbonate and poly (hexamethylene carbonate) glycol. The hydrocarbon chain can have saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups. In one example, the molecular weight of the polyol is from about 200 to about 4000.

  Polyamine curing agents are also suitable for use in the polyurethane compositions of this invention and have been found to improve the cut resistance, shear resistance, and impact resistance of product balls. Preferred polyamine curing agents include, but are not limited to, 3,5-dimethylthio-2,4-toluenediamine and its isomer; 3,5-diethyltoluene-2,4-diamine and its isomer, such as 3,5-diethyl Toluene-2,6-diamine; 4,4′-bis- (sec-butylamino) -diphenylmethane; 1,4-bis- (sec-butylamino) -benzene, 4,4′-methylene-bis- (2 -Chloroaniline); 4,4'-methylene-bis- (3-chloro-2,6-diethylaniline) ("MCDEA"); polytetramethylene oxide-di-p-aminobenzoate; N, N'-dialkyl Diaminodiphenylmethane; p, p'-methylenedianiline ("MDA"); m-phenylenediamine ("MPDA"); 4 4'-methylene-bis- (2-chloroaniline) ("MOCA"); 4,4'-methylene-bis- (2,6-diethylaniline) ("MDEA"); 4,4'-methylene-bis -(2,3-dichloroaniline) ("MDCA"); 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane; 2,2'-3,3'-tetrachlorodiamino Diphenylmethane; trimethylene glycol di-p-aminobenzoate; and mixtures thereof. Preferably, the curing agent of the present invention is 3,5-dimethylthio-2,4-toluenediamine and its isomers, such as Ethacure® available from Albemarle Corporation of Baton Rouge, LA. 300. Suitable polyamine curing agents include both primary and secondary amines, and preferably have a molecular weight in the range of about 64 to about 2000.

  At least one diol, triol, tetraol, or hydroxy-terminated curing agent can be added to the polyurethane composition described above. Suitable diol, triol, and tetraol groups include: ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; polypropylene glycol; low molecular weight polytetramethylene ether glycol; 1,3-bis- [2- (2-hydroxyethoxy) ethoxy] benzene; 1,3-bis- {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} benzene; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; resorcinol-di- (β-hydroxyethyl) ether; hydroquinone-di- (β-hydroxyethyl) ether; and mixtures thereof. Preferred hydroxy-terminated curing agents are 1,3-bis (2-hydroxyethoxy) benzene; 1,3-bis- [2- (2-hydroxyethoxy) ethoxy] benzene; 1,3-bis- {2- [2 -(2-hydroxyethoxy) ethoxy] ethoxy} benzene; 1,4-butanediol, and mixtures thereof. Preferably, the molecular weight of the hydroxy-terminated curing agent ranges from about 48 to about 2000. Here, the molecular weight is an absolute weight average molecular weight, as understood by those skilled in the art.

  Both the hydroxy terminus and the amine curing agent can contain one or more saturated, unsaturated, aromatic, and cyclic groups. In addition, the hydroxy terminus and the amine curing agent can include one or more halogen groups. Polyurethane compositions can be made by blends or mixtures of curing agents. However, if desired, the polyurethane composition can be made with a single curing agent.

  In a preferred embodiment of the invention, the saturated polyurethane used to form the cover layer, particularly the outer cover layer, can be selected from both castable thermoset and thermoplastic polyurethane.

  In this example, the saturated polyurethane of this invention is substantially free of aromatic groups or moieties. Saturated polyurethanes suitable for use in the present invention are reaction products of at least one polyurethane prepolymer and at least one saturated curing agent. The polyurethane prepolymer is a reaction product of at least one polyol and at least one saturated diisocyanate. As is well known in the art, a catalyst may be employed to promote the reaction of the curing agent and the isocyanate and polyol.

  Saturated diisocyanates that can be used include, but are not limited to, ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene-1,4-diisocyanate; 1,6-hexamethylene diisocyanate ("HDI"); 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1 , 4-diisocyanate; 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane; isophorone diisocyanate ("IPDI"); Hexylene diisocyanate; HDI triisocyanate, 2,2,4-trimethyl-1,6-hexane diisocyanate triisocyanate ( "TMDI"). The most preferred saturated diisocyanates are 4,4'-dicyclohexylmethane diisocyanate ("HMDI") and isophorone diisocyanate ("IPDI").

  Saturated polyols suitable for use in this invention are, but not limited to, polyether polyols such as polytetramethylene ether glycol and poly (oxypropylene) glycol. Suitable saturated polyester polyols are polyethylene adipate glycol, polyethylene propylene adipate glycol, polybutylene adipate glycol, polycarbonate polyol and polyoxypropylene diol capped with ethylene oxide. Saturated polycaprolactone polyols useful in this invention include diethylene glycol initiated polycaprolactone, 1,4-butanediol initiated polycaprolactone, 1,6-hexanediol initiated polycaprolactone; trimethylolpropane initiated polycaprolactone, neopentyl glycol initiated polycaprolactone, And polytetremethyl ether glycol initiated polycaprolactone. The most preferred saturated polyols are PTMEG and PTMEG-initiated polycaprolactone.

  Suitable saturated hardeners are 1,4-butanediol, ethylene glycol, diethylene glycol, polytetramethylene ether glycol, propylene glycol; trimethanol propane; tetra- (2-hydroxypropyl) -ethylenediamine; isomers of cyclohexyldimethylol isomers. And mixtures, isomers and mixtures of cyclohexanebis (methylamine) isomers; triisopropanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 4,4'-dicyclohexylmethanediamine, 2,2,4-trimethyl- 1,6-hexanediamine; 2,4,4-trimethyl-1,6-hexanediamine; diethylene glycol di- (aminopropyl) A 4,4′-bis- (sec-butylamino) -dicyclohexylmethane; 1,2-bis- (sec-butylamino) cyclohexane; 1,4-bis- (sec-butylamino) cyclohexane; isophoronediamine, Hexamethylenediamine, propylenediamine, 1-methyl-2,4-cyclohexyldiamine, 1-methyl-2,6-cyclohexyldiamine, 1,3-diaminopropane, dimethylaminopropylamine, diethylaminopropylamine, imido-bis-propyl Amines, isomers and mixtures of diaminocyclohexane isomers, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, and diisopropanolamine. The most preferred saturated curing agents are 1,4-butanediol, 1,4-cyclohexyldimethylol and 4,4'-bis- (sec-butylamino) -dicyclohexylmethane.

  The compositions of this invention may be based on polyurea, which obviously differ from those based on polyurethane, but provide the desired aerodynamic and aesthetic properties when used in golf ball components. The polyurea-based composition is preferably saturated in nature.

  Without being bound by any particular theory, by replacing the long-chain polyol segment in the polyurethane prepolymer with a long-chain polyetherdiamine oligomer soft segment to form a polyurea prepolymer, shear, cutability and It is currently believed that the impact resilience is improved and the adhesion to other components is improved. Accordingly, the polyurea composition of the present invention comprises a reaction product of an isocyanate and a polyamine prepolymer crosslinked with a curing agent. For example, the polyurea-based composition of the present invention may be prepared from at least one isocyanate, at least one polyetheramine, and at least one diol curing agent or at least one diamine curing agent.

  All polyamines available to those skilled in the art are suitable for use in the polyurea prepolymer. Polyether amines are particularly suitable in the prepolymer. As used herein, the term “polyetheramine” means at least a polyoxyalkyleneamine comprising a primary amino group bonded to the end of the polyether backbone. However, the choice of diamines and polyetheramines is limited to those that allow the formation of polyurea prepolymers due to the rapid reaction of isocyanate and amine and the insolubility of many urea products. In one example, the polyether backbone is based on tetramethylene, propylene, ethylene, trimethylolpropane, glycerin, and mixtures thereof.

  Suitable polyether amines include, but are not limited to, polytetramethylene ether diamine, polyoxypropylene diamine, poly (ethylene oxide terminated oxypropylene) ether diamine, triethylene glycol diamine, propylene oxide based triamine, trimethylol propane Based triamines, glycerin based triamines, and mixtures thereof. In one example, the polyetheramine used to make the prepolymer is JEFFAMINE ™ D2000 (Huntsman, Austin, Texas).

  The molecular weight of the polyetheramine used in this invention ranges from about 100 to about 5000. The term “about” as used herein with respect to one or more numerical values or numerical ranges should be understood to include all numerical values within the range and mean all those numerical values. In one embodiment, the molecular weight of the polyetheramine is about 230 or greater. In other examples, the molecular weight of the polyetheramine is about 4000 or less. In yet another embodiment, the molecular weight of the polyetheramine is about 600 or greater. In yet another embodiment, the molecular weight of the polyetheramine is about 3000 or less. In yet another embodiment, the molecular weight of the polyetheramine is about 1000 to about 3000, more preferably about 1500 to about 2500. Since low molecular weight polyether ethers tend to form solid polyureas, large molecular weight oligomers such as JEFFAMINE D2000 are preferred.

  As mentioned briefly above, many amines are unsuitable for reaction with isocyanates due to the rapid reaction of amines with isocyanates. In particular, short-chain amines react quickly. However, in certain embodiments, a sterically hindered second diamine may be suitable for use in the prepolymer. Without being bound by any particular theory, amines with a high degree of steric hindrance, such as amines having a tertiary butyl group attached to the nitrogen atom, are more kinetic than amines with no or less hindrance. Is thought to be slow. For example, 4,4'-bis- (sec-butylamino) -dicyclohexylmethane (CLEARLINK ™ 1000) may be suitable for producing a polyurea prepolymer in combination with an isocyanate.

  Any isocyanate available to those skilled in the art is suitable for use in the polyurea prepolymer. The isocyanates used in the present invention include aliphatic, cycloaliphatic, araliphatic, aromatic, any of these derivatives, and combinations of these compounds having two or more isocyanate (NCO) groups per molecule. Including. Isocyanates can be organic polyisocyanate-terminated prepolymers, lower free isocyanates, and mixtures thereof. The reactive component comprising an isocyanate can include any isocyanate functional monomer, dimer, trimer, or multimeric adducts, prepolymers, pseudoprepolymers, or mixtures thereof. Isocyanate functional compounds can include monoisocyanates or polyisocyanates containing two or more isocyanate functional groups.

  Suitable isocyanate-containing components include diisocyanates having the following general formula: O═C═N—R—N═C═O, wherein R is preferably cyclic, aromatic containing from about 1 to about 20 carbon atoms. Or a linear or branched hydrocarbon moiety. The diisocyanate may further comprise one or more cyclic groups or one or more phenyl groups. When a polycyclic group or aromatic group is present, linear and / or branched hydrocarbons containing from about 1 to about 10 carbon atoms can be present as a spacer between the cyclic group or aromatic group. . In some cases, the cyclic or aromatic group may be substituted in the 2-, 3-, and / or 4-position, or in the ortho-, meta- and / or para-position, respectively. The substituted group is, but is not limited to, a halogen, a first, second, or third hydrocarbon group, or a mixture thereof.

Examples of diisocyanates that can be used in this invention include, but are not limited to, substituted and isomeric mixtures including 2,2'-, 2,4'-, and 4,4'-diphenylmethane diisocyanate (MDI). 3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI); toluene diisocyanate (TDI); polymer MDI; carbodiimide-modified liquid 4,4′-diphenylmethane diisocyanate; para-phenylene diisocyanate (PPDI); Phenylene diisocyanate (MPDI); triphenylmethane-4,4′- and triphenylmethane-4,4′-triisocyanate; naphthylene-1,5-diisocyanate; 2,4′-, 4,4′-, and 2 , 2-biphenyl diisocyanate; polyphenyl poly Limethylene polyisocyanate (PMDI); mixture of MDI and PMDI; mixture of PMDI and TDI; ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene-1,2-diisocyanate; tetramethylene-1,3-diisocyanate; 1,6-hexamethylene diisocyanate (HDI); octamethylene diisocyanate; decamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane -1,12-diisocyanate; dicyclohexylmethane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,2-diisocyanate; Cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methyl-cyclohexylene diisocyanate (HTDI); 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4'-dicyclohexyl diisocyanate; 1,4'-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanate methylcyclohexane isocyanate; 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane; isocyanate ethylcyclohexane isocyanate; bis (isocyanate methyl) Cyclohexane diisocyanate; 4,4′-bis (isocyanatomethyl) dicyclohexane; 2,4 ′ Bis (isocyanatomethyl) dicyclohexane; isophorone diisocyanate (IPDI); HDI triisocyanate; 2,2,4 trimethyl-1,6 hexane diisocyanate triisocyanate (TMDI); 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI); 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; 1,2-, 1,3- and 1,4-phenylene diisocyanates; aromatic aliphatic isocyanates such as 1,2 -, 1,3- and 1,4-xylene diisocyanates; meta-tetramethylxylene diisocyanate (m-TMXDI); para-tetramethylxylene diisocyanate (p-TMXDI); any polyisocyanate Trimerized isocyanurates of silicates, for example, isocyanurates of toluene diisocyanate, trimers of diphenylmethane diisocyanate, trimers of tetramethylxylene diisocyanate, isocyanurates of hexamethylene diisocyanate, and mixtures thereof; Dimerized ureasiions, such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, and mixtures thereof; modified polyisocyanates derived from the above-mentioned isocyanates and polyisocyanates; and mixtures thereof.

Examples of saturated diisocyanates that can be used in this invention include, but are not limited to, ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene-diisocyanate; tetramethylene-1,4-diisocyanate; 1,6-hexa Octamethylene diisocyanate; decamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate; cyclobutane- 1,3-diisocyanate; cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4- Isocyanate; methyl-cyclohexylene diisocyanate (HTDI); 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4'-dicyclohexyl diisocyanate; 2,4'-dicyclohexyl diisocyanate; 1,3,5-cyclohexane Isocyanate methylcyclohexane isocyanate; 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane; isocyanate ethylcyclohexane isocyanate; bis (isocyanate methyl) -cyclohexane diisocyanate; 4,4′-bis (isocyanate methyl) Dicyclohexane; 2,4'-bis (isocyanatomethyl) dicyclohexane; isophorone diiso Aneto (IPDI); HDI triisocyanate; 2,2,4 trimethyl-1,6 hexane diisocyanate triisocyanate (TMDI); 4,4'-dicyclohexylmethane diisocyanate _(H 12 MDI); 2,4- hexa Hydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; and mixtures thereof. Aromatic aliphatic isocyanates can also be used to produce light stable materials. Examples of these isocyanates include: 1,2-, 1,3- and 1,4-xylene diisocyanates; meta-tetramethylxylene diisocyanate (m-TMXDI); para-tetramethylxylene diisocyanate (p-TMXDI) ); Trimerized isocyanurate of any polyisocyanate, such as isocyanurate of toluene diisocyanate, trimer of diphenylmethane diisocyanate, trimer of tetramethylxylene diisocyanate, isocyanurate of hexamethylene diisocyanate, and mixtures thereof; A dimerized ureizion of any of the polyisocyanates, such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, and mixtures thereof; Modified polyisocyanates derived from cyanate and a polyisocyanate; and mixtures thereof. Furthermore, aromatic aliphatic isocyanates can be mixed with any of the saturated isocyanates listed above for the purposes of the present invention.

  By varying the number of unreacted NCO groups in the polyurea prepolymer of isocyanate and polyetheramine, factors such as the rate of reaction and the hardness of the resulting composition can be controlled. For example, the number of unreacted NCO groups in the polyurea prepolymer of isocyanate and polyetheramine can be less than about 14%. In one example, the polyurea prepolymer has from about 5% to about 11% unreacted NCO groups, more preferably from about 6% to about 9.5% unreacted NCO groups. In one example, the proportion of unreacted NCO groups is about 3% to about 9%. Alternatively, the proportion of unreacted NCO groups is about 7.5% or lower, more preferably about 7% or lower. In other examples, the proportion of unreacted NCO groups is from about 2.5% to about 7.5%, more preferably from about 4% to about 6.5%.

  As produced, the polyurea prepolymer may comprise from about 10% to about 20% by weight of the free isocyanate monomer of the prepolymer. As a result, in one embodiment, free isocyanate monomer may be removed from the polyurea prepolymer. For example, after removal, the prepolymer will contain 1% or less of free isocyanate monomer. In other examples, the prepolymer may comprise about 0.5% by weight or less than free isocyanate monomer.

  Polyetheramine can also be blended with additional polyol to form a copolymer that can be reacted with excess isocyanate to produce a polyurea prepolymer. In one embodiment, less than about 30% by weight of the copolymer is blended with a saturated polyetheramine. In other examples, less than about 20% by weight of the copolymer, preferably less than about 15% by weight of the copolymer is blended with a saturated polyetheramine. Any saturated polyol available to those skilled in the art, such as polyether polyols, polycaprolactone polyols, polyester polyols, polycarbonate polyols, hydrocarbon polyols, other polyols, and mixtures thereof are suitable for blending in accordance with the present invention. Yes. The molecular weight of these polymers can be from about 200 to about 4000, but can be from about 1000 to about 3000, more preferably from about 1500 to about 2500.

  Polyurea compositions can be made by cross-linking a polyurea prepolymer with a single curing agent or blend thereof. The curing agent used in this invention is preferably an amine-terminated curing agent, more preferably a second diamine curing agent, so that the composition contains only a single urea bond. In one embodiment, the molecular weight of the amine-terminated curing agent is about 64 or greater. In other examples, the molecular weight of the amine-terminated curing agent is about 2000 or less. As noted above, certain amine-terminal curing agents may be modified with a compatible amine-terminal freezing point depressant or mixture thereof.

  Suitable amine-terminated curing agents include, but are not limited to, ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; tetrahydroxypropyleneethylenediamine; 2,2,4- and 2,4,4- Trimethyl-1,6-hexanediamine; 4,4′-bis- (sec-butylamino) -dicyclohexylmethane; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (sec- Butylamino) -cyclohexane; 4,4′-bis- (sec-butylamino) -dicyclohexylmethane derivative; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis- (methylamine); -Cyclohexane-bis- (methylamine); diethylene glycol di- (a 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamine; imido-bis-propyl Amine; monoethanolamine, diethanolamine; triethanolamine; monoisopropanolamine, diisopropanolamine; isophoronediamine; 4,4′-methylenebis- (2-chloroaniline); 3,5-dimethylthio-2,4-toluenediamine; 3,5-dimethylthio-2,6-toluenediamine; 3,5-diethylthio-2,4-toluenediamine; 3,5-diethylthio-2,6-toluenediamine 4,4′-bis- (sec-butylamino) -diphenylmethane and its derivatives; 1,4-bis- (sec-butylamino) -benzene; 1,2-bis- (sec-butylamino) -benzene; N, N′-dialkylamino-diphenylmethane; trimethylene glycol-di-aminobenzoate; polytetramethylene oxide-di-p-aminobenzoate; 4,4′-methylenebis- (3-chloro-2,6-diethyleneaniline) 4,4'-methylenebis- (2,6-diethylaniline); meta-phenylenediamine; para-phenylenediamine; cyclohexyldimethol; and mixtures thereof. In one example, the amine-terminated curing agent is 4,4'-bis- (sec-butylamino) -dicyclohexylmethane.

  Suitable saturated amine-terminated curing agents include, but are not limited to, ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; tetrahydroxypropylene ethylenediamine; 2,2,4- and 2,4,4. -Trimethyl-1,6-hexanediamine; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (sec -Butylamino) -cyclohexane; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane derivative; 4,4'-dicyclohexylmethanediamine; 1,4-cyclohexane-bis- (methylamine); 3-cyclohexane-bis- (methylamine); diethylene glycol di- 2-aminopentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamine; Monoethanolamine, diethanolamine; triethanolamine; monoisopropanolamine, diisopropanolamine; isophoronediamine; triisopropanolamine; and mixtures thereof. In one example, the amine-curing agent has a molecular weight of about 64 or greater. In addition, any of the above polyether amines can be used as a curing agent to react with the polyurea prepolymer.

  Suitable catalysts include, but are not limited to, bismuth catalyst, oleic acid, triethylenediamine (DABCO ™ -33LV), di-butyltin dilaurate (DABCO ™ -T12) and acetyl acid. The most preferred catalyst is di-butyltin dilaurate (DABCO ™ -T12). The DABCO ™ product is manufactured by Air Products and Chemicals.

  Thermoplastic materials may be blended with other thermoplastic materials, but thermosetting materials are difficult to blend uniformly after the thermosetting material is produced, even if blending is not possible. Preferably, the saturated polyurethane has from about 1% to about 100%, more preferably from about 10% to about 75% of the cover composition and / or interlayer composition. About 90% to about 10%, more preferably about 90% to about 25% of the cover and / or interlayer composition is composed of one or more other polymers and / or other materials as described below. May be. Such polymers include, but are not limited to, polyurethane / polyurea ionomers, polyurethanes or polyureas, epoxy resins, polyethylenes, polyamides and polyesters, polycarbonates and polyacrylins. Unless otherwise noted, percentages are weight percentages of the total composition of the subject golf ball layer.

  The polyurethane prepolymer is produced by combining at least one polyol, such as polyether, polycaprolactone, polycarbonate or polyester, and at least one isocyanate. The thermosetting polyurethane can be obtained by curing at least one polyurethane prepolymer with a curing agent selected from polyamine, triol or tetraol. The thermoplastic polyurethane can be obtained by curing at least one polyurethane prepolymer with a diol curing agent. Curing agent selection is critical because some urethane elastomers cured with diols and / or blends of diols do not produce urethane elastomers with the impact resistance required by golf ball covers. Blending a diol-cured urethane elastomer formulation with a polyamine curing agent results in a thermoset urethane with improved impact and cut resistance.

  Thermoplastic polyurethanes can be blended with suitable materials to produce thermoplastic objects. Examples of these additional materials can include ionomers such as the SURLYN ™, ESCOR ™ and IOTEK ™ copolymers described above.

  Other suitable materials that can be combined with saturated polyurethanes in the production of golf ball covers and / or interlayers of this invention are ionic or non-ionic polyurethanes and polyureas, epoxy resins, polyethylene, polyamides and polyesters. For example, the cover and / or intermediate layer may comprise at least one saturated polyurethane and thermoplastic or thermosetting ionic and non-ionic urethanes and polyurethanes, cationic urethane ionomers and urethane epoxides, ionic and non-ionic polyureas and these Can be made from a blend with. Examples of suitable urethane ionomers are disclosed in US Pat. No. 5,692,974 entitled “Golf Ball Cover”, which is incorporated herein by reference. Other examples of suitable polyurethanes are described in US Pat. No. 5,334,673. Examples of suitable polyureas are described in US Pat. No. 5,484,870, and examples of suitable polyurethanes cured with epoxy group-containing curing agents are described in US Pat. No. 5,908,358. The disclosures of which are incorporated herein by reference.

Various additional ingredients can also be added to the cover composition of this invention. These are, but not limited to, white pigments such as TiO ₂ , ZnO, optical brighteners, surfactants, processing aids, blowing agents, UV stabilizers, and light stabilizers. Saturated polyurethane is fade resistant. However, it is not resistant to the deterioration of mechanical properties due to the weather. UV absorbers and light stabilizers can be added to maintain the tensile strength and elongation of the saturated polyurethane elastomer. Suitable UV absorbers and light stabilizers include but are not limited to TINUVIN ™ 328, TINUVIN ™ 213, TINUVIN ™ 765, TINUVIN ™ 770, and TINUVIN ™ 622. A preferred UV absorber is TINUVIN ™ 328 and a preferred light stabilizer is TINUVIN ™ 765. TINUVIN ™ products are available from Ciba-Geigy. Dyes, optical brighteners and fluorescent pigments can be included in golf ball covers made with polymers made in accordance with the present invention. These additional ingredients can be added in any amount that achieves their desired purpose.

  Any technique known to those skilled in the art for the polyurethanes of this invention can be employed. One commonly employed technique is known as the one-shot method, in which polyisocyanate, polyol and curing agent are mixed simultaneously. With this approach, the resulting mixture is non-uniform (more random), making it difficult for the manufacturer to control the molecular structure of the product composition. A preferred mixing method is known as the prepolymer method. In this method, the polyisocyanate and the polyol are mixed separately before adding the curing agent. This method results in a more uniform mixture and results in a more consistent polymer composition. Other suitable methods for producing the layers of this invention include reaction injection molding ("RIM"), liquid injection molding ("LIM"), pre-reacting components to produce an injection moldable thermoplastic polyurethane and then injection. These are all known to those skilled in the art.

  Additional components that can be added to the polyurethane composition are UV stabilizers and other dyes, as well as optical brighteners and fluorescent dyes and pigments. Such additional ingredients can be added in any amount that achieves their desired purpose.

  It has been found according to the present invention that castable reactive materials can be applied in fluid form, enabling a very thin outer cover layer on a golf ball. Specifically, the castable reactive liquid reacts to form a urethane elastomer material, which achieves the desired very thin outer cover layer.

  The castable reactive liquid employed to form the urethane elastomer material can be applied to the core using a variety of application methods well known in the art, such as spraying, dipping, spin coating, or flow coating methods. Can be applied. An example of a suitable coating technique is disclosed in US Pat. No. 5,733,428, which is incorporated herein by reference.

  The outer cover is preferably formed around the inner cover by mixing the materials and guiding them to the mold. It is important to measure the viscosity over that time. With this measurement, the subsequent steps of filling the mold, introducing the individual into the opposite side, and closing the mold are performed in a timely manner, resulting in a fusion core opposite the core and cover. , Overall integrity is achieved. It has been found that the viscosity range of a cured urethane mix suitable for introducing the core into the mold is between about 2000 cP and about 30000 cP, with a preferred range between about 8000 pC and 15000 cP.

  To begin the production of the cover, the prepolymer and hardener are mixed by feeding metered amounts of hardener and prepolymer through a line in a mixing head fitted with a motor driven mixer. A centering pin that fills the upper half of the preheated mold and moves to the opening of each mold is placed on the mounting unit. Later, the lower half mold or series of lower half molds retains the same amount of mixture introduced into the cavity. After the reaction material is present in the upper mold for about 40 to about 80 seconds, the core is dropped at a controlled rate to form a gel-like reaction mixture.

  A ball cup holds the ball core by reduced pressure (or partial vacuum). After gelling for about 40 to about 80 seconds, place the core on both halves of the mold, release the vacuum and release the core. The mold half with the core and the solidified cover half is removed from the centering fixture and flipped to fit the second mold half and the selected amount introduced into the second mold The reactive polyurea prepolymer and curing agent of this begin to gel at an appropriate time before being combined.

  Similarly, both US Pat. No. 5,0062,977 and US Pat. No. 5,334,673 disclose suitable molding techniques that can be used to apply the castable reactive liquid used in this invention. is doing. In addition, U.S. Pat. Nos. 6,618,0040 and 6,180,722 disclose a method for preparing a dual core golf ball. These are incorporated individually by reference. Note that the method of the present invention is not limited to these techniques.

  Balls prepared in accordance with the present invention achieve substantially the same or greater resilience or coefficient of restitution ("COR") compared to conventional structured balls, depending on the desired properties, and then compression or Decrease the elastic modulus. Further, balls prepared in accordance with the present invention substantially increase resiliency or COR without increasing compression when compared to normal balls. Another measure of this elasticity is the “loss tangent” or tan δ, which is obtained by measuring the dynamic stiffness of the object. The terms loss tangent and such dynamic characteristics are typically described according to ASTM D4092-90. The low loss tangent means that much of the energy applied from the club to the golf ball has been converted to dynamic energy. That is, energy means that the launch measure has been converted to a long flight distance. The rigidity or compression rigidity of a golf ball can be measured by, for example, dynamic rigidity. A large dynamic stiffness means a large compression stiffness. In order to produce a golf ball with the desired compression stiffness, the dynamic stiffness of the cross-linked reaction product must be less than about 50,000 N / m-50 ° C. Preferably, the dynamic stiffness should be between about 10,000 and about 40000 N / m-50 ° C, more preferably the dynamic stiffness should be between about 20000 and about 30000 N / m-50 ° C. .

  The coefficient of restitution (COR) measures the innateness between a ball and a relatively larger object. One conventional technique for measuring COR uses a golf ball or golf ball subassembly, an air cannon, and a stationary vertical steel plate. The steel sheet forms an impact surface weighing about 100 pounds or about 45 kg. A pair of ballistic light screens are spaced apart between the air cannon and the steel plate to speed up the ball. The ball is fired from the air cannon toward the steel plate over a range from 50 ft / s (15.2 m / s), which is a test speed, to 180 ft / s (54.9 m / s). Unless otherwise stated, the COR data presented in this application was measured using a speed of 125 ft / s (38.1 m / s). While the ball is facing the steel plate, the ball activates each light screen and the time on each light screen is measured. In this measurement, the incident time interval is proportional to the incident speed of the ball. The ball hits the steel plate, reflects and passes through the light screen. This again measures the time interval required to travel between the light screens. For this reason, the time interval at the time of reflection is proportional to the ball speed at the time of reflection. For COR, the coefficient of restitution can be calculated as the ratio of the reflection time interval to the incident time interval.

  The COR of the material is between 0.25 inches and 1.68 inches, preferably between 1.00 inches and 1.62 inches, more preferably between 1.30 inches and 1.60 inches. It is defined as the COR of a sphere molded with the material, and COR is tested as described above. The COR of the material can also be tested for plaque, button or slab material, for example, Bayshore elasticity, tangent delta. This is done by dynamic mechanical analysis. A technique for measuring the coefficient of restitution is described in US patent application Ser. No. 10 / 914,289, filed by the present applicant, incorporated herein by reference. With a COR value defined above according to the present invention at 125 ft / sec, the coefficient of restitution of the material may be between about 0.500 and about 0.900, preferably about 0.700 to about 0. .875, more preferably between about 0.750 and about 0.850. The COR of the material used to form the layer (center, outer core, middle layer, inner or outer cover, etc.) is “extrapolated” or standardized with respect to the COR of a standard sphere, and as described above, the composite sub The same formula used for the assembly is used for “Material COR”.

  Compression is an important factor in golf ball design. For example, the compression of the core affects the spin rate and feeling when the ball driver is off. Several techniques are used to measure compression, including Atti compression, Riehle compression, load / deflection measurements at various fixed loads and offsets, and effective modulus. For details, see Jeff Dalton, Compression by Any Other Name, Science and Golf IV, Proceedings of the World Scientific of Golf (referred to as "Eric Thane ed. 200"). To convert Atti compression into Riehle (core), Riehle (ball), 100 kg deflection, 130-10 kg deflection or effective elastic modulus, it can be performed using the formula shown in “J. Dalton”. Similarly, the golf balls of this invention are not constrained by individual developments in modulus, hardness or compression. The coating or paint layer on the dimple surface of the ball is not considered a part or layer of the structure considered here.

  The molding process and composition of each part of the golf ball typically results in a gradient of material properties. The technique employed in the prior art generally adjusts the hardness to achieve the gradient. Hardness is a static elastic modulus quantification technique and does not represent the elastic modulus of a material at the rate of deformation associated with golf ball use, ie, hitting by a club. As is well known in the field of polymer science, alternative deformation rates can be emulated using the time-temperature superposition principle. For golf ball portions containing polybutadiene, 1-Hz oscillation at temperatures between 0 ° C. and −50 ° C. is believed to be quantitatively equivalent to the golf ball impact velocity. Therefore, by measuring the loss tangent and dynamic stiffness from 0 ° C. to −50 ° C., preferably from −20 ° C. to −50 ° C., the performance of the golf ball can be accurately estimated.

  In another embodiment of the present invention, the golf ball of the present invention is substantially spherical and the cover has a plurality of dimples on the outer surface.

  U.S. Patent Application No. 10/203015, i.e. U.S. Patent Application Publication No. 2003/0114565, and U.S. Patent Application No. 10/108793, i.e. U.S. Patent Application Publication No. 2003/0050373, disclose soft and highly flexible ionomers. The disclosure of which is incorporated herein by reference. The ionomer is preferably an acid copolymer consisting of at least one E / X / Y copolymer, where E is ethylene, X is an α, β-ethylenically unsaturated carboxylic acid, and Y is a softening comonomer. It is. X is preferably present in an amount of 2-30% by weight of the polymer (more preferably 4-20% by weight, most preferably 5-15% by weight). Y is preferably present in an amount of 17-40% by weight of the polymer (more preferably 20-40% by weight, most preferably 24-35% by weight). Preferably, the base resin has a melt index (MI) of at least 20 or at least 40, more preferably at least 75, and most preferably at least 150. The specific soft elastic ionomer included in this invention is a partially neutralized ethylene / (meth) acrylic acid with MI and neutralization levels that provide a melt processable polymer with beneficial physical properties. / Butyl (meth) acrylate copolymer. These copolymers are at least partially neutralized. Preferably, the acid moiety in the acid copolymer of at least 40 or more preferably at least 55, even more preferably about 70, most preferably about 80, is neutralized by one or more alkali metal, transition metal or alkaline earth metal cations. Has been. Useful cations for preparing the ionomers of this invention are lithium, sodium, potassium, magnesium, calcium, barium, or zinc or combinations of these cations.

An additional optional additive useful in the practice of this invention is an acid copolymer wax (e.g., Allied Wax AC143, which is ethylene / 16-18% acrylic acid coparmer and is considered to have an average molecular weight of 2040. Which helps to prevent reaction between the filler material (e.g. ZnO) and the acid portion of the ethylene coparimer. Other optional additives include a TiO _2, which bleaches, brighteners, surfactants, used as a processing aid.

  Ionomers (may be blended with conventional ionomer copolymers (di-, ter-, etc.) and product properties are adjusted to the desired one using well-known techniques. Even after blending, conventional ionomers are still based. Compared with blending, the hardness is small and the elastic modulus is large.

  The ionomer may be blended with a nonionic thermoplastic resin to adjust the product characteristics. Nonionic thermoplastic resins are not limited to these examples, but are based on thermoplastic elastomers such as polyurethane, polyether-ester, poly-amide-ether, polyether-urea, PEBAX (polyether-block-amide). (Commercially available from Atochem), styrene-butadiene-styrene (SBS) block copolymers, styrene (ethylene-butylene) -styrene block copolymers, other polyamides (oligomers or polymers), polyesters, polyolefins (Including PE, PP, E / P coparimer, etc.), ethylene copolymers with various comonomers (for example, vinyl acetate, (meth) acrylate, (meth) acrylic acid, epoxy functionalized monomers, C Etc.), including maleic anhydride-grafted, functionality copolymers with epoxy, etc., elastomers such as EPDM, metallocene catalyzed PE and copolymer, ground powder of thermosetting elastomer, and the like. In such thermoplastic blends, the first thermoplastic material may be from about 1% to about 99% by weight, and the second thermoplastic material may be from about 99% to about 1% by weight. Good.

  In addition, US Pat. No. 6,953,820 and US Pat. No. 6,653,382 are discussing high COR compositions manufactured as solid spheres, the disclosure of which is incorporated herein by reference. Incorporate here.

  The cover must be selected from conventional materials that are employed as golf ball covers based on the desired performance characteristics. The cover may have one or more layers. Cover materials such as ionomer resins, blends of ionomer resins, and thermoplastic or thermoset urethanes and balatas may be employed as is known in the art. In other embodiments, additional layers may be added to the layers described above, and existing layers may be fabricated from multiple materials.

  When manufacturing a golf ball according to the present invention, the golf ball typically has a dimple region greater than about 60 percent, preferably greater than about 65 percent, and more preferably greater than about 75 percent. The flexural modulus of the golf ball cover is typically greater than about 500 psi, preferably from about 500 psi to about 150,000 psi, as measured by ASTM method D6272098, Procedure B. As mentioned above, the outer cover layer is preferably formed from a relatively soft polyurethane material. Specifically, the material hardness of the outer core layer material is less than about 45 Shore D, preferably less than about 40 Shore D, more preferably about 25 and about 40, as measured by ASTM-D2240. Between Shore D, most preferably between about 30 and about 40 Shore D. The material hardness of the casing is preferably less than about 70 Shore D, more preferably between about 30 and about 70 Shore D, and most preferably between about 50 and about 65 Shore D.

  The overall outer diameter of the multilayer golf ball may be any size. The National Golf Association ("USGA") regulations limit the minimum size of a competitive golf ball to 1.680 inches. There is no provision for maximum diameter. However, any size golf ball can be used for play. The preferred diameter of the golf ball is about 1.680 inches to about 1.800 inches. A more preferred diameter is from about 1.680 inches to about 1.760 inches. The most preferred diameter is from about 1.680 inches to about 1.740 inches.

  The golf ball of the present invention has a moment of inertia (“MOI”) of less than about 85, preferably less than 83. The MOI is typically measured by a model number MOI-005-104 moment of inertia device manufactured by Inertia Dynamic, Inc., Corinthville, Connecticut. This device is connected to a PC by a COMM port and is driven by MOI device software version 1.2.

  U.S. Patent Nos. 6,193,619, 6,207,784, and 6,221,960 and U.S. Patent Application Nos. 09 / 590,401 (filed Jun. 15, 2000), 09/678771 (October 2000). No. 3, filed on Nov. 3, 1999, and 09/44752 (filed Nov. 23, 1999).

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

  Although the numerical ranges and parameters representing the broad scope of the invention are approximate, the numerical values shown in the examples were recorded as accurately as possible. Any numerical value still contains errors necessarily resulting from the standard deviation found in each test measurement. Further, it should be understood that any combination of values, including the exemplified values, can be used where numerical ranges of various scopes are indicated.

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

  The accompanying drawings constitute a part of the specification and are to be understood in relation to the specification, in which similar reference desires indicate portions of the analogy in the various figures.

1 is a front view of a golf ball with dimples according to the present invention. FIG. 2 is a cross-sectional view of the golf ball of FIG. 1 showing a solid core encased by a thin water vapor barrier layer and a cover. FIG. 6 is a cross-sectional view of another golf ball according to the present invention, showing a solid core in which a multi-layer solid core is wrapped with a thin water vapor barrier layer.

Explanation of symbols

10 golf ball 12 solid core 12a center 12b inner core layer 12c outer core layer 14 intermediate layer 16 cover

Claims (5)

At least three core layers including a center, an inner core layer, and an outer core layer;
At least one cover layer;
At least one water vapor barrier layer between the outer core layer and the at least one cover layer that achieves a water vapor transmission rate smaller than that of the cover layer, and includes a butyl rubber, a polysulfide rubber, and a uretdione. the water vapor containing one pack castable polymers, single pack castable polymers, local curable material selected from the group consisting of single Ichipa click castable polymer containing isocyanate and polyol containing isocyanate and amine A barrier layer,
The center, the inner core layer, and the outer core layer are provided with a hardness gradient,
The hardness gradient increases toward the at least one intermediate water vapor barrier layer;
The center has a hardness of 50 Shore C or less, or
The hardness of the inner core is greater than 50 Shore C, or the hardness of the outer core is greater than 65 Shore C, or
Meet these combinations,
The thickness of the at least one water vapor barrier layer is relatively uniform and is less than or equal to 0.135 cm (0.020 inches), and the at least one water vapor barrier layer includes a thermoplastic elastomer binder, and a low water vapor transmission rate. A multi-layer golf ball characterized by having a granular material . The multilayer golf ball of claim 1, wherein the ratio of the particulate material to the binder material is 1: 1. The multilayer golf ball according to claim 1, wherein the moment of inertia is less than 85 kg · m ² . The multilayer golf ball of claim 1, wherein the coefficient of restitution is greater than 0.7. The multilayer golf ball of claim 1, wherein the ATTI compression is at least 40.

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