JP4021424B2 - Water resistant polyurea elastomer for golf equipment - Google Patents

Description

This application is a U.S. Patent Application No. 10 / 066,637 filed on Feb. 6, 2002 (which was filed on Dec. 3, 1999 and is currently U.S. Patent No. 09,435,986). No. 10 / 228,311 filed on Aug. 27, 2002 (the application was filed on Dec. 17, 1999). A continuation-in-part of US patent application 09 / 466,434, filed on the same day, currently US Pat. No. 6,476,176, and one of currently pending US patent application 09 / 951,963, filed September 13, 2001 And claims the priority of US Provisional Patent Application No. 60 / 401,047, filed Aug. 6, 2002. The disclosures of these applications are all incorporated herein by reference.
The present invention relates to a golf equipment comprising a polyurea composition. In particular, the present invention relates to golf equipment comprising a composition prepared from a polyurea prepolymer, ie, an amine-terminated compound and an isocyanate, and crosslinked with a curing agent, and a method for producing the golf equipment. Preferably, the components of the composition are saturated, i.e. substantially free of unsaturated carbon-carbon bonds or aromatic groups to prepare a light stable composition. The present invention also relates to a golf ball constituent formed from a water-resistant polyurea elastomer.

Golf equipment, i.e. clubs and balls, are manufactured from various compositions. For example, golf ball covers are formed from a variety of materials such as balata and ionomer resins. Balata is a natural or synthetic trans-polyisoprene rubber. Balata-coated balls are preferred by highly skilled golfers because their cover flexibility allows players to get enough spin speed to more accurately control the ball direction and distance, especially in short shots. It is rare.
However, balata-coated balls are easily damaged and thus lack the durability required by average golfers. Accordingly, other cover compositions have been developed in an attempt to provide a golf ball having a spin rate and feel close to that of a balata-coated ball, yet having high durability and overall distance.
Ionomer resins have replaced balata as a cover material to a considerable extent. Chemically, ionomer resins are α, β-ethylenically unsaturated carboxylic acids having 10-90% carboxylic acid groups neutralized with olefins and metal ions as disclosed in US Pat. No. 3,264,272. And a copolymer. Commercially available ionomer resins include, for example, copolymers of methacrylic acid or acrylic acid and ethylene neutralized with metal salts. Examples of commercially available ionomer resins include, but are not limited to, SURLYN® from DuPont de Nemours and Company, and ESCOR® and IOTEK® from Exxon Corporation. ) These ionomer resins are distinguished by the type of metal ion, the amount of acid and the degree of neutralization.

U.S. Pat. Nos. 3,454,280, 3,819,768, 4,323,247, 4,526,375, 4,884,814, and 4,911,451 all relate to the use of SURLYN® type compositions in golf ball covers. However, although SURLYN®-coated golf balls as described in these patent documents have a substantially cut-resistant cover, the spin and feel are inferior to balata-coated balls. .
Polyurethane has also been recognized as a useful material for golf ball covers since approximately 1960. U.S. Pat. No. 3,147,324 relates to a method for manufacturing a golf ball having a polyurethane cover. The resulting golf ball is durable and maintains the “feel” of a balata ball.
Various companies are studying the usefulness of polyurethane as a golf ball cover material. U.S. Pat. No. 4,123,061 teaches a golf ball made from a polyurethane prepolymer prepared from a polyether and a diisocyanate, cured with either a polyol or an amine type curing agent. US Pat. No. 5,334,673 discloses two categories of polyurethanes available on the market for golf ball cover formation, namely thermosetting and thermoplastic polyurethanes, in particular polyurethane prepolymers and slow-reactive amine curing agents, and / or A thermoset polyurethane coated golf ball made from a composition with glycol is disclosed.

Unlike SURLYN® coated golf balls, polyurethane golf ball covers can be manufactured to have the soft “feel” of balata coated golf balls. However, golf ball covers made from polyurethane have so far been sufficient for SURLYN® golf balls in terms of the elasticity and resilience of the golf ball cover as a function of the initial velocity of the golf ball after impact by the golf grab. Is not comparable.
Furthermore, the polyurethanes used to make such golf ball covers generally contain aromatic components, such as aromatic diisocyanates, polyols or polyamines, so that they are sensitive to light, especially ultraviolet (UV) light. Susceptible to discoloration upon exposure. In order to retard the color change, light and UV stabilizers such as TINUVIN® 770, 765, and 328 are added to these aromatic polymeric materials. However, in order to further ensure that the cover formed from aromatic polyurethanes does not change color, the cover is coated with a white paint and then covered with a clear coat to maintain the whiteness of the golf ball. The application of a uniform white colored coat to the dimple surface of a golf ball is a difficult process that adds time and cost to the manufacture of a golf ball.

Furthermore, although polyurethanes prepared from polyether polyols are more stable in moisture resistance than polyurethanes prepared using polyester polyols, polyurethanes are highly sensitive to changes in their properties due to moisture absorption. is there. In order to avoid moisture absorption, manufacturers have attempted to use a moisture barrier layer placed between the core and the cover (eg, US Pat. No. 5,820,488). However, there remains a need for materials that are resistant to moisture absorption that are suitable for forming golf ball components.
Polyurea has also been proposed as a cover material for golf balls. For example, US Pat. No. 5,484,870 discloses a polyurea composition comprising a reaction product of an organic isocyanate and an organic amine, each having at least two functional groups. As soon as these two components are mixed, a polyurea is formed, thus limiting the ability to change the physical properties of the composition. Like polyurethanes, polyureas have not been able to fully combat SURLYN® golf balls with respect to the resilience or resilience or damping behavior of golf ball covers.

  Thus, golf having a soft component that provides improved resilience, increased cutting, scratch and abrasion resistance, moisture resistance, and enhanced adhesion without adversely affecting the overall performance characteristics of the golf ball. Tools are continually sought. In addition, it would be beneficial to provide a composition that combines cutting and scratch resistance with improved resistance to discoloration suitable for the manufacture of golf ball components and other golf-related equipment.

The present invention generally relates to golf equipment having at least a portion formed from a polyurea composition. In one embodiment, the present invention relates to a one-piece golf ball comprising polyurea. In another embodiment, the composition of the present invention is used in two-piece and multi-component golf balls including at least one cover layer and one core, such as three-piece, four-piece golf balls, and at least one cover layer. Includes at least one polyurea, and similarly, a multi-component golf ball includes a core and / or cover having two or more layers, at least one of such layers being formed from at least one polyurea Is done.
For example, one aspect of the invention relates to a golf ball having a core and a cover, wherein the cover is formed from a reactive product composition comprising an isocyanate and an amine-terminated compound selected from the group consisting of: :

Wherein n, x, y and z are about 1 or more, preferably about 1 to about 20, and R is about 1 to about 20 carbon atoms, preferably about 1 to about 12 carbons. An alkyl group having an atom, a phenyl group, a cyclic group, or a mixture thereof; R ₁ and R ₂ are alkylene having from about 1 to about 20 carbon atoms, preferably from about 1 to about 12 carbon atoms A group, a phenylene group, a cyclic group, or a mixture thereof; R ₃ is hydrogen, a methyl group, or a mixture thereof).
In one embodiment, the composition comprises a bond having the general formula: or a mixture thereof:

(Wherein x is, for example, a chain length of about 1 or greater; R and R ₁ are straight or branched hydrocarbon chains having from about 1 to about 20 carbons).
In another embodiment, the composition comprises only bonds having the general formula:

(Wherein x is, for example, a chain length of about 1 or greater; R and R ₁ are straight or branched hydrocarbon chains having from about 1 to about 20 carbons).
The composition may further comprise a curing agent selected from the group consisting of hydroxy-terminated curing agents, amine-terminated curing agents, and mixtures thereof. In one embodiment, the amine-terminated curing agent is a secondary diamine curing agent. In another embodiment, the amine-terminated curing agent is ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6. -Hexanediamine; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane; N, N'-diisopropyl-isophoronediamine; 1,4-bis- (sec-butylamino) -cyclohexane; Bis- (sec-butylamino) -cyclohexane; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane derivative; 4,4'-dicyclohexylmethanediamine; 1,4-cyclohexane-bis- (methylamine) 1,3-cyclohexane-bis- (methylamine); diethylene glycol bis- (aminopropyl) ether; 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamine; imido-bis- (propylamine); monoethanolamine; diethanolamine; triethanolamine; monoisopropanolamine; diisopropanolamine; Selected from the group consisting of isophoronediamine; polyoxypropylenediamine; propylene oxide-based triamine; 3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixtures thereof.

The cover preferably has a yellowness index difference (ΔYI) of about 12 or less after 5 days of UV light exposure. Furthermore, the cover preferably has a b chromaticity range difference of about 6 or less after 5 days of UV light exposure.
In one embodiment, the composition may include at least one density adjusting filler.
The present invention also includes a core; a layer that may be placed around the core to form an internal ball, which may include at least one thermoplastic or thermosetting non-ionomeric material; and a cover cast on the internal ball The cover also includes at least one isocyanate, at least one amine-terminated compound, and at least one curing agent that includes a hydroxy-terminated curing agent, an amine-terminated curing agent, or a mixture thereof. Contains light stable polyurea material. The amine-terminated compound is selected from the group consisting of amine-terminated hydrocarbons, amine-terminated polyethers, amine-terminated polyesters, amine-terminated polycaprolactones, amine-terminated polycarbonates, amine-terminated polyamides, and mixtures thereof. In one embodiment, the amine-terminated compound comprises primary amines, secondary amines, triamines, or combinations thereof.
In another embodiment, the cover has a thickness of about 0.02 inches to about 0.035 inches (about 0.508 mm to about 0.889 mm). In yet another embodiment, the layer has a first Shore D hardness, the cover has a second Shore D hardness, and the ratio of the second Shore hardness to the first Shore D hardness is about 0.7 or less. It is. In yet another embodiment, the core has a diameter of about 1.55 or greater.

The inner ball may include a moisture resistant barrier layer. In one embodiment, the internal ball is surface treated.
The present invention also relates to a golf ball comprising a core, an intermediate layer having a hardness of about 60 Shore D or greater, and a cover formed from a polyurea material comprising at least one isocyanate and at least one amine-terminated compound. The cover has a hardness of about 30 Shore D to about Shore 60, and the golf ball has a COR of about 0.800 or more.
The amine-terminated compound is selected from the group consisting of amine-terminated hydrocarbons, amine-terminated polyethers, amine-terminated polyesters, amine-terminated polycaprolactones, amine-terminated polycarbonates, amine-terminated polyamides, and mixtures thereof. Further, the polyurea material may further include a curing agent selected from the group consisting of a hydroxy-terminated curing agent, an amine-terminated curing agent, and a mixture thereof.
In one embodiment, the ratio of the cover hardness to the intermediate layer hardness is about 0.7 or less. In another embodiment, the cover has a thickness of about 0.2 inches to about 0.035 inches (about 5.08 mm to about 0.889 mm).
In yet another embodiment, the intermediate layer includes an ionomer material. In another embodiment, the intermediate layer comprises a thermosetting non-ionomeric material, a thermoplastic non-ionomeric material, or a mixture thereof.

The present invention also relates to a golf ball comprising at least one cover and at least one core layer, the cover comprising at least one polyurea composition prepared from a polyurea prepolymer, ie, an isocyanate and an amine-terminated compound. And is formed from a composition cured with a curing agent.
The present invention further relates to a golf ball comprising a cover, a core, and at least one intermediate layer inserted between the cover and the outermost core layer, wherein the intermediate layer comprises a polyurea prepolymer, ie, isocyanate. And an amine-terminated compound and formed from a composition cured with a curing agent.
Furthermore, the present invention also relates to a golf ball comprising a cover, a core, and at least one intermediate layer inserted between the cover and the core, wherein the outermost cover layer and the at least one intermediate layer are both: Formed from a polyurea prepolymer, ie, a polyurea composition comprising an isocyanate and an amine terminated compound and cured with a curing agent.
In another embodiment of the invention, the cover preferably comprises from about 1 to about 100% by weight of polyurea, the remainder of the cover (if present) being at least one known to those skilled in the art. Other polymers. In another embodiment, the cover preferably comprises about 1 to about 100 weight percent polyurea, the remainder of the cover (if present) being one or more as known to those skilled in the art. Of compatible elastic polymers.
The present invention further relates to a golf ball comprising at least one light-stable cover layer formed from a composition comprising at least one polyurea prepared from a polyurea prepolymer and a curing agent. In one embodiment, the polyurea prepolymer comprises at least one isocyanate and at least one amine-terminated compound.

  In this aspect of the invention, the isocyanate is saturated and is ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene diisocyanate; tetramethylene-1,4-diisocyanate; 1,6-hexamethylene diisocyanate; Decamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,2 -Diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methylcyclohexylene diisocyanate; 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate 4,4'-dicyclohexyl diisocyanate; 2,4'-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanate methylcyclohexane isocyanate; 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane; Isocyanatoethylcyclohexaneisocyanate; bis (isocyanatemethyl) -cyclohexanediisocyanate; 4,4'-bis (isocyanatemethyl) dicyclohexane; 2,4'-bis (isocyanatemethyl) dicyclohexane; isophorone diisocyanate; HDI triisocyanate; 2,4-trimethyl-1,6-hexane diisocyanate triisocyanate; dicyclohexylmethane diisocyanate; 4,4'-dicyclohexylmethane diisocyanate; 2,4-hexahydrotoluene diisocyanate Sulfonate; is selected from and mixtures thereof; 2,6-hexahydrotoluene diisocyanate. The saturated diisocyanate is preferably selected from the group consisting of isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, or combinations thereof.

In another embodiment, the isocyanate is meta-tetramethylxylene diisocyanate; para-tetramethylxylene diisocyanate; trimerized isocyanurate of polyisocyanate; dimerized uretdione of polyisocyanate; An aromatic aliphatic isocyanate selected from the group consisting of isocyanates; and mixtures thereof.
The amine-terminated compounds are polytetramethylene ether diamine, polyoxypropylene diamines, poly (ethylene oxide capped oxypropylene) ether diamines, triethylene glycol diamines, propylene oxide triamines, trimethylolpropane triamines, It may be a polyetheramine selected from the group consisting of glycerin-based triamines and mixtures thereof. In one embodiment, the polyetheramine has a molecular weight of about 1000 to about 3000.

  The curing agent may be selected from the group consisting of hydroxy-terminated curing agents, amine-terminated curing agents, and mixtures thereof. In one embodiment, the hydroxy-terminated curing agent is ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol; dipropylene glycol. Polypropylene glycol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; trimethylolpropane; cyclohexyl Dimethylol; triisopropanolamine; N, N, N ′, N′-tetra- (2-hydroxypropyl) -ethylenediamine; diethylene glycol bis- (aminopropyl) ether; 1,5-pentanediol; 1,6-hexanediol 1,3-bis- (2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol; 1,3-bis- [2- (2-hydride); Xyloxy) ethoxy] cyclohexane; 1,3-bis- {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} cyclohexane; trimethylolpropane; preferably polytetramethylene ether glycol having a molecular weight of about 250 to about 3900 And a mixture thereof.

The amine-terminated curing agent is ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine; -Bis- (sec-butylamino) -dicyclohexylmethane; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (sec-butylamino) -cyclohexane; 4,4'-bis- Derivatives of (sec-butylamino) -dicyclohexylmethane; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis- (methylamine); 1,3-cyclohexane-bis- (methylamine); diethylene glycol bis- (Aminopropyl) ether; 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; Aminopropyl amine; diethylaminopropylamine; imide - (bis - propylamine); may be selected from and mixtures thereof; monoethanolamine; diethanolamine; triethanolamine; monoisopropanolamine; diisopropanolamine; isophoronediamine.
In one embodiment, the composition comprises a bismuth catalyst, zinc octoate, bis-butyltin dilaurate, bis-butyltin diacetate, tin (II) chloride, tin (IV) chloride, bis-butyltin dimethoxide, From the group consisting of dimethyl-bis [1-oxondecyl] oxy] stannane, di-n-octyltin bis-isooctyl mercaptoacetate, triethylenediamine, triethylamine, tributylamine, oleic acid, acetic acid, delayed catalysts, and mixtures thereof Further comprising a selected catalyst. The catalyst may be present from about 0.005% to about 1% by weight of the composition.

In another embodiment, the cover layer has a yellowness index difference (ΔYI) of about 12 or less after 5 days of UV light exposure. In yet another embodiment, the cover layer has a b * range difference of about 6 or less after 5 days of UV light exposure.
In this aspect of the invention, the cover layer may be formed by casting, injection molding, compression molding, reaction injection molding, and mixing methods thereof, as well as other polymer processes known to those skilled in the art.
The present invention also relates to a golf ball comprising a core, a layer placed around the core to form a center, and a cover cast on the center, the cover comprising at least one isocyanate and amine A light-stable polyurea material comprising a terminal compound and at least one hydroxy-terminated curing agent, amine-terminated curing agent, or a mixture thereof.
In one embodiment, the layer comprises ionomers, polyamides, highly neutralized polymers, polyesters, polycarbonates, polyimides, polyolefins, acid copolymers, polyurethanes, vinyl resins, acrylic resins, polyphenylene. Oxide resins, metallocene catalyzed polymers, and mixtures thereof. In another embodiment, the layer is a moisture barrier layer.
In yet another embodiment, the cover has a thickness of about 0.02 inches to about 0.035 inches (about 0.508 mm to about 0.889 mm). Further, the layer has a first Shore D hardness, the cover has a second Shore D hardness, and a ratio of the second Shore D hardness to the first Shore D hardness is about 0.7 or less.

The core can include polybutadiene and can have a diameter of about 1.55 or greater. In one embodiment, the core includes a cis-trans-conversion catalyst, an elastic polymer component, and a free radical source. The cis-trans-conversion catalyst may preferably be an organic sulfur component containing a metal salt, a Group VIA component, an inorganic sulfide component, an aromatic organic compound, or a mixture thereof.
In one embodiment, at least one of the core, the layer, the cover, or a combination thereof includes a density adjusting filler.
The present invention also provides a golf ball center; a polyurea prepolymer and at least one curing agent are mixed to prepare a castable reactive polyurea liquid material; Filled with a first amount of the material; lowering the center into the first half group of the mold after a first predetermined time, maintaining the center in a vacuum for a second predetermined time, the second predetermined time being the second predetermined time Sufficient for a fully exothermic reaction of one quantity of material; releasing the center from the vacuum to obtain a partially coated center; filling a second group of molds with a second quantity of the material, the first and second A golf course including the steps wherein the second amount of exothermic reaction begins; the second half group of the mold merges with the partial coating center and the second amount of exothermic reaction ends; It also relates to the ball forming method.

In one embodiment, the first predetermined time is about 40 seconds to about 100 seconds. In another embodiment, the second predetermined time is about 4 seconds to about 12 seconds.
The polyurea prepolymer can include at least one isocyanate and at least one amine-terminated compound. In one embodiment, the step of mixing the polyurea prepolymer and at least one curing agent further comprises mixing at least one triol or at least one tetraol, or a mixture thereof. In another embodiment, the step of mixing the polyurea prepolymer and at least one curing agent comprises at least one catalyst, at least one light stabilizer, at least one defoaming agent, at least one. Further comprising mixing the acid-functionalized components of, or combinations thereof.
In yet another embodiment, the step of manufacturing the golf ball center includes the steps of manufacturing a golf ball core and forming a layer positioned around the golf ball core. In yet another embodiment, the golf ball core includes a polybutadiene reaction product, the core has a diameter of about 1.55 inches or more and the layer is about 0.02 inches to about 0.035 inches. (About 0.508 mm to about 0.889 mm).

The present invention also relates to a golf ball that includes at least one layer formed from a water resistant polyurea or polyurethane elastomer. In particular, this aspect of the invention relates to golf balls having at least one layer, where such layers (one or more) are formed from water resistant polyurea or polyurethane. In one embodiment, the one-piece golf ball is formed from a water resistant elastomer. In other embodiments, multi-layer balls are formed that include at least a portion of the water resistant elastomer of the present invention. In this aspect of the invention, the intermediate layer, the cover layer (one or more layers), and / or the core may be formed in whole or in part by the water resistant elastomer composition.
The water resistant polyurethane elastomer of the present invention is a reaction product of at least one isocyanate, at least one polyol and at least one curing agent, the polyol and / or curing agent being based on a hydrophobic backbone. . The water-resistant polyurea elastomer is a reaction product of at least one isocyanate and at least one amine-terminated polyol, and the amine-terminated polyol and / or the curing agent is based on a hydrophobic backbone.

The water resistant elastomers of the present invention may be used in the manufacture of any part of a golf ball, part of a golf club, shoes, or bags. When used in a golf ball, the water resistant elastomer is preferably included in the layer composition at about 1 to about 100 weight percent of the layer composition.
In one embodiment, the golf ball of the present invention comprises a core and a cover, at least a portion of the golf ball comprising a water resistant polyurea comprising an isocyanate, an amine-terminated compound comprising a hydrophobic backbone, and a curing agent. Formed from the composition. The amine-terminated compound can include at least one of an unsaturated amine-terminated hydrocarbon, a saturated amine-terminated hydrocarbon, or a mixture thereof. Further, the curing agent may be selected from the group consisting of hydroxy-terminated curing agents, amine-terminated curing agents, and mixtures thereof. In another embodiment, the curing agent is selected from the group consisting of primary diamine curing agents, secondary diamine curing agents, triamines, and combinations thereof, preferably secondary diamine curing agents. is there. In this aspect of the invention, the golf ball preferably has a mass gain of about 0.15 grams or less after 7 weeks storage at 72 ° F. (22.2 ° C.) and 100% humidity. In one embodiment, the golf ball has a mass gain of less than or equal to about 0.09 grams after 7 weeks storage at 72 ° F. (22.2 ° C.) and 100% humidity. The water resistant polyurea composition may also include at least one density adjusting filler. Further, in one embodiment, the water-resistant polyurea composition consists only of urea bonds.

In a second embodiment of this aspect of the invention, a golf ball is placed on a core having a diameter of about 1.55 or greater, an intermediate layer disposed around the core to form a center, and the center. A cover having a thickness of about 0.02 inches to about 0.035 inches (about 0.508 mm to about 0.889 mm), the cover comprising at least one amine-terminated compound comprising a hydrophobic backbone and at least one isocyanate. A water resistant polyurea material. In this embodiment, the golf ball preferably has a mass gain of about 0.05 grams or less after 7 weeks storage at 72 ° F. (22.2 ° C.) and 100% humidity.
In one embodiment, the amine-terminated compound comprises at least one amine-terminated hydrocarbon. In another embodiment, the cover has a first hardness and the intermediate layer has a second hardness greater than the first hardness. For example, the first hardness can be about 40 Shore D to about 55 Shore D, and the second hardness can be about 60 Shore D or greater. The core can also include a first layer and a second layer. In one embodiment, the core hardness is about 60 Shore D or less.

  In a third embodiment of this aspect of the invention, the golf ball may comprise a water resistant polyurea composition comprising at least one amine-terminated compound having at least one hydrophobic backbone, wherein the golf ball comprises Having a mass increase of about 0.15 grams or less and a size increase of about 0.001 inches (about 25.4 microns) or less after 7 weeks storage at 100% humidity at 72 ° F. (22.2 ° C.). In one embodiment, the water resistant polyurea composition further comprises an isocyanate and a curing agent. In another embodiment, the curing agent is ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexane. Diamine; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane and derivatives thereof; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (sec-butylamino)- Cyclohexane; 4,4'-dicyclohexylmethanediamine; 1,4-cyclohexane-bis- (methylamine); 1,3-cyclohexane-bis- (methylamine); diethylene glycol bis- (aminopropyl) ether; 2-methylpenta Methylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; Diethylaminopropylamine; imido-bis- (propylamine); monoethanolamine; diethanolamine; triethanolamine; monoisopropanolamine; diisopropanolamine; isophoronediamine; 4,4'-methylenebis- (2-chloroaniline); 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-p-aminobenzoate; polytetramethylene oxide-di-p-aminobenzoate; 4,4'-methylenebis- (3-chloro- 2,4-diethyleneaniline); 4,4'-methylenebis- (2,6-diethylaniline); meta-phenylenediamine; paraphenylenediamine; cyclohexyldimethol; N, N'-diisopropyl-isophoronediamine; polyoxypropylene Selected from the group consisting of diamines; propylene oxide triamines; 3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixtures thereof. In this aspect of the invention, the golf ball may have a polybutadiene core.

The golf ball of the present invention may be formed to have at least one cover and at least one core layer, and at least one water-resistant polyurethane elastomer is included in the golf ball cover. In another embodiment, the golf ball has a cover, a core, and at least one intermediate layer inserted between the cover and the outermost core layer, the intermediate layer comprising at least one water-resistant layer. It is formed from a composition comprising a polyurethane elastomer. In yet another embodiment, the golf ball has a cover, a core, and at least one intermediate layer inserted between the cover and the core layer, the outermost cover layer and the at least one intermediate layer being , Both of which are formed from a composition comprising at least one water resistant polyurethane elastomer.
The water resistant polyurethane elastomers used to form the golf balls of the present invention can be prepared according to the teachings described in US Pat. Nos. 5,334,673 and 5,733,428, the disclosures of which are fully incorporated herein by reference. Incorporated in the description.
Further features and advantages of the present invention may be ascertained from the following detailed description taken in conjunction with the accompanying drawings.

The present invention contemplates an improved light stable and moisture resistant composition for use in golf equipment such as golf balls or golf clubs. Specifically, the compositions of the present invention are polyurea-based and are included in various golf ball constructions, ie, one-piece, two-piece or multi-layer balls, as well as golf club components, such as club head inserts.
The light stable compositions of the present invention are better than golf balls containing polyurea or polyurethane compositions without light stable blends when included in various golf equipment components such as covers. A golf ball having equivalent physical and aerodynamic properties is formed.
Light stability can be achieved in various ways for the purpose of this application. For example, the compositions of the present invention may include only saturated components, ie, components that are substantially free of unsaturated carbon-carbon bonds or aromatic groups. As used herein, the term “saturated” refers to a compound having a saturated aliphatic and alicyclic polymer backbone, ie, no carbon-carbon double bonds. Moreover, although the composition of this invention can also use the light stabilizer for improving light stability, when using an aromatic component, Preferably it is a saturated type. These compositions are either inherently thermoplastic or thermoset.
Furthermore, the use of the water resistant elastomers of the present invention in golf ball components results in golf balls that exhibit improved stability with respect to their resistance to moisture absorption. Conventional polyurethane and polyurea elastomers absorb water more easily than the elastomers of the present invention based on a hydrophobic backbone. That is, the improved performance characteristics of the golf balls of the present invention demonstrate a clear benefit to golfers by providing golf balls that exhibit consistent behavior over a wide range of environmental conditions.

Polyurea Compositions The compositions of the present invention can be a polyurea system that is distinctly different from polyurethane compositions, but provides desirable aerodynamic and aesthetic properties when used in golf ball components.
Conventional aromatic polyurethane / urethane elastomers and polyurethane / urea elastomers are generally prepared by curing a prepolymer of diisocyanate and polyol, respectively, with at least one diol curing agent or at least one diamine curing agent. Without being bound by any particular theory, at present, the preparation of polyurea prepolymers by replacing long-chain polyol segments in polyurethane prepolymers with long-chain amine-terminated compounds is shearing, cutting and elastic It is believed to improve force, as well as adhesion to other components.
That is, the polyurea composition of the present invention can be prepared from the reaction product of a prepolymer of isocyanate and amine-terminated compound 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 amine-terminated compound, and at least one diol curing agent or at least one diamine curing agent. In one embodiment, the polyurea composition of the present invention is prepared from at least one isocyanate, at least one amine-terminated compound, and at least one diamine curing agent. The curing agent is preferably a secondary diamine curing agent. Specific components of the polyurea composition of the present invention are described in further detail below.

Polyamine Component Any amine-terminated compound available to those skilled in the art is suitable for use in the polyurea prepolymer. Amine-terminated compounds can include amine-terminated hydrocarbons, amine-terminated polyethers, amine-terminated polyesters, amine-terminated polycarbonates, amine-terminated polycaprolactones, and mixtures thereof. The amine end segment can be in the form of a primary amine (NH ₂ ) or a secondary amine (NHR).
The molecular weight of the amine-terminated compounds used in the present invention can range from about 100 to about 10,000. As used herein, the term “about” as used in connection with one or more numerical values or numerical ranges shall be understood to refer to all such numerical values, including all numerical values within the range. It is. In one embodiment, the amine-terminated compound is about 500 or more, preferably about 1000 or more, more preferably about 2000 or more. In another embodiment, the molecular weight of the amine-terminated compound is about 8000 or less, preferably about 4,000 or less, more preferably about 3,000 or less. For example, in one embodiment, the molecular weight of the amine-terminated compound is from about 1000 to about 4000. Since low molecular weight polyetheramines may have a tendency to produce solid polyureas, high molecular weight oligomers may be used to avoid solid formation.
In one embodiment, amine-terminated compounds include amine-terminated hydrocarbons having the following general structure:

Wherein x is a chain length, ie, 1 or more; n is preferably from about 1 to about 12; R is from about 1 to about 20 carbon atoms, preferably from about 1 to about 12 Any alkyl group, phenyl group, cyclic group, or a mixture thereof.
Also, amine-terminated compounds include amine-terminated polyethers having the following general structure:

Wherein x is a chain length, ie, 1 or more; n is preferably from about 1 to about 12; R is from about 1 to about 20 carbon atoms, preferably from about 1 to about 12 Any alkyl group, phenyl group, cyclic group, or a mixture thereof. One example of an amine-terminated polyether is a polyetheramine. As used herein, “polyetheramine” refers to a polyoxyalkyleneamine containing a primary amino group attached to the end of the polyether backbone. However, due to the rapid reaction of isocyanates with amines and the insolubility of many urea products, the choice of diamines and polyetheramines is limited to those that allow for the successful production of polyurea prepolymers. Yes. In one embodiment, the polyether backbone is based on tetramethylene, propylene, ethylene, trimethylolpropane, glycerin and mixtures thereof.
In one embodiment, the polyetheramine has the following general structure:

Wherein repeat unit x has a value in the range of about 1 to about 70; R is any alkyl having from about 1 to about 20 carbon atoms, preferably from about 1 to about 12 carbon atoms Groups, phenyl groups, cyclic groups, or mixtures thereof; R ₃ is hydrogen, methyl groups, or mixtures thereof). More preferably, the repeat unit may be from about 5 to about 50, even more preferably from about 12 to about 35.
In another embodiment, the polyetheramine has the following general structure:

Wherein repeat units x and z have a total value of about 3.6 to about 8; repeat unit y has a value in the range of about 9 to about 50; R is about 1 to about 20 An alkyl group having carbon, a phenyl group, a cyclic group, or a mixture thereof; R ₁ is — (CH ₂ ) _a — (“a” can be a repeating unit ranging from about 1 to about 10), phenylene A group, a cyclic group, or a mixture thereof; R ₃ is hydrogen, a methyl group, or a mixture thereof).
In yet another embodiment, the polyetheramine has the following general structure:

Wherein R is an alkyl group having from about 1 to about 20 carbons, a phenyl group, a cyclic group, or a mixture thereof; R ₁ is — (CH ₂ ) _a — (“a” is about 1 to about 10 repeating units), a phenylene group, a cyclic group, or a mixture thereof).
Suitable polyether amines include, but are not limited to, methyldiethanolamine; polyoxyalkylene diamines such as polytetramethylene ether diamines, polyoxypropylene triamines, polyoxyethylene diamines, and polyoxypropylene diamines. Poly (ethylene oxide capped oxypropylene) ether diamines; propylene oxide triamines; triethylene glycol diamines; trimethylolpropane triamines; glycerin triamines; and mixtures thereof. In one embodiment, the polyetheramine used to prepare the prepolymer is Jeffamine® D2000 (Huntsman Corporation, Austin, Texas).

The molecular weight of the polyetheramine used in the present invention can range from about 100 to about 5000. In one embodiment, the molecular weight of the polyetheramine is about 200 or higher, preferably about 230 or higher. In another embodiment, the molecular weight of the polyetheramine is about 4000 or less. In yet another embodiment, the polyetheramine has a molecular weight of about 600 or greater. In yet another embodiment, the polyetheramine has a molecular weight of about 3000 or less. In yet another embodiment, the molecular weight of the polyetheramine is from about 1000 to about 4000, preferably from about 1000 to about 4000, more preferably from about 1500 to about 2500. High molecular weight oligomers such as Jeffamine® D2000 are preferred because low molecular weight polyetheramines may have a tendency to form solid polyurea during prepolymer preparation.
In addition, amine-terminated compounds include amine-terminated polyesters having the following general structure:

Wherein x is a chain length, ie, 1 or more, preferably from about 1 to about 20; R has from about 1 to about 20 carbon atoms, preferably from about 1 to about 12 carbon atoms Any alkyl group, phenyl group, cyclic group, or mixtures thereof; R ₁ and R ₂ are straight or branched hydrocarbon chains, eg, alkyl or aryl chains).
Copolymers of polycaprolactone and polyamines can also be used to prepare the polyurea prepolymers of the present invention. These copolymers include, but are not limited to, bis (2-aminoethyl) ether initiated polycaprolactone; 2- (2-aminoethylamino) ethanol, 2-2 (aminoethylamino) ethanol; polyoxyethylenediamine Initiated polycaprolactone; propylenediamine-initiated polycaprolactone; polyoxypropylenediamine-initiated polycaprolactone; 1,4-butanediamine-initiated polycaprolactone; trimethylolpropane-based triamine-initiated polycaprolactone; neopentyldiamine-initiated polycaprolactone; Hexanediamine-initiated polycaprolactone; polytetramethylene ether diamine-initiated polycaprolactone; and mixtures thereof. In addition, polycaprolactone polyamines having the following structure may also be useful in preparing the polyurea prepolymers of the present invention:

Wherein x is a chain length, ie, one or more, preferably from about 1 to about 20, and R is an alkyl group having from about 1 to about 20 carbons, preferably from about 1 to about 12 carbons. , A phenyl group, or a cyclic group; R ₁ is a straight or branched hydrocarbon chain containing from about 1 to about 20 carbons).

Wherein x is a chain length, ie, one or more, preferably from about 1 to about 20, and R is an alkyl having from about 1 to about 20 carbons, preferably from about 1 to about 12 carbons. One of a group, a phenyl group, or a cyclic group; R ₁ is a straight or branched hydrocarbon chain containing from about 1 to about 20 carbons).
In another embodiment, the amine-terminated compound can be an amine-terminated polycarbonate having one of the following general structures:

Wherein x is preferably a chain length in the range of about 1 to about 20; R is an alkyl group, phenyl group having about 1 to about 20 carbons, preferably about 1 to about 12 carbons Or one of the cyclic groups; R ₁ is a linear hydrocarbon chain or primarily a bisphenol A unit or derivative thereof).
Amine-terminated polyamides can also be reacted with the isocyanate component to produce the polyurea prepolymer component of the present invention. Suitable amine-terminated polyamides include, but are not limited to, those having the following structure:

Wherein x is a chain length, ie, about 1 or more; R is an alkyl group, phenyl group, or cyclic group having about 1 to about 20 carbons, preferably about 1 to about 12 carbons. R ₁ is an alkyl group having from about 1 to about 12 carbon atoms, a phenyl group, or a cyclic group; R ₂ is an alkyl group having from about 1 to about 12 carbon atoms (Straight or branched), phenyl, or cyclic).
Also, additional amine-terminated compounds that are useful in preparing the polyurea prepolymers of the present invention include, but are not limited to, poly (acrylonitrile-co-butadiene); poly (1 , 4-butanediol) bis (4-aminobenzoate); linear and branched polyethyleneimines; low and high molecular weight polyethyleneimines having an average molecular weight of about 500 to about 30,000; having an average molecular weight of about 200 to about 5,000 Poly (propylene glycol) bis (2-aminopropyl ether); polytetrahydrofuran bis (3-aminopropyl) terminated product having an average molecular weight of about 200 to about 2000; and mixtures thereof, all of which are Available from Aldrich, Milwaukee.
Thus, in one embodiment, the polyurea composition of the present invention comprises poly (acrylonitrile-co-butadiene) having one of the following structures:

Wherein x and y are chain lengths, ie greater than about 1; R is any alkyl group having from about 1 to about 20 carbon atoms, preferably from about 1 to about 12 carbon atoms; R ₁ is hydrogen, a methyl group, a cyano group, a phenyl group, or a mixture thereof; R ₂ is hydrogen, a methyl group, chlorine, or a mixture thereof; is there). In one embodiment, the y: x ratio is from about 82:18 to about 90:10. In other words, the poly (acrylonitrile-co-butadiene) can comprise about 10 to about 18 weight percent acrylonitrile.
In another embodiment, the polyurea composition of the present invention comprises poly (1,4-butanediol) bis (4-aminobenzoate) having one of the following structures:

In which x and n are chain lengths, ie greater than or equal to 1, n is preferably about 1 to about 12; R and R ₁ are linear or branched hydrocarbon chains, about 1 to An alkyl group having about 20 carbons, preferably about 1 to about 12 carbons, a phenyl group, a cyclic group, or a mixture thereof; R ₂ is hydrogen, a methyl group, or a mixture thereof). In one embodiment, R ₁ is phenyl, R ₂ is hydrogen, and n is about 2.
In yet another embodiment, the polyurea composition of the present invention comprises at least one linear or branched polyethyleneimine having one of the following structures:

Wherein x and y are chain lengths, ie greater than about 1, R is any alkyl group having from about 1 to about 20 carbon atoms, preferably from about 1 to about 12 carbon atoms, A phenyl group, a cyclic group, or a mixture thereof; R ₁ is hydrogen, a methyl group, or a mixture thereof). In one embodiment, R ₁ is hydrogen. In another embodiment, the polyurea composition comprises a mixture of linear and branched polyethyleneimines.
In yet another embodiment, the polyurea composition of the present invention comprises a polytetrahydrofuran bis (3-aminopropyl) terminated compound having one of the following structures:

Wherein m and n are chain lengths, ie, 1 or more, n is preferably from about 1 to about 12, m is preferably from about 1 to about 6; R is about 1 From about 20 carbons, preferably from about 1 to about 12 carbons, alkyl groups, phenyl groups, cyclic groups, or mixtures thereof; R ₁ and R ₂ are hydrogen, methyl groups, or mixtures thereof Is). In one embodiment, R ₁ and R ₂ are both hydrogen and m and n are both about 2.
In addition, diamines and triamines can be used in conjunction with isocyanates to prepare the polyurea prepolymers of the present invention. In one embodiment, aromatic diamines may also be used if it is intended to incorporate UV stabilizers or whitening agents in post processing. US Pat. No. 5,484,870 provides aromatic diamines suitable for use in the present invention, the entire description of which is hereby incorporated by reference. For example, useful aromatic polyamines include polymethylene-di-p-aminobenzoate, polyethylene glycol-bis (4-aminobenzoate), polytetramethylene ether glycol-di-p-aminobenzoate, polypropylene glycol-di-p -Aminobenzoates, and mixtures thereof. Further, the triamines that can be used to prepare the prepolymers of the present invention include N, N, N ′, N′-tetramethyl-ethylenediamine, 1,4-diazobicyclo (2,2,2) -octane. N-methyl-N'-dimethylaminoethylpiperazine, N, N-dimethylbenzylamine, bis- (N, N-diethylaminoethyl) -adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N- There are dimethylcyclohexylamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine, N, N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, and 2-methylimidazole.

By using amine-terminated components based on hydrophobic segments, the polyurea compositions of the present invention can be more water resistant than polyurea compositions prepared with amine-terminated hydrophilic segments. That is, in one embodiment, the amine-terminated compound comprises a hydrophobic backbone, such as an unsaturated or saturated hydrocarbon amine-terminated compound. One example of an amine-terminated hydrocarbon is amine-terminated polybutadiene.
The amine-terminated compounds can also be mixed with additional polyols as described below in connection with the polyurethane compositions of the present invention to prepare copolymers that form polyurea prepolymers by reaction with excess isocyanate. . However, as soon as a polyol is used, excess isocyanate in the polyurea prepolymer reacts with hydroxyl groups in the polyol to form urethane linkages, resulting in a composition that is no longer pure polyurea (instead of polyurea / Urethane composition). Such compositions differ from polyurea compositions that contain only isocyanates, amine-terminated compounds, and curing agents.

Isocyanate Component Any isocyanate available to those skilled in the art is suitable for use in accordance with the present invention. The isocyanates used in the present invention include aliphatic, alicyclic, aromatic aliphatic, aromatic compounds having two or more isocyanate (NCO) groups per molecule; any derivatives thereof; and combinations of these compounds There is. As used herein, an aromatic aliphatic compound is to be understood as a compound containing an aromatic ring in which the isocyanate group is not directly bonded to the aromatic ring. One example of an aromatic aliphatic compound is tetramethylene diisocyanate (TMXDI).
Isocyanates can be organic polyisocyanate-terminated prepolymers, low free isocyanate prepolymers, and mixtures thereof. The isocyanate-containing reactive component can also be any isocyanate functional monomer, dimer, trimer or their polymeric adducts, prepolymers, quasi-prepolymers, or mixtures thereof. Isocyanate functional compounds can be monoisocyanates or polyisocyanates containing two or more optional isocyanate functionalities.
Suitable isocyanate-containing components include diisocyanates having the general structure: O = C = NRN = C = O, where R is preferably a cyclic containing from about 1 to about 20 carbon atoms. , Aromatic or linear or branched hydrocarbon components. Isocyanates can also contain one or more cyclic groups or one or more phenyl groups. When multiple cyclic or aromatic groups are present, linear and / or branched hydrocarbons containing from about 1 to about 10 carbon atoms are present as spacers between the cyclic or aromatic groups. obtain. In some cases, the cyclic or aromatic group may be substituted in the 2-, 3- and / or 4-position, or ortho-, meta- and / or para-position, respectively. Substituents can include, but are not limited to, halogens; primary, secondary, or tertiary hydrocarbon groups; or mixtures thereof.

Examples of isocyanates that can be used in the present 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); polymeric MDI; carbodiimide-modified liquid 4,4'-diphenylmethane diisocyanate; para-phenylene diisocyanate (PPDI); meta-phenylene Diisocyanate (MPDI); triphenylmethane-4,4'- and triphenylmethane-4,4 "-triisocyanate;naphthylene-1,5-diisocyanate;2,4'-,4,4'- and 2,2 -Biphenyl diisocyanate; polyphenylene polymethylene polyisocyanate (PMDI) (also known as polymeric PMDI); a mixture of MDI and PMDI; a mixture of PMDI and TDI; an ethylene diisocyanate Propylene-1,2-diisocyanate; tetramethylene-1,2-diisocyanate; tetramethylene-1,3-diisocyanate; tetramethylene-1,4-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; 1,2-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methylcyclohexylene diisocyanate (HTDI); 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate 4,4'-dicyclohexyl diisocyanate; 2,4'-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 (isocyanate methyl) dicyclohexane; 2,4'-bis (isocyanate methyl) dicyclohexane; isophorone diisocyanate (IPDI); Triisocyanate of 2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI); 4,4′-dicyclohexylmethane diisocyanate (H ₁₂ MDI); 2,4-hexahydrotoluene diisocyanate; 2,6-hexa Hydrotor 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); such as isocyanurate of toluene diisocyanate, trimer of diphenylmethane diisocyanate, trimer of tetramethylxylene diisocyanate, isocyanurate of hexamethylene diisocyanate and mixtures thereof Trimerized isocyanurate of any polyisocyanate; dimerized uretdione of any polyisocyanate such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate and mixtures thereof; Modified polyisocyanates derived from the isocyanates and polyisocyanates; as well as mixtures thereof.

When preparing saturated polyurea prepolymers, the following saturated isocyanates are preferably used: ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene diisocyanate; tetramethylene-1,4-diisocyanate; 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; methylcyclohexylene diisocyanate (HTDI); 2,4-methyl 2,6-methylcyclohexane diisocyanate; 4,4'-dicyclohexyl diisocyanate; 2,4'-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanate methylcyclohexane isocyanate; 1-isocyanate-3,3 , 5-trimethyl-5-isocyanate methylcyclohexane; isocyanate ethylcyclohexane isocyanate; bis (isocyanatemethyl) -cyclohexane diisocyanate; 4,4'-bis (isocyanatemethyl) dicyclohexane; 2,4'-bis (isocyanatemethyl) dicyclohexane Isophorone diisocyanate (IPDI); triisocyanate of HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI); 4,4'-dicyclohexylmethane diisocyanate Over preparative (H ₁₂ MDI); 2,4- hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; and mixtures thereof. Aromatic aliphatic isocyanates can also be used to prepare light stable materials. Examples of such isocyanates are 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; uretdione of toluene diisocyanate, hexa Dimerized uretdiones of any polyisocyanate, such as uretdione of methylene diisocyanate and mixtures thereof; modified polyily derived from the above isocyanates and polyisocyanates Cyanate; and mixtures thereof. Furthermore, the aromatic aliphatic isocyanates may be mixed with any of the saturated isocyanates listed above for the purposes of the present invention.

By changing the number of unreacted NCO groups in the polyurea prepolymer of isocyanate and polyetheramine, it is possible to adjust factors such as reaction rate, hardness of the resulting composition, and the like. For example, as the weight percent of unreacted isocyanate groups increases, the hardness also increases somewhat linearly. That is, when the NCO content is about 10.5% by weight, the hardness can be less than about 55 Shore A, whereas when the NCO is increased to about 15% by weight, the hardness is higher than about 80 Shore A.
In one embodiment, the number of unreacted NCO groups in the polyurea prepolymer of isocyanate and polyetheramine can be less than about 14%. In one embodiment, 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 embodiment, the proportion of unreacted NCO groups is from about 3% to about 9%. Also, the proportion of unreacted NCO groups can be about 7.5% or less, preferably about 7% or less. In another embodiment, the unreacted NCO content is about 2.5% to about 7.5%, more preferably about 4% to about 6.5%.

Curing Agent The polyurea composition may be produced by crosslinking the polyurea prepolymer with a single curing agent or mixture of curing agents. The compositions of the present invention can be selected from both castable thermosetting and thermoplastic materials, which are determined by the ratio of prepolymer to curing agent. For example, the castable thermoplastic composition of the present invention typically comprises a linear polymer, and the prepolymer is cured 1: 1 stoichiometrically with a diol or secondary diamine in the absence of moisture. Form. On the other hand, the thermosetting composition of the present invention is a cross-linked polymer and is typically formed from the reaction of a diisocyanate cured with a primary diamine or polyfunctional glycol and a polyol.

  The curing agent of the present invention is preferably an amine-terminated curing agent, more preferably a secondary diamine curing agent, so that the composition contains only urea bonds. Suitable amine-terminated curing agents include, but are not limited to, ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1, 6-hexanediamine; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane and derivatives thereof; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (sec-butyl Amino) -cyclohexane; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis- (methylamine); 1,3-cyclohexane-bis- (methylamine); diethylene glycol bis- (aminopropyl) ether; Dimethylcyclohexane; Diethylenetriamine; Triethylenetetramine; Tetraethylenepentamine; Propylenediamine; 1,3-Diaminopropane; Dimethylamino Diethylaminopropylamine; imido-bis- (propylamine); 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-toluene Diamine; 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-p-aminobenzoate; polytetramethylene oxide-di-p-aminobenzoate; 4,4'-methylene Su- (3-chloro-2,6-diethyleneaniline); 4,4'-methylenebis- (2,6-diethylaniline); meta-phenylenediamine; paraphenylenediamine; N, N'-diisopropyl-isophoronediamine; Polyoxypropylenediamine; propylene oxide triamine; 3,3'-dimethyl-4,4'-diaminocyclohexylmethane; and mixtures thereof. In one embodiment, the amine-terminated curing agent is 4,4′-bis- (sec-butylamino) -dicyclohexylmethane. In one embodiment, the amine terminated curing agent can have a molecular weight of about 64 or greater. In another embodiment, the amine curing agent has a molecular weight of about 2000 or less. In addition, any amine-terminated component listed above can be used as a curing agent to react with a polyurea prepolymer.

  Of the above listed, saturated amine terminal curing agents suitable for use in the present invention include, but are not limited to, ethylene diamine; hexamethylene diamine; 1-methyl-2,6-cyclohexyl diamine; , 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); 1,3-cyclohexane-bis- (methylamine); diethylene glycol bis- (aminopropyl) ether; 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; Tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamine; imido-bis- (propylamine); monoethanolamine; diethanolamine; triethanolamine; monoisopropanolamine; Isopropanolamine; isophoronediamine; and mixtures thereof.

As briefly mentioned above, many amines may be unsuitable for reaction with isocyanates due to the rapid reaction between these two components. In general, unhindered primary diamines are rapidly reactive. However, in one embodiment, hindered secondary diamines are suitable for use in the prepolymer. Without being bound by any particular theory, high levels of stearic acid hindrance, such as amines with tertiary butyl groups on the nitrogen atom, have slower reaction rates than amines with no or low levels of hindrance. It is believed to have For example, 4,4′-bis- (sec-butylamino) -dicyclohexylmethane (Clearlink 1000) is suitable for preparing polyurea prepolymers in combination with isocyanates. In addition, N, N′-diisopropyl-isophoronediamine, available from Huntsman Corporation under the trade name Jefflink, can also be used as a secondary diamine curing agent.
Furthermore, the polyurea prepolymer can also be cured by one hydroxy-terminated curing agent or a hydroxy-terminated curing agent mixture. However, when using a hydroxy-terminated curing agent, excess isocyanate in the polyurea prepolymer reacts with hydroxyl groups in the curing agent to form urethane bonds, resulting in a composition that is no longer pure polyurea (instead, Polyurea / urethane composition).
For the purposes of the present invention, a pure polyurea composition, ie polyurea / urea, contains only urea bonds having the following general structure:

(Wherein x is the chain length, ie about 1 or greater; R and R ₁ are straight or branched hydrocarbon chains having from about 1 to about 20 carbons). On the other hand, the polyurea / urethane composition contains both urea and urethane bonds, which have the following general structure:

(Wherein x is the chain length, ie about 1 or greater; R and R ₁ are straight or branched hydrocarbon chains having from about 1 to about 20 carbons).
Suitable hydroxy-terminated curing agents include, but are not limited to, ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol; Propylene glycol; polypropylene glycol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; trimethylolpropane Cyclohexyldimethylol; triisopropanolamine; N, N, N ′, N′-tetra- (2-hydroxypropyl) -ethylenediamine; diethylene glycol bis- (aminopropyl) ether; 1,5-pentanediol; Hexanediol; 1,3-bis- (2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol; 1,3-bis- [2- ( 2-hydroxyethoxy) ethoxy] cyclohexane; 1,3-bis- {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} cyclohexane; preferably polytetramethylene ether glycol having a molecular weight in the range of about 250 to about 3900 Resorcinol-di- (β-hydroxyethyl) ether and its derivatives; hydroquinone-di- (β-hydroxyethyl) ether and its derivatives; 1,3-bis- (2-hydroxyethoxy) benzene; -[2- (2-hydroxyethoxy) ethoxy] benzene; N, N'-bis (β-hydroxypropyl) aniline; 2-propanol 1,1'-phenylaminobis; and mixtures thereof. The hydroxy-terminated curing agent can have a molecular weight of at least about 50. In one embodiment, the hydroxy terminated curing agent has a molecular weight of about 2000 or less.

  When preparing a photostable composition, saturated hydroxy-terminated curing agents included in the above list are preferred. Saturated hydroxy-terminated curing agents include, but are not limited to, ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol; Polypropylene glycol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; trimethylolpropane; Cyclohexyldimethylol; triisopropanolamine; N, N, N ′, N′-tetra- (2-hydroxypropyl) -ethylenediamine; diethylene glycol bis- (aminopropyl) ether; 1,5-pentanediol; 1,6-hexane Diol; 1,3-bis- (2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol; 1,3-bis- [2- (2- Droxyethoxy) ethoxy] cyclohexane; 1,3-bis- {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} cyclohexane; polytetramethylene ether glycol having a molecular weight in the range of about 250 to about 3900; and these There is a mixture of

As noted above, both types of curing agents, i.e., hydroxy-terminated curing agents and amine curing agents, may contain one or more saturated, unsaturated, aromatic, and cyclic groups. In addition, the hydroxy-terminated curing agent and the amine curing agent can also include one or more halogen groups. In order to further improve the shear resistance of the resulting polyurea elastomer, trifunctional curing agents can be used to help improve cross-linking. For example, a hydroxy terminated curing agent can be used. Preferably, a triol such as trimethylolpropane or a tetraol such as N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine may be added to the formulation.
A skilled technician can adjust various properties of a golf ball or golf ball component, such as hardness, which is a function of the NCO content of the prepolymer and the molecular weight of the curing agent, by adjusting the prepolymer to curing agent ratio. It is recognized that it can be controlled. For example, the above ratio for a polyurea prepolymer containing 6% unreacted NCO groups cured with 1,4-butanediol is 15.6: 1 whereas 4,4'-bis- (sec-butylamino) The above ratio of the same prepolymer cured with -dicyclohexylmethane (Clearlink 1000) is 4.36: 1. The ratio of prepolymer to curing agent for purposes of the present invention is preferably from about 0.5: 1 to about 16: 1.
Since the choice of curing agent determines whether the composition of the present invention is thermoplastic or thermosetting, the method of molding the composition of the present invention on a ball will vary depending on the type of composition. For example, the thermoplastic polyurea composition of the present invention can be used to produce thermoplastic pellets that can be formed on balls by injection molding or compression molding. The thermosetting polyurea composition can be cast on a ball. Furthermore, both the thermoplastic and thermosetting polyurea compositions of the present invention can be molded around the core using reaction injection molding (RIM) and liquid injection molding (LIM) methods.

  In one embodiment, the curing agent is modified as disclosed in pending US patent application Ser. No. 10 / 339,603 filed Jan. 10, 2003 and entitled “Polyurethane Compositions for Golf Balls”. Curing agent mixtures, all of which are incorporated herein by reference. For example, the curing agent of the present invention can be modified with a freezing point depressant to produce a curing agent mixture having slower solidification initiation and storage stable pigment dispersibility. Many amine-terminated curing agents have relatively high freezing points, such as hexamethylenediamine (105.8 ° F (41 ° C)), diethanolamine (82.4 ° F (28 ° C)), triethanolamine (69.8 ° F ( 21 ° C)), diisopropanolamine (73.4 ° F (23 ° C)), and triisopropanolamine (111.2 ° F (44 ° C)). Such amine-terminated hardeners can be modified with amine-terminated freezing point depressants or amine-terminated freezing point depressant mixtures. Suitable amine-terminated freezing point depressants include but are not limited to ethylenediamine, 1,3-diaminopropane, dimethylaminopropylamine, tetraethylenepentamine, 1,2-propylenediamine, diethylaminopropylamine, 2,2 2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, and mixtures thereof.

The freezing point depressant is preferably added in an amount sufficient to reduce the freezing point of the curing agent by an appropriate amount that prevents loss of pigment dispersibility but does not affect the physical properties of the golf ball. In one embodiment, the freezing point depressant is added to the curing agent in an amount of about 5% by weight or more of the curing agent blend, ie, curing agent (s) + freezing point depressant. In another embodiment, the freezing point depressant is present in an amount greater than or equal to about 8% by weight of the curative blend. In yet another embodiment, the freezing point depressant is present in an amount greater than or equal to about 10% by weight. In yet another embodiment, the curing agent blend includes the freezing point curing agent in an amount of about 12% by weight or more of the curing agent blend. The curing agent blend may also include the freezing point depressant in an amount of about 14% or more by weight of the curing agent blend.
Further, after solidification and subsequent melting, the modified curative mixture of the present invention preferably has a pigment dispersibility of greater than 0, preferably about 1 or more, more preferably about 2 or more on the Hegman scale. . In one embodiment, the modified hardener mixture after the solidification / melting cycle has a pigment dispersibility of about 3 or greater on the Hegman scale. In another embodiment, the modified hardener mixture after solidification and melting is about 4 or more, preferably about 5 or more on the Hegman scale. In yet another embodiment, the modified hardener mixture after solidification and melting is about 6 or greater on the Hegman scale. In yet another embodiment, the modified hardener mixture after solidification and melting is about 7 or greater on the Hegman scale.
There are two basic methods used to process urea elastomers: the one-shot method and the prepolymer method. The one-shot method reacts the isocyanate, amine-terminated compound, and curing agent in one step, while the prepolymer method is the first reaction to produce a polyurea prepolymer between the amine-terminated compound and the isocyanate, and A subsequent reaction between the prepolymer and the curing agent is required. Either method can be used to produce the polyurea composition of the present invention, but the prepolymer method provides better control of the chemical reaction, resulting in more uniform properties for the elastomer. Therefore, it is preferable.

Polyurethane Compositions The compositions of the present invention can also be polyurethane-based and are distinctly different from the polyurea compositions described above, but produce desirable aerodynamic and aesthetic properties when used in golf ball components. That is, the composition of the present invention can be a reaction product between at least one polyurethane prepolymer and a curing agent, the polyurethane prepolymer formed by a reaction between at least one polyol and at least one diisocyanate. Product. The polyurethane-based composition of the present invention is preferably saturated, so in one embodiment, the composition of the present invention is at least formed from at least one saturated diisocyanate and at least one saturated polyol. A reaction product between one saturated polyurethane prepolymer and at least one saturated curing agent.

Isocyanate component The isocyanates used in the polyurethane prepolymer include aliphatic, alicyclic and aromatic aliphatic compounds having two or more isocyanate (NCO) groups per molecule; derivatives thereof; and combinations of these compounds. is there. These isocyanates can be organic, modified organic, organic polyisocyanate-terminated prepolymers, and mixtures thereof. The isocyanate-containing reactive component can also be any isocyanate functional monomer, dimer, trimer or multipolymer adduct, prepolymer, quasi-prepolymer, or mixtures thereof. Isocyanate functional compounds can be monoisocyanates or polyisocyanates containing two or more optional isocyanate functionalities.
Suitable isocyanate-containing components include diisocyanates having the general structure: O = C = NRN = C = O, where R is preferably a cyclic containing about 1 to about 20 carbon atoms. Or a linear or branched hydrocarbon component. The diisocyanate may also contain one or more cyclic groups. When multiple cyclic groups are present, linear and / or branched hydrocarbons containing from about 1 to about 10 carbon atoms can be present as spacers between the cyclic groups. In some cases, the cyclic group (s) can be substituted at the 2-, 3- and / or 4-position, respectively. Substituents can include, but are not limited to, halogens; primary, secondary, or tertiary hydrocarbon groups; or mixtures thereof.

Examples of saturated diisocyanates that can be used in the polyurethane prepolymer include, but are not limited to, ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene diisocyanate; tetramethylene-1,4-diisocyanate; -Hexamethylene diisocyanate (HDI); octamethylene diisocyanate; decamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1, 3-diisocyanate; cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methylcyclohexylene diisocyanate (HTDI); 2,4-methylcyclohexane diisocyanate 2,4-methylcyclohexane diisocyanate; 4,4'-dicyclohexyl diisocyanate; 2,4'-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanate methylcyclohexane isocyanate; 1-isocyanate-3,3,5 -Trimethyl-5-isocyanatomethylcyclohexane; Isocyanatoethylcyclohexaneisocyanate; Bis (isocyanatemethyl) -cyclohexanediisocyanate; 4,4'-bis (isocyanatemethyl) dicyclohexane; 2,4'-bis (isocyanatemethyl) dicyclohexane; Isophorone Diisocyanate (IPDI); HDI triisocyanate; 2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI) triisocyanate; 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI); 2,4-hexahi 2,6-hexahydrotoluene diisocyanate; aromatic aliphatic isocyanates such as 1,2-, 1,3- and 1,4-xylene diisocyanates; meta-tetramethylxylene diisocyanate (m-TMXDI); Para-tetramethylxylene diisocyanate (p-TMXDI); optional such as isocyanurate of toluene diisocyanate, trimer of diphenylmethane diisocyanate, trimer of tetramethylxylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate and mixtures thereof Polyisocyanate trimerized isocyanurates; such as toluene diisocyanate uretdione, hexamethylene diisocyanate uretdione and mixtures thereof Dimerization uretdione meaning polyisocyanates; modified polyisocyanates derived from the isocyanates and polyisocyanates; as well as mixtures thereof. In one embodiment, the saturated diisocyanates include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (H ₁₂ MDI), 1,6-hexamethylene diisocyanate (HDI), or combinations thereof. is there.

  By changing the number of unreacted NCO groups in the polyurethane prepolymer, it is possible to adjust factors such as reaction rate and hardness of the resulting composition. For example, the number of unreacted NCO groups in the polyurethane prepolymer of isocyanate and polyol can be less than about 14%. In one embodiment, the polyurethane 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 embodiment, the proportion of unreacted NCO groups is from about 3% to about 9%. Also, the proportion of unreacted NCO groups in the polyurethane polymer can be about 7.5% or less, preferably about 7% or less. In another embodiment, the unreacted NCO content is from about 2.5% to about 7.5%, more preferably from about 4% to about 6.5%.

Unsaturated diisocyanates, i.e. aromatic compounds, may also be used in the present invention, but the use of unsaturated compounds in the prepolymer is preferably combined with the use of light stabilizers or pigments as described below. Examples of unsaturated diisocyanates include, but are not limited to, substituted and isomeric mixtures including 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI); -Dimethyl-4,4'-biphenyl diisocyanate (TODI); Toluene diisocyanate (TDI); Polymer MDI; Carbodiimide-modified liquid 4,4'-diphenylmethane diisocyanate; Para-phenylene diisocyanate (PPDI); Meta-phenylene diisocyanate (MPDI) Triphenylmethane-4,4'- and triphenylmethane-4,4'-triisocyanate;naphthylene-1,5-diisocyanate;2,4'-,4,4'- and 2,2'-biphenyl diisocyanate Polyphenylene polymethylene polyisocyanate (PMDI) (also known as polymeric PMDI); and mixtures thereof.
When formed, the polyurethane prepolymer may contain from about 10% to about 20% by weight of the free isocyanate monomer of the prepolymer. That is, in one embodiment, the polyurethane prepolymer can strip free isocyanate monomers. For example, after stripping, the prepolymer may contain up to about 1% free isocyanate monomer. In another embodiment, the prepolymer contains no more than about 0.5% by weight free isocyanate monomer.

Polyol Component Any polyol available to those skilled in the art is suitable for use in the polyurethane prepolymer. Examples of polyols include, but are not limited to, polyether polyols, polycaprolactone polyols, polyester polyols, polycarbonate polyols, hydrocarbon polyols, and mixtures thereof. Both saturated and unsaturated polyols are suitable for use in the present invention.
Suitable polyether polyols for use in the present invention include, but are not limited to, polytetramethylene ether glycol (PTMEG); polytetramethylene ether glycol and 2-methyl-1,4-butanediol (PTG-L Poly (oxyethylene) glycol; poly (oxypropylene) glycol; ethylene oxide capped (polyoxypropylene) glycol; poly (oxypropyleneoxyethylene) glycol; and mixtures thereof.
Suitable polycaprolactone polyols include, but are not limited to, diethylene glycol initiated polycaprolactone; propylene glycol initiated polycaprolactone; 1,4-butanediol initiated polycaprolactone; trimethylolpropane initiated polycaprolactone; neopentyl. 1,6-hexanediol-initiated polycaprolactone; polytetramethylene ether glycol (PTMEG) -initiated polycaprolactone; ethylene glycol-initiated polycaprolactone; dipropylene glycol-initiated polycaprolactone; and mixtures thereof is there.

Suitable polyester polyols include, but are not limited to, polyethylene adipate glycol; polyethylene propylene adipate glycol; polybutylene adipate glycol; polyethylene butylene adipate glycol; polyhexamethylene adipate glycol; polyhexamethylene butylene adipate glycol; ortho-phthalate -1,6-hexanediol polyester polyol; polyethylene terephthalate polyester polyol; and mixtures thereof.
Examples of polycarbonate polyols that can be used in the present invention include, but are not limited to, poly (phthalate carbonate) glycol, poly (hexamethylene carbonate) glycol, polycarbonate polyols containing bisphenol A, and mixtures thereof. .

Hydrocarbon polyols include, but are not limited to, hydroxy-terminated liquid isoprene rubber (LIR), hydroxy-terminated polybutadiene polyols, hydroxy-terminated polyolefin polyols, hydroxy-terminated hydrocarbon polyols, and mixtures thereof. is there.
Other polyols that can be used to prepare the prepolymers of the present invention include, but are not limited to, glycerols; castor oil and derivatives thereof; Polytail H; Polytail HA; Kraton polyols; acrylic polyols Acid functionalized polyols based on carboxylic acid, sulfonic acid or phosphoric acid groups; dimer alcohols converted from saturated dimerized fatty acids; and mixtures thereof.
By using polyols based on a hydrophobic backbone, the polyurethane compositions of the present invention can be more water resistant than polyurethane compositions containing polyols that do not have a hydrophobic backbone. Some non-limiting examples of polyols based on a hydrophobic backbone include hydrocarbon polyols, hydroxy-terminated polybutadiene polyols, polyethers, polycaprolactones, and polyesters.

Curing Agent The polyurethane prepolymer can be cured by a single curing agent or curing agent blend or mixture. The curing agent of the present invention can be modified with a freezing point depressant as described above.
Curing agents used in the present invention include, but are not limited to, hydroxy terminal curing agents, amine terminal curing agents, and mixtures thereof. Depending on the prepolymer to curing agent ratio, the castable polyurethane composition can be inherently thermoplastic or thermosetting. For example, polyurethane prepolymers cured with 1: 1 stoichiometric diols or secondary diamines are inherently thermoplastic. On the other hand, thermosetting polyurethanes are generally produced from prepolymers cured with primary diamines or polyfunctional glycols. In another embodiment, a thermoset polyurethane may be produced when a prepolymer to hardener ratio is less than about 1 when a secondary diamine is used. For example, the composition of the present invention can be a thermosetting polyurethane when the prepolymer to secondary diamine curing agent is 1: 0.95. The curing agent can be saturated or unsaturated.

Furthermore, the type of curing agent used determines whether the polyurethane composition is polyurethane / urethane or polyurethane / urea. For example, a polyurethane prepolymer cured with a hydroxy-terminated curing agent is a polyurethane / urethane because excess isocyanate groups that may be present react with the hydroxyl groups of the curing agent to form additional urethane bonds. In contrast, when an amine-terminated curing agent is used with the polyurethane prepolymer, excess isocyanate groups react with the amine groups of the amine-terminated curing agent to form urea bonds, resulting in a polyurethane / urea composition.
That is, for the purposes of the present invention, the polyurethane / urethane contains only urethane bonds as shown in the following general structure:

(Wherein x is the chain length, ie about 1 or greater; R and R ₁ are straight or branched hydrocarbon chains having from about 1 to about 20 carbons). On the other hand, polyurethane / urea contains both the urethane bond shown in the above structural formula and the following urea bond:

(Wherein x is the chain length, ie about 1 or greater; R and R ₁ are straight or branched hydrocarbon chains having from about 1 to about 20 carbons).
Suitable curing agents include, but are not limited to, 1,4-butanediol; 1,3-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; propylene glycol Dipropylene glycol; polypropylene glycol; ethylene glycol; diethylene glycol; polyethylene glycol; resorcinol-di (β-hydroxyethyl) ether and derivatives thereof; hydroquinone-di (β-hydroxyethyl) ether and derivatives thereof; 1'-phenylaminobis;trimethylolpropane;4,4'-methylenebis(2-chloroaniline);3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine;4,4'-methylenebis(2-ethylaniline);4,4'-bis- (sec-butylamino) -diphenylmethane; 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-bis -(sec-butylamino) benzene; 1,2-bis- (sec-butylamino) benzene; 3,5-diethyltoluene-2,4-diamine; 3,5-diethyltoluene-2,6-diamine; tetra -(2-hydroxypropyl) -ethylenediamine; N, N'-dialkyldiaminodiphenylmethane; trimethylene glycol-di-p-aminobenzoate; polytetramethylene oxide-di-p-aminobenzoate; 4,4'-methylenebis- ( 3-chloro-2,6-diethylaniline); 1,4-cyclohexyldimethylol; 2-methylpentamethylenediamine; isomers and mixtures of diaminocyclohexane; isomers and mixtures of cyclohexanebis (methylamine); poly Tetramethylene ether Recycles; Cyclohexyl dimethylol isomers and mixtures; Triisopropanolamine; Diethylenetriamine; Triethylenetetramine; Tetraethylenepentamine; Propylenediamine; 1,3-Diaminopropane; Dimethylaminopropylamine; Diethylaminopropylamine; (Propylamine); monoethanolamine; diethanolamine; triethanolamine; monoisopropanolamine; diisopropanolamine; N, N'-diisopropyl-isophoronediamine; polyoxypropylenediamine, propylene oxide triamine; and mixtures thereof. In one embodiment, the curing agent used with the prepolymer includes 3,5-dimethylthio-2,4-toluenediamine; 3,5-dimethyl-thio-2,6-toluenediamine; 4'-bis- (sec-butylamino) -diphenylmethane; N, N'-diisopropyl-isophoronediamine;polyoxypropylenediamine; propylene oxide triamine; 3,3'-dimethyl-4,4'-diaminocyclohexylmethane; And a mixture of these.

  Suitable saturated hydroxy-terminated curing agents include, but are not limited to, ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; trimethylol Propane; triisopropanolamine; diethylene glycol bis- (aminopropyl) ether; 1,5-pentanediol; 1,6-hexanediol; 1,3-bis- (2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol 1,3-bis- [2- (2-hydroxyethoxy) ethoxy] cyclohexane; 1,3-bis- {2- [2- (2-hydroxyethoxy) Ethoxy] ethoxy} cyclohexane; N, N, N ′, N′-tetra- (2-hydroxypropyl-ethylene) diamine; polytetramethylene ether glycol having a molecular weight in the range of about 250 to about 3900; and mixtures thereof . In one embodiment, the hydroxy-terminated curing agent has a molecular weight of at least 50. In another embodiment, the hydroxy-terminated curing agent has a molecular weight of about 2000 or less. In yet another embodiment, the hydroxy-terminated curing agent has a molecular weight of about 250 to about 3900. As used herein, molecular weight is to be understood as an absolute mass average molecular weight and will be understood by those skilled in the art.

  Suitable saturated amine-terminated curing agents include, but are not limited to, ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1. 4,4 -'- bis- (sec-butylamino) -dicyclohexylmethane; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (sec-butylamino) -Cyclohexane; derivatives of 4,4'-bis- (sec-butylamino) -dicyclohexylmethane; 4,4'-dicyclohexylmethanediamine; 1.4-cyclohexane-bis- (methylamine); 1,3-cyclohexane-bis- (Methylamine); diethylene glycol bis- (aminopropyl) ether; 2-methylpentamethylene-diamine; N, N'-diisopropylisophoronediamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; Tetraethylenepentamine; Propylenediamine; Dipropylenetriamine; 1,3-Diaminopropane; Dimethylaminopropylamine; Diethylaminopropylamine; Imido-bis- (propylamine); Monoethanolamine; Diethanolamine; Triethanolamine; Monoisopropanolamine Diisopropanolamine; triisopropanolamine; isophoronediamine; and mixtures thereof. In one embodiment, the amine curing agent has a molecular weight of about 64 or greater. In another embodiment, the amine curing agent has a molecular weight of about 2000 or less.

Composition Additives Additional materials usually included in polyurethane and polyurea compositions can be added to the polyurethane and polyurea prepolymers, modified curative blends, or composite compositions of the present invention. These additional materials include, but are not limited to, catalysts, wetting agents, colorants, optical brighteners, cross-linking agents, whitening agents such as TiO ₂ and ZnO, UV absorbers, hindered amine light stabilizers, There are defoamers, processing aids, surfactants, and other conventional additives. For example, a wet additive can be added to the modified curative mixture of the present invention to more efficiently disperse the pigment (s). Suitable wetting agents are available from Byk-Chemle and Crompton Corporation, among others.
Also, antioxidants, stabilizers, softeners, plasticizers such as internal and external plasticizers, impact modifiers, foaming agents, density-controlling fillers, reinforcing materials, and compatibilizers are any of the present invention. It can also be added to the composition. Those skilled in the art are aware of the purpose of these additives and the amounts used to meet those purposes.

Catalyst The catalyst can also be used to promote the reaction between the prepolymer and the curing agent in both polyurethane and polyurea compositions. Suitable catalysts include, but are not limited to, bismuth catalyst; zinc octoate; tin octoate; bis-butyltin dilaurate (DABCO® T-12 from Air Products and Chemicals), bis-butyl Tin catalysts such as tin diacetate (DABCO® T-1); tin octoate (DABCO® T-9); tin (II) chloride, tin (IV) chloride; bis-butyltin dimethoxide (FASCAT®-4211); dimethyl-bis [1- (oxondecyl) oxy] stannane (FORMEZ® UL-28); di-n-octyltin bis-isooctyl mercaptoacetate (FASCAT®) ) UL-29); amine catalysts such as triethylenediamine (DABCO® 33-LV), triethylamine and tributylamine; organic acids such as oleic acid and acetic acid; POLYCAT ™ SA-1, POLYCAT ™ ) Delayed catalysts such as SA-2 and POLYCAT (trademark), etc. Beauty mixtures thereof. In one embodiment, the catalyst is bis-butyltin dilaurate. The catalyst is preferably added in an amount sufficient to catalyze the reaction of the components in the reactive mixture. In one embodiment, the catalyst is present in an amount from about 0.001% to about 5% by weight of the composition. For example, when using a tin catalyst such as bis-butyltin dilaurate, the catalyst is preferably present in an amount of from about 0.005% to about 1% by weight. In another embodiment, the catalyst is present in an amount greater than about 0.05% by weight. In another embodiment, the catalyst is present in an amount greater than about 0.5% by weight.

  The use of low amounts of tin catalyst, typically about 0 to about 0.04% by weight of the total composition, requires high temperatures that can cause prepolymer degradation to achieve adequate reaction rates. Increasing the amount of catalyst to an unusually high level allows a reduction in process temperature while maintaining a comparable cure stage. The use of a higher amount of catalyst also allows the mixing rate to be delayed. That is, in one embodiment, the tin catalyst is present in an amount from about 0.01% to about 0.55% by weight of the composition. In another embodiment, from about 0.05% to about 0.4% tin catalyst is present in the composition. In yet another embodiment, the tin catalyst is present in an amount from about 0.1% to about 0.25%.

Density adjusting filler fillers can be added to the polyurethane and polyurea compositions of the present invention to affect flow and mixing properties, specific gravity (ie, density modifying filler), modulus, tear strength, reinforcement, etc. . Fillers are generally inorganic and suitable fillers include many metals; zinc oxide and tin oxide, and metal oxides and salts such as barium sulfate, zinc sulfate, calcium carbonate, zinc carbonate, barium carbonate. Clay; tungsten; tungsten carbide; an array of silicas; regrind (recycled core, typically ground to about 30 mesh particles), high Mooney viscosity rubber regrinde; and mixtures thereof.
For example, the compositions of the present invention include a wide range of density adjusting fillers, such as ceramics; glass spheres (solid or hollow, filled or unfilled) and fibers, as known to those skilled in the art; inorganic; It can be reinforced by mixing with particles; and metal particles such as metal flakes, metal powders, oxides; and their derivatives. The selection of such filler (s) will depend on the type of golf ball desired, ie, one piece, two piece, multi-component, or wound, as more fully detailed below. Generally, the filler is an inorganic substance having a density higher than 4 g / cc, and is present in an amount of about 5 to about 65% by mass based on the total mass of the polymer components contained in the corresponding layer (one or more layers). . Examples of useful fillers include zinc oxide, barium sulfate, calcium oxide, calcium carbonate, and silica, and other known corresponding salts and oxides.
Fillers can also be used to modify the mass of the core or at least one additional layer in a specialty ball, for example, lower mass balls are preferred by players with low swing speeds.

Foaming or foaming agent The composition of the present invention may be foamed by adding at least one physical or chemical foaming or foaming agent. The use of foamed polymer allows golf ball designers to adjust the density or mass distribution of the ball to adjust the angular moment of inertia and thus the spin rate and performance of the ball. Foamed materials also provide potential cost savings due to reduced use of polymeric materials.
Useful foaming or foaming agents include, but are not limited to, azobisformamide; azobisisobutyronitrile; diazoaminobenzene; N, N-dimethyl-N, N-dinitrosotephthalamide; N, N -Dinitrosopentamethylene-tetramine; benzenesulfonyl-hydrazide; benzene-1,3-disulfonylhydrazide; diphenylsulfone 3-3, disulfonylhydrazide; 4,4'-oxybisbenzenesulfonylhydrazide; p-toluenesulfonyl semicarbi Dimethylamine; barium azodicarboxylate; butylamine nitrile; nitroureas; trihydrazinotriazine; phenyl-methyl-uranium; p-sulfone hydrazide; organic blowing agents such as peroxides; There are such inorganic foaming agents. Gases such as air, nitrogen, carbon dioxide, etc. can also be injected into the composition during the injection molding process.

Furthermore, the foam composition of the present invention can also be formed by mixing the microspheres with the composition either during or before the molding process. Polymers, ceramics, metals and glass microspheres are useful in the present invention and can be solid or hollow, filled or unfilled. In particular, microspheres up to about 1000 micrometers in diameter are useful. Furthermore, the use of liquid nitrogen for foaming as disclosed in US Pat. No. 6,386,992 (which is incorporated herein by reference) also provides a highly uniform use for the present invention. A foam composition may be produced.
Either injection molding or compression molding can be used to form a layer or core comprising a foamed polymeric material. For example, the compositions of the present invention can be thermoformed and thus compression molded. In compression molded grafted metallocene catalyzed polymer blend layers, half shells are injection molded with a grafted metallocene catalyzed polymer blend in a normal half shell mold or foam grafted metallocene catalyzed polymer sheet is compression molded. Can be manufactured. Place the half shell around the preformed center or core, cover, or mantle layer and introduce the assembly into the compression molding machine, about 250 ° F to 400 ° F (about 121.1 ° C to 204.4 ° C) Compression molding with. Thereafter, the molded ball is still cooled in the mold and finally removed when the layer of grafted metallocene catalyzed polymer blend is sufficiently hard to handle without deformation. Thereafter, additional cores, mantles, and covers are molded onto the previously molded layer as needed until a complete ball is formed.

Light Stabilizer The composition of the present invention may contain at least one light stabilizer component to prevent significant yellowing from the unsaturated component contained therein. The use of light stabilizers is preferred, for example, in compositions having a yellowness difference (ΔY) of about 15 or greater, but can also be added to compositions having a yellowness difference of about 12 to about 15. As used herein, light stabilizers can be understood to include hindered amine light stabilizers, ultraviolet (UV) absorbers, and antioxidants.
Suitable light stabilizers include, but are not limited to, TINUVIN® 292, TINUVIN® 328, TINUVIN® 213, TINUVIN® 765, TINUVIN® 770, and There is TINUVIN® 622. TINUVIN® products are available from Ciba Specialty Chemicals, Tarrytown, NY. In one embodiment, the light stabilizer is the UV absorber TINUVIN® 328, which is useful in aromatic compounds. In another embodiment, the hindered amine light stabilizer TINUVIN® 765 is used in aromatic or aliphatic compounds. Furthermore, TINUVIN® 292 may also be used in the aromatic or aliphatic compounds of the present invention.
As noted above, dyes, and optical brighteners and fluorescent pigments may also be included in golf ball covers made with polymers prepared in accordance with the present invention. Such additional ingredients may be added in any amount that achieves its desired purpose.
The composition of the present invention preferably contains only a saturated component because the unsaturated component turns yellow over time. However, although saturated compositions are resistant to discoloration, they are not immune to deterioration of mechanical properties upon weathering. The addition of UV absorbers and light stabilizers to any of the above compositions helps maintain tensile strength, elongation, and hue stability. The use of a light stabilizing component also helps prevent cover surface damage due to photolysis. That is, suitable UV absorbers and light stabilizers as listed above may also be included in the saturated composition of the present invention.

  In order to further improve the shear resistance and heat resistance of the resulting polyurea elastomer, a polyfunctional curing agent can be used to help improve crosslinkability. In one embodiment of the invention, the multifunctional curing agent is modified with a compatible freezing point depressant as detailed above. For example, a triol such as trimethylolpropane or a tetraol such as N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine may be added to the composition. In one embodiment, a primary diamine such as 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane or 4,4′-diaminodicyclohexylmethane is added to the polyurea composition. Useful triamine curing agents to improve the crosslinkability of the polyurea elastomer include, but are not limited to, propylene oxide triamines; trimethylolpropane triamines; glycerin triamines; N, N-bis { 2-[(aminocarbonyl) amino] ethyl} -urea; N, N ′, N ″ -tris (2-aminoethyl) -methanetriamine; N1- (5-aminopentyl) -1,2,6-hexanetriamine 1,1,2-ethanetriamine; N, N ′, N ″ -tris (3-aminopropyl) -methanetriamine; N1- (2-aminoethyl) -1,2,6-hexanetriamine; N1- ( 10-aminodecyl) -1,2,6-hexanetriamine; 1,9,18-octadecanetriamine; 4,10,16,22-tetraazapentacosane-1,13,25-triamine; N1- {3- [ [4-[(3-aminopropyl) amino] butyl] amino] propyl} -1,2,6-hexanetriamine; di-9-octadecenyl- (Z, Z) -1, 1,3-propanetriamine; 1,4,8-octanetriamine; 1,5,9-nonanetriamine; 1,9,10-octadecanetriamine; 1,4,7-heptanetriamine; 1,5,10-decane Triamine, 1,8,17-heptadecanetriamine; 1,2,4-butanetriamine; propanetriamine; 1,3,5-pentanetriamine; N1- {3-[[4-[(3-aminopropyl) amino ] Butyl] amino] propyl} -1,2,6-hexanetriamine; N1- {4-[(3-aminopropyl) amino] butyl} -1,2,6-hexanetriamine; 2,5-dimethyl-1 , 4,7-heptanetriamine; N1- (6-aminohexyl) -1,2,6-hexanetriamine; 6-ethyl-3,9-dimethyl-3,6,9-undecantriamine; -Undecanetriamine; 1,6,11-undecanetriamine; N, N-bis (aminomethyl) -methanediamine; N, N-bis (2-aminoethyl) -1,3-propanediamine; methanetriamine; N1- (2-aminoethyl) -N2- (3-aminopropyl) -1,2,5-pentanetriamine; N1- (2-aminoethyl) -1,2,6-hexanetriamine; 2,6,11-trimethyl-2,6,11 -Dodecanetriamine; 1,1,3-propanetriamine; 6- (aminomethyl) -1,4,9-nonanetriamine; 1,2,6-hexanetriamine; N2- (2-aminoethyl) -1,1 , 2-ethanetriamine; 1,3,6-hexanetriamine; N, N-bis (2-aminoethyl) -1,2-ethanediamine; 3- (aminomethyl) -1,2,4-butanetriamine; 1,1,1-ethanetriamine; N1, N1-bis (2-aminoethyl) -1,2-propanediamine; 1,2,3-propanetriamine; 2-methyl-1,2,3-propanetriamine; And a mixture of these.

Fragrance Components Some materials used in the polyurea or polyurethane compositions of the present invention are odorous in nature or generate odors during reaction with other materials or oxygen. For example, the odor of curing agent Ethacure 300 is attributed to dimethyl disulfide (DMDS) immediately after the product has reacted with oxygen. As used herein, a substance or component is odorous if the odor threshold is above a threshold of 0.029 mg / m ^{3 in} air. A fragrance or masking component can be added to the composition of the present invention to eliminate odor. The fragrance component is preferably added in an amount of about 0.01% to about 1.5% by weight of the composition. In one embodiment, the fragrance component is added to the composition in an amount greater than or equal to about 0.03% by weight of the composition. In another embodiment, the fragrance component is added to the composition in an amount up to about 1.2% by weight of the composition. In yet another embodiment, the fragrance component is added in an amount from about 0.5% to about 1% by weight of the composition. For example, the optimum addition amount of the fragrance component can be about 0.08% by weight of the composition, but more addition can enhance the effect if necessary.
Suitable fragrance ingredients include, but are not limited to, Long Lasting Fragrance Mask # 59672, Long Lasting Fragrance Mask # 46064, Long Lasting Fragrance Mask # 55248, Non-Descript Fragrance Mask # 97779, Fresh and Clean Fragrance Mask # 88177 , And Garden Fresh Fragrance Mask # 87473, all manufactured by Flavor and Fragrance Specialties of Morwor, New Jersey. Other non-limiting examples of fragrance ingredients that can be added to the compositions of the present invention include benzaldehyde, benzyl benzoate, benzyl propionate, benzyl salicylate, benzyl alcohol, cinnamic aldehyde, natural and aromatic from plant sources. There are oils, and mixtures thereof.

Composition Blends The compositions of the present invention preferably comprise from about 1% to about 100% polyurea or polyurethane, depending on whether the composition is polyurethane-based or polyurea-based, but blends with other materials can do. In one embodiment, the compositions of the present invention contain from about 10% to about 90% polyurea or polyurethane, preferably from about 10% to about 75% polyurea or polyurethane, and from about 90% to about 90%. 10%, preferably about 90% to about 25% of other polymers and / or other materials as described below. Unless otherwise noted, all percentages are given by weight percent of the total composition of the golf ball layer.
Other polymeric materials suitable for blending with the compositions of the present invention include castable thermoplastics, cationic and anionic urethane ionomers and urethane epoxies, polyurethane ionomers, polyurea ionomers, epoxy resins Polyethylenes, polyamides and polyesters, polycarbonates, polyacrylines, siloxanes and epoxy resins or blends thereof, and mixtures thereof. Those skilled in the art will be familiar with methods for blending polymeric materials with the compositions of the present invention.

  Examples of suitable urethane ionomers are disclosed in US Pat. No. 5,692,974, the disclosure of which is incorporated herein by reference in its entirety. Other examples of suitable polyurethanes are disclosed in US Pat. No. 5,334,673, the disclosure of which is incorporated herein by reference. Examples of suitable polyureas used to prepare the polyurea ionomers described above are disclosed in US Pat. No. 5,484,870. Specifically, the polyurea of US Pat. No. 5,484,870 is prepared by reacting a polyisocyanate and a polyamine curing agent to obtain a polyurea, and the present invention is prepared from a polyurea prepolymer and a curing agent. Different from polyurea. Examples of suitable polyurethanes cured with epoxy group-containing curing agents are disclosed in US Pat. No. 5,908,358. The disclosures of these patents are incorporated herein by reference in their entirety.

Acid-functionalized compositions The present invention also filed February 5, 2002, "Golf Ball Compositions Comprising a Novel Acid Functional Polyurethane, Polyurea, or Copolymer Thereof" entitled U.S. patent application Ser. No. 10 / 072,395 As also disclosed, the acid functionalization of the polyurethane and polyurea compositions of the present invention is also contemplated and the US patent application is hereby incorporated by reference in its entirety. Without being bound by any particular theory, it is believed that polyurethanes and polyureas containing acid functional components or groups have improved adhesion to other components or layers. The acid functional group is preferably based on a sulfone group (HSO ₃ ), a carboxyl group (HCO ₂ ), a phosphate group (H ₂ PO ₃ ), or a combination thereof. One or more types of acid functional groups can be introduced into the polyurea or polyurethane.
In one embodiment, the acid functional polyurea or polyurethane is prepared from a prepolymer having an acid functional component. Acid groups (one or more) can be introduced on the isocyanate component or polyol component when preparing the polyurethane composition. In preparing the polyurea composition of the present invention, acid group (s) can be introduced onto the isocyanate or polyetheramine component.

  Suitable acid functional polyols for use in the polyurethane compositions of the present invention are described in US Pat. Nos. 5,661,207 and 6,103,822, along with reagents and methods used to derive such acid functional polyols. The disclosures of these US patents are hereby incorporated by reference in their entirety. In one embodiment, the acid functional polyols used in the polyurethane prepolymer comprise carboxylated, sulfonated or phosphorylated derivatives of polyester polyols. Suitable acid functional polyols are acid numbers (acid equivalents divided by 56,100) of at least about 10, preferably from about 20 to about 420, more preferably from about 25 to about 150, and most preferably from about 30 to about 75. Calculated by). Furthermore, the hydroxyl number of the polyols (calculated by dividing the number of hydroxyl group equivalents by 56,100) is at least about 10, preferably from about 20 to about 840, more preferably from about 20 to about 175, most preferably about It can be 50 to about 150. Polyols may also have a hydroxyl functionality (average number of hydroxyl groups per polyol molecule) of at least about 1.8, preferably from about 2 to about 4.

  Suitable acid functional isocyanates include those having acid functional groups that can be prepared by reacting isocyanates and acid functional group containing compounds as described in U.S. Pat.Nos. 4,956,438 and 5,071,578. There are isocyanates, the disclosures of these US patents are hereby incorporated by reference in their entirety. Acid groups (one or more) can also be introduced during the post-polymerization reaction, in which acid functional groups (one or more) are introduced or bonded to the polyurea or polyurethane. Furthermore, an acid-functional polyurea or polyurethane prepared by the copolymerization method as described above can be further introduced with an additional acid-functional group by such a post-polymerization reaction. Suitable agents and preparation methods for introducing acid functional groups on polyurea or polyurethane are described in US Pat. No. 6,207,784, the entire disclosure of which is incorporated herein by reference. Those skilled in the art will be aware of other methods of preparing acid functional polyureas or polyurethanes. For example, combinations of the embodiments described above can be used as described in US Pat. No. 5,661,207, the disclosure of which is incorporated herein by reference in its entirety.

The acid functional polyurethane or polyurea can be partially or fully neutralized with an organic or inorganic metal base and / or a tertiary amine to produce anionic polyurethane / polyurea ionomers. The base can be added during the preparation of the prepolymer or as a separate neutralization step on the acid-functional polyurethanes and polyureas already polymerized. If these aspects occur simultaneously, the base is preferably present in all stages.
Suitable metal bases for use in partial or complete neutralization may include compounds such as metal oxides, metal hydroxides, metal carbonates, metal bicarbonates and metal acetates. Metal ions can include, but are not limited to, Group IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIB, and VIIIB metal ions. Preferred metal ions for such bases include lithium, sodium, potassium, magnesium, zinc, calcium, manganese, aluminum, tungsten, zirconium, titanium and hafnium. The amines are preferably hindered tertiary amines such as tributylamine, triethylamine, triethylenediamine, dimethylcetylamine and similar compounds. Primary or secondary amines are used when a neutralization step occurs after the polymer has been formed because the amine hydrogen easily reacts with isocyanate groups and thereby interferes with polyurea or polyurethane polymerization. Only preferably can be used. The person skilled in the art is aware of further suitable chemicals for neutralization.

Golf Ball Core Layer Golf ball cores formed in accordance with the present invention can be solid, semi-solid, hollow, fluid-filled or powder-filled, one-piece or multi-component cores. The term “semi-solid” as used herein refers to pastes, gels and the like. Any core material known to those skilled in the art is suitable for use in the golf ball of the present invention. Suitable core materials include: thermosetting materials such as rubber, styrene butadiene, polybutadiene, isoprene, polyisoprene, trans-isoprene; thermoplastic materials such as ionomer resins, polyamides or polyesters; and thermoplastic and thermal There are curable polyurethane elastomers. As previously mentioned, the polyurethane or polyurea compositions of the present invention can be incorporated into any golf ball component that includes a core. For example, the core layer may contain at least one of the polyurea / urea composition, polyurea / urethane composition, polyurethane / urethane composition, or polyurethane / urea composition of the present invention.

In one embodiment, the golf ball core is formed from a composition comprising a base rubber (natural, synthetic or a combination thereof), a crosslinker and a filler. In another embodiment, the golf ball core is a reaction comprising a cis-trans-conversion catalyst, an elastic polymer component comprising polybutadiene, a free radical source, and optional crosslinkers, fillers, or both. Form from product. U.S. Patent Application No. 10 / 190,705, filed July 9, 2,002, entitled “Low Compression, Resilient Golf Balls With Rubber Core”, co-assigned and co-assigned. Various combinations of polymers, cis-trans-conversion catalysts, fillers, crosslinkers, and free radical sources, such as those disclosed in (incorporated herein), are used to produce the reaction product. Can be prepared. Although the polybutadiene reaction product is described in the section relating to the core composition, the present invention also contemplates the use of the reaction product that constitutes at least a portion of any golf ball component.
As used herein, the terms core and center are generally used interchangeably to represent the innermost component of the ball. However, in some embodiments, the term “center” is used when there are multiple core layers, ie, a center and an outer core layer.

In order to obtain higher elasticity and lower compressibility of the polybutadiene component, the high molecular weight polybutadiene having a cis-isomer content of preferably greater than about 40% is preferably converted and optionally in the golf ball or part thereof. Increase the percentage of trans-isomer content at this point. In one embodiment, the cis-isomer is present in an amount greater than about 70%, preferably greater than about 80%, more preferably greater than about 90% of the total polybutadiene content. In yet another embodiment, the cis-isomer is present in an amount greater than about 95%, more preferably greater than about 96% of the total polybutadiene content.
A low amount of 1,2-polybutadiene isomer (“vinyl-polybutadiene”) is desired in the initial polybutadiene and reaction product. In one embodiment, the vinyl polybutadiene isomer content is less than about 7%, preferably less than about 4%, more preferably less than about 2%.
The polybutadiene material can have an absolute molecular weight greater than about 200,000. In one embodiment, the polybutadiene molecular weight is greater than about 250,000, preferably from about 300,000 to 500,000. In another embodiment, the polybutadiene molecular weight is about 400,000 or greater. It is preferred that the polydispersity of the material is not higher than about 2, more preferably not higher than 1.8, even more preferably not higher than 1.6.

In one embodiment, the polybutadiene has a Mooney viscosity higher than about 20, preferably higher than about 30, more preferably higher than about 40. Mooney viscosity is typically measured according to ASTM D-1646. In another embodiment, the polybutadiene has a Mooney viscosity of greater than about 35, preferably greater than about 50. In yet another embodiment, the Mooney viscosity is about 120 or less. For example, the Mooney viscosity of the unvulcanized polybutadiene can be from about 40 to about 120. In one embodiment, the Mooney viscosity is from about 40 to about 80. In another embodiment, the Mooney viscosity is from about 45 to about 60, more preferably from about 45 to about 55.
In one embodiment, the central composition includes at least one rubber material having a resilience index of at least about 40. In another embodiment, the elasticity index of the at least one rubber material is at least about 50.
Examples of desirable polybutadiene rubbers include BUNA® CB22 and BUNA® CB23, commercially available from Bayer, Akron, Ohio; UBEPOL (commercially available from Ube Industries, Tokyo, Japan) (Registered trademark) 360L and UBEPOL (registered trademark) 150L; commercially available CARIFLEX (registered trademark) BCP820, CARIFLEX (registered trademark) BCP824, CARIFLEX (registered trademark) BR1220; available from Shell, Houston, Texas; There are KINEX® 7245 and KINEX® 7665 commercially available from Goodyear. If desired, the polybutadiene can be mixed with other elastomers known in the art such as natural rubber, polyisoprene rubber and / or styrene-butadiene rubber to modify the properties of the core.

Without being bound by catalytic any theory, cis - & trans - conversion catalyst, together with a source of free radicals, the proportion of the polybutadiene polymer component cis - believed that acts to convert into a form - from the transformer It has been. That is, the cis-trans-transformation is preferably organic sulfur or metal-containing organic sulfur compound, sulfur or metal-free substituted or unsubstituted aromatic organic compound, inorganic sulfide compound, aromatic organometallic compound, or these Including the presence of a cis-trans-conversion catalyst such as a mixture.
As used herein, “cis-trans-conversion catalyst” means any component or combination thereof that converts at least a portion of the cis-isomer to the trans-isomer at a constant temperature. The cis-trans-converting catalyst component can include one or more cis-trans-converting catalysts described herein, but typically includes at least one organic sulfur component, a Group VIA component, Inorganic sulfides, or combinations thereof. In one embodiment, the cis-trans-conversion catalyst is a blend of an organic sulfur compound and an inorganic sulfide component or a Group VIA component.

As used herein in connection with the present invention, the term “organic sulfur compound” or “organic sulfur component” refers to any compound containing carbon, hydrogen and sulfur. As used herein, the term “sulfur component” means a component that is elemental sulfur, polymeric sulfur, or a combination thereof. It should also be understood that “elemental sulfur” refers to the ring structure of S ₈ and “polymeric sulfur” is a structure containing at least one additional sulfur relative to elemental sulfur. is there.
The cis-trans-conversion catalyst produces reaction products that increase the trans-polybutadiene isomer content to contain about 5% to 70% trans-isomer polybutadiene, based on total elastic polymer component. Typically present in an amount sufficient to cause Preferably, the cis-trans-conversion catalyst is in an amount sufficient to increase the trans-polybutadiene isomer content by at least about 15%, more preferably at least about 20%, even more preferably at least about 25%. Exists.

  Accordingly, the cis-trans-converting catalyst is present in an amount of about 0.1 to about 25 parts per 100 parts of the total resilient polymer component. As used herein, “parts per hundred”, also known as “pph”, is the number of parts by weight of a particular component present in a mixture with respect to 100 parts by weight of the total polymer component. Define. Mathematically, this number can be expressed as the mass of one component divided by the total mass of the polymer and multiplied by a factor of 100. In one embodiment, the cis-trans-converting catalyst is present in an amount from about 0.1 to about 12 pph of the total resilient polymer component. In another embodiment, the cis-trans-converting catalyst is present in an amount from about 0.1 to about 10 pph of the total resilient polymer component. In yet another embodiment, the cis-trans-converting catalyst is present in an amount from about 0.1 to about 8 pph of the total resilient polymer component. In yet another embodiment, the cis-trans-converting catalyst is present in an amount from about 0.1 to about 5 pph of the total resilient polymer component. Also, the lower limit of the above range can be increased if it is determined that 0.1 pph does not give the desired amount of conversion. For example, the amount of cis-trans-conversion catalyst present can be about 0.5 or more, 0.75 or more, 1.0 or more, or 1.5 or more.

Suitable organic sulfur components for use in the present invention include, but are not limited to, diphenyl disulfide; 4,4′-ditolyl disulfide; 2,2′-benzamide diphenyl disulfide; bis (2-aminophenyl) disulfide; Bis (4-aminophenyl) disulfide; bis (3-aminophenyl) disulfide; 2,2'-bis (4-aminonaphthyl) disulfide; 2,2'-bis (3-aminonaphthyl) disulfide; -Bis (4-aminonaphthyl) disulfide; 2,2'-bis (5-aminonaphthyl) disulfide; 2,2'-bis (6-aminonaphthyl) disulfide; 2,2'-bis (7-aminonaphthyl) Disulfide; 2,2'-bis (8-aminonaphthyl) disulfide; 1,1'-bis (2-aminonaphthyl) disulfide; 1,1'-bis (3-aminonaphthyl) disulfide; 1,1'-bis (3-aminonaphthyl) disulfide; 1,1'-bis (4-aminonaphthyl) 1,1'-bis (5-aminonaphthyl) disulfide; 1,1'-bis (6-aminonaphthyl) disulfide; 1,1'-bis (7-aminonaphthyl) disulfide; 1,1 ' -Bis (8-aminonaphthyl) disulfide; 1,2'-diamino-1,2'-dithiodinaphthalene;2,3'-diamino-1,2'-dithiodinaphthalene; bis (4-chlorophenyl) disulfide; Bis (2-chlorophenyl) disulfide; bis (3-chlorophenyl) disulfide; bis (4-bromophenyl) disulfide; bis (2-bromophenyl) disulfide; bis (3-bromophenyl) disulfide; bis (4-fluorophenyl) Bis (4-iodophenyl) disulfide; bis (2,5-dichlorophenyl) disulfide; bis (3,5-dichlorophenyl) disulfide; bis (2,4-dichlorophenyl) disulfide; bis (2,6-dichlorophenyl) disulfide Bis (2,5-dibromophenyl) disulfide; bis (3,5-dibromophenyl) disulfide; bis (2-chloro-5-bromophenyl) disulfide; bis (2,4,6-trichlorophenyl) disulfide; Bis (2,3,4,5,6-pentachlorophenyl) disulfide; bis (4-cyanophenyl) disulfide; bis (2-cyanophenyl) disulfide; bis (4-nitrophenyl) disulfide; bis (2-nitrophenyl) 2,2'-dithiobenzoic ethyl; 2,2'-dithiobenzoic methyl; 2,2'-dithiobenzoic acid; 4,4'-dithiobenzoic ethyl; bis (4-acetylphenyl) disulfide Bis (2-acetylphenyl) disulfide; bis (4-formylphenyl) disulfide; bis (4-carbamoylphenyl) disulfide; 1,1'-dinaphthyl disulfide; 2,2'-dinaphthyl disulfide; 2'-dinaphthyl disulfide; 2,2'-bis (1-chlorodinaphthyl) disulfide; 2,2'-bis (1-bromonaphthyl) disulfide; 1,1'-bis (2-chloronaphthyl) disulfide; There is at least one such as 2,2′-bis (1-cyanonaphthyl) disulfide; 2,2′-bis (1-acetylnaphthyl) disulfide, or a mixture thereof. The most preferred organic sulfur component comprises diphenyl disulfide, 4,4′-ditolyl disulfide or mixtures thereof, especially 4,4′-ditolyl disulfide. In one embodiment, the at least one organic sulfur component is substantially free of metals. As used herein, the term “substantially free of metal” means less than about 10% by weight, preferably less than about 5% by weight, more preferably less than about 3% by weight, even more preferably about 1%. It means less than% by weight, most preferably less than about 0.01% by weight. Suitable substituted or unsubstituted aromatic organic compounds that do not contain sulfur or metal include, but are not limited to, diphenylacetylene, azobenzene, or mixtures thereof. As aromatic organic group is preferably in the size range of C ₆ -C _20, more preferably C ₆ -C _10.

In one embodiment, the organic sulfur-trans-conversion catalyst is present in the reaction product in an amount greater than about 0.5 pph. In another embodiment, the cis-trans-conversion catalyst comprising an organic sulfur component is present in the reaction product in an amount greater than about 0.6 pph. In yet another embodiment, the cis-trans-conversion catalyst comprising an organic sulfur component is present in the reaction product in an amount greater than about 1.0 pph. In yet another embodiment, the cis-trans-conversion catalyst comprising an organic sulfur component is present in the reaction product in an amount greater than about 2.0 pph.
Suitable metal-containing organic sulfur components include, but are not limited to, cadmium, copper, lead and tellurium analogs of diethyldithiocarbonate, diamyldithiocarbonate and dimethyldithiocarbonate, and mixtures thereof. In one embodiment, the metal-containing organic sulfur cis-trans-conversion catalyst is present in the reaction product in an amount of about 1.0 pph or greater. In another embodiment, the cis-trans-conversion catalyst comprising a Group VIA component is present in the reaction product in an amount greater than about 2.0 pph. In yet another embodiment, the cis-trans-conversion catalyst comprising a Group VIA component is present in the reaction product in an amount greater than about 2.5 pph. In yet another embodiment, the cis-trans-conversion catalyst comprising a Group VIA component is present in the reaction product in an amount greater than or equal to about 3.0 pph. The organic sulfur component may also be a halogenated organic sulfur compound. Halogenated organic sulfur compounds include, but are not limited to, compounds having the following general formula:

Wherein R ₁ -R ₅ can be C ₁ -C ₈ alkyl groups in any order; halogen groups; thiol groups (—SH); carboxylated groups; sulfonated groups; and hydrogen);
Furthermore, pentafluorothiophenol; 2-fluorothiophenol; 3-fluorothiophenol; 4-fluorothiophenol; 2,3-fluorothiophenol; 2,4-fluorothiophenol; 3,4-fluorothiophenol; 3,5-fluorothiophenol; 2,3,4-fluorothiophenol; 3,4,5-fluorothiophenol; 2,3,4,5-tetrafluorothiophenol; 2,3,5,6-tetra 4-chlorotetrafluorothiophenol; pentachlorothiophenol; 2-chlorothiophenol; 3-chlorothiophenol; 4-chlorothiophenol; 2,3-chlorothiophenol; 2,4-chlorothiophenol 3,4-chlorothiophenol; 3,5-chlorothiophenol; 2,3,4-chlorothiophenol; 3,4,5-chlorothiophenol; 2,3,4,5-tetrachlorothiopheno 2,3,5,6-tetrachlorothiophenol; pentabromothiophenol; 2-bromothiophenol; 3-bromothiophenol; 4-bromothiophenol; 2,3-bromothiophenol; 3,4-bromothiophenol; 3,3,4-bromothiophenol; 3,3,4-bromothiophenol; 2,3,4,5-tetrabromo 2,3,5,6-tetrabromothiophenol; pentaiodothiophenol; 2-iodothiophenol; 3-iodothiophenol; 4-iodothiophenol; 2,3-iodothio 2,4-iodothiophenol; 3,4-iodothiophenol; 3,5-iodothiophenol; 2,3,4-iodothiophenol; 3,4,5-iodothiophenol 2,3,4,5-tetraiodothiophenol; 2,3,5,6-tetraiodothiophenol And their metal salts, e.g., zinc, magnesium, lithium, calcium, potassium, manganese, there is a salt of nickel. Preferably, the halogenated organic sulfur compound is pentachlorothiophenol, and the sulfur compound pentachlorothio loaded in pure form or under the trade name STRUKTOL®, ie 45% (equivalent to 2.4 parts of PCTP). It is commercially available as a phenol-containing clay-based carrier. STRUKTOL®, commercially available from Struktol Company of America, Stow, Ohio. PCTP is commercially available in pure form from eChinachem, San Francisco, California, and in salt form from eChinachem, San Francisco, California. Most preferably, the halogenated organic sulfur compound is a zinc salt of pentachlorothiophenol and is commercially available from eChinachem, San Francisco, California. The halogenated organic sulfur compounds of the present invention are preferably present in an amount greater than about 2.2 pph, more preferably from about 2.3 pph to about 5 pph, and most preferably from about 2.3 to about 4 pph.

The cis-trans-conversion catalyst may also include a Group VIA component. As used herein, the term “Group VIA component” or “Group VIA element” means a component that includes a sulfur component, selenium, tellurium, or a combination thereof. Elemental sulfur and polymeric sulfur are commercially available from, for example, Elastochem, Chardon, Ohio. Examples of sulfur catalyst compounds include PB (RM-S) -80 elemental sulfur and PB (CRST) -65 polymeric sulfur, each available from Elastochem. An exemplary tellurium catalyst under the trade name TELLOY and an exemplary selenium catalyst under the trade name VANDEX are each commercially available from RT Vanderbilt, Norwalk, Connecticut.
In one embodiment, a cis-trans-conversion catalyst comprising a Group VIA component is present in the reaction product in an amount greater than or equal to about 0.25 pph. In another embodiment, a cis-trans-conversion catalyst comprising a Group VIA component is present in the reaction product in an amount of about 0.5 pph or greater. In yet another embodiment, a cis-trans-conversion catalyst comprising a Group VIA component is present in the reaction product in an amount of about 1.0 pph or greater.

  Suitable inorganic sulfide components include, but are not limited to, titanium sulfide, magnesium sulfide, and sulfide analogs of iron, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, tin and bismuth. is there. In one embodiment, a cis-trans-conversion catalyst comprising an inorganic sulfide component is present in the reaction product in an amount greater than about 0.5 pph. In another embodiment, a cis-trans-conversion catalyst comprising a Group VIA component is present in the reaction product in an amount greater than or equal to about 0.75 pph. In yet another embodiment, a cis-trans-conversion catalyst comprising a Group VIA component is present in the reaction product in an amount of about 1.0 pph or greater. When the reaction product comprises a mixture of cis-trans-conversion catalyst comprising an organic sulfur component and an inorganic sulfide component, the organic sulfur component is preferably about 0.5 or higher, preferably 1.0 or higher, more preferably about 1.5 or higher. The inorganic sulfide component is preferably present in an amount of about 0.5 pph or more, preferably 0.75 pph or more, more preferably about 1.0 pph or more.

Substituted or unsubstituted aromatic organic compounds can also be included in the cis-trans-conversion catalyst. In one embodiment, the aromatic organic compound is substantially free of metals. Suitable substituted or unsubstituted aromatic organic compounds, but are not limited to, the formula _{(R 1) x -R 3 -MR} 4 - (R 2) there is a component having a _y, wherein, R ₁ and R ₂ is hydrogen, or substituted or unsubstituted C _{1 to} C ₂₀ linear, branched or cyclic alkyl, alkoxy or alkylthio groups, or monocyclic, polycyclic or condensed ring C _{6 to} C _{24, respectively.} X and y are each an integer from 0 to 5; R ₃ and R ₄ are each selected from monocyclic, polycyclic or fused ring C ₆ -C ₂₄ aromatic groups; M is an azo group or a metal component. R ₃ and R ₄ are each preferably selected from C ₆ -C ₁₀ aromatic groups, more preferably selected from phenyl, benzyl, naphthyl, benzamide and benzothiazyl. R ₁ and R ₂ are each preferably selected from substituted or unsubstituted C ₁ -C ₁₀ linear, branched or cyclic alkyl, alkoxy or alkylthio groups, or C ₆ -C ₁₀ aromatic groups . When R ₁ , R ₂ , R ₃ or R ₄ is substituted, the substituent may include one or more of the following substituents: hydroxy and its metal salts; mercapto and its metal salts; halogen; Amino, nitro, cyano and amide; carboxyls including esters, acids and metal salts thereof; silyl; acrylates and metal salts thereof; sulfonyl or sulfonamides; and phosphates and phosphites. When M is a metal component, M can be any suitable elemental metal available to those skilled in the art. Typically, the metal is a transition metal, but is preferably tellurium or selenium.

Free radical sources Free radical sources, often referred to as free radical initiators, are preferred in the compositions and methods of the present invention. The free radical source is typically a peroxide, preferably an organic peroxide, which decomposes during the cure cycle. Suitable free radical sources include di-t-amyl peroxide, di (2-t-butyl-peroxyisopropyl) benzene peroxide or -bis (t-butylperoxy) diisopropylbenzene, 1,1-bis ( (t-butylperoxy) -3,3,5-trimethylcyclohexane or 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, dicumyl peroxide, di-t-butyl peroxide 2,5-di- (t-butylperoxy) -2,5-dimethylhexane, n-butyl-4,4-bis (t-butylperoxy) valate, lauryl peroxide, benzoyl peroxide, t- There are organic peroxide compounds such as butyl hydroperoxide, and any mixtures thereof.

Other examples include, but are not limited to, VAROX® 231 XL and Varox® DCP-R, commercially available from Elf Atochem, Philadelphia, Pa .; Chicago, Illinois PERKADOX® BC and PERKADOX® 14 commercially available from Akzo Nobel; and ELASTOCHEM® DCP-70, commercially available from Rhein Chemie, Trenton, NJ is there. It is well known that peroxides are available in various forms with different activities. Its activity is typically defined as “active oxygen content”. For example, PERKADOX® BC peroxide is 98% active and has an active oxygen content of 5.8%, while PERKADOX® DCP-70 is 70% active and 4.18% Has an active oxygen content. The peroxide is greater than about 0.1 parts per 100 parts of the total elastic polymer component, preferably about 0.1 to 15 parts per 100 parts of the total elastic polymer component, more preferably about 0.2 to 5 per 100 parts of the total elastic polymer component. May be present in parts. When the peroxide is present in pure form, the peroxide is preferably present in an amount of at least about 0.25 pph, more preferably from about 0.35 pph to about 2.5 pph, and most preferably from about 0.5 pph to about 2 pph.
Further, as described above, peroxides can also be obtained in concentrated forms well known to have various activities. In this case, if concentrate peroxide is used in the present invention, one skilled in the art can easily adjust the appropriate concentration as pure peroxide by dividing it in the concentrate peroxide by the above activity. I know. For example, 2pph of pure peroxide is equivalent to 4pph of concentrate peroxide that is 50% active (ie 2 ÷ 0.5 = 4).

In one embodiment, the amount of free radical source is about 5 pph or less, but may be about 3 pph or less. In another embodiment, the amount of free radical source is about 2.5 pph or less. In yet another embodiment, the amount of free radical source is about 2 pph or less. In yet another embodiment, the amount of free radical source is about 1 pph or less, preferably about 0.75 pph or less.
Those skilled in the art will appreciate that the presence of certain cis-trans-conversion catalysts according to the present invention is more suitable for a large amount of free radical sources, such as those described above, compared to conventional crosslinking reactions. Should be understood. The free radical source can alternatively or additionally be one or more of an electron beam, UV or gamma rays, x-rays, or any other high energy radiation source that can generate free radicals. Skilled engineers are aware that heating can often facilitate the initiation of free radical generation.
In one embodiment, the ratio of the free radical source to the cis-trans-conversion catalyst is about 10 or less, but may be about 5 or less. Further, the ratio of the free radical source to the cis-trans-conversion catalyst can be about 4 or less, but can be about 2 or less, or about 1 or less. In another embodiment, the ratio of the free radical source to the cis-trans-conversion catalyst is about 0.5 or less, preferably about 0.4 or less. In yet another embodiment, the ratio of the free radical source to the cis-trans-conversion catalyst is greater than about 1.0. In yet another embodiment, the ratio of the free radical source to the cis-trans-conversion catalyst is about 1.5 or higher, preferably about 1.75 or higher.

A crosslinking agent may be included to increase the hardness of the reaction product. Suitable crosslinking agents include unsaturated fatty acids having 3 to 8 carbon atoms such as acrylic acid, methacrylic acid or monocarboxylic acids, such as zinc, calcium or magnesium acrylates, and mixtures thereof. There are one or more salts. Examples include, but are not limited to, diacrylates, dimethacrylates and monomethacrylates of one or more metals, where the metal is magnesium, calcium, zinc, aluminum, sodium, lithium or nickel. is there. Preferred acrylates include zinc acrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate, and mixtures thereof. In one embodiment, zinc methacrylate is used in combination with a zinc salt of pentachlorothiophenol. The cross-linking agent must be present in an amount sufficient to cross-link portions of the polymer chain in the resilient polymer component. For example, the desired compressibility can be obtained by adjusting the amount of crosslinker. This can be accomplished, for example, by varying the type and amount of crosslinker in a manner well known to those skilled in the art. The cross-linking agent is typically present in an amount greater than about 0.1% of the polymer component, preferably about 10-50% of the polymer component, more preferably about 10-40% of the polymer component.
In one embodiment, the crosslinking agent is greater than about 10 parts ("pph") per 100 parts of base polymer, preferably from about 20 to about 40 pph of base polymer, more preferably from about 25 to about base polymer. Present in an amount of 35 pph. When organic sulfur is selected as the cis-trans-conversion catalyst, zinc diacrylate can be selected as the cross-linking agent and is present in an amount of less than about 25 pph.

When promoter elemental sulfur or polymeric sulfur is included in the cis-trans-conversion catalyst, it should be understood that promoters may be used to improve the performance of the cis-trans-conversion catalyst. . Suitable accelerators include, but are not limited to, sulfenamides such as N-oxydiethylene-2-benzothiazole-sulfenamide, thiazoles such as benzothiazyl disulfide, and bismuth dimethyldithiocarbamate. Dithiocarbamates, thiurams such as tetrabenzylthiuram disulfide, xanthates such as zinc isopropylxanthate, thiadiazines, thioureas such as trimethylthiourea, guanazines such as N, N'-di-ortho-tolylguanazine, or butyraldehyde -Aldehyde-amines such as aniline condensation products, or mixtures thereof.

Antioxidants Typically, antioxidants are included in the usual golf ball core compositions because the antioxidants are included in the materials supplied by the manufacturers of the compounds used in the golf ball core. Is included. Without being bound by any particular theory, a high amount of antioxidant in the reaction product can result in a low trans-isomer content because the antioxidant consumes at least a portion of the free radical source. Can occur. Thus, an amount of antioxidant greater than about 0.3 pph facilitates cis-trans-transformation, even at high levels of free radicals in the aforementioned reaction product, eg, about 3 pph. The effective amount of free radicals actually available can be significantly reduced.
The presence of antioxidants in the composition is believed to reduce the ability of free radicals to properly facilitate cis-trans conversion, thus ensuring a sufficient amount of free radicals to be used in the conversion. One way is to increase the initial amount of free radicals present in the composition so that a sufficient amount of free radicals remain in the composition after interaction with the antioxidant. That is, the initial amount of free radicals used in the composition can be increased by at least about 10%, and more preferably by at least about 25%, sufficient to effect the desired cis-trans-conversion appropriately. To leave a quantity of free radicals. Depending on the amount of antioxidant present in the composition, the initial amount of free radicals can be increased by at least 50%, 100%, or even more as needed. As described below, the selection of the amount of free radicals in the composition can be determined based on the desired ratio of free radicals to antioxidants.

Another method is to reduce or reduce the amount of antioxidant in the composition. For example, the reaction product of the present invention is substantially free of antioxidants, thereby achieving greater utilization of free radicals towards cis-trans-transformation. As used herein, the term “substantially free” means that the polybutadiene reaction product has an antioxidant of less than about 0.3 phh, preferably less than about 0.1 phh, more preferably less than about 0.05 phh. Is generally meant to contain no more than about 0.01 phh of antioxidant.
It has been shown in the present invention that the amount of antioxidant correlates with the trans-isomer content after conversion. For example, a polybutadiene reaction product containing 0.5 pph antioxidant cured at 335 ° F. (168.3 ° C.) for 11 minutes, after conversion, has about 15% trans- The isomer content is generated. In contrast, the same polybutadiene reaction product substantially free of antioxidants results in a trans-isomer content of about 32% at the outer surface and about 21.4% at the inner position after the conversion reaction.

In one embodiment, the ratio of free radical source to antioxidant is greater than about 10. In another embodiment, the ratio of free radical source to antioxidant is greater than about 25, preferably greater than about 50. In yet another embodiment, the ratio of free radical source to antioxidant is about 100 or greater. In yet another embodiment, the ratio of free radical source to antioxidant is about 200 or higher, preferably 250 or higher, more preferably about 300 or higher.
When the reaction product is substantially free of antioxidants, the amount of free radical source is preferably about 3 pph or less. In one embodiment, the free radical source is present in an amount of about 2.5 pph or less, preferably about 2 pph or less. In yet another embodiment, the amount of free radical source in the reaction product is about 1.5 pph or less, preferably about 1 pph or less. In yet another embodiment, the free radical source is present in an amount of about 0.75 pph or less.

When the reaction product contains about 0.1 pph or more of antioxidant, the free radical source is preferably present in an amount of about 1 pph or more. In another embodiment, when the reaction product contains about 0.1 pph or more of antioxidant, the free radical source is present in an amount of about 2 pph or more. In another embodiment, the free radical source is present in an amount greater than about 2.5 pph when the antioxidant is present in an amount greater than about 0.1 pph.
In one embodiment, when the reaction product contains greater than about 0.05 pph antioxidant, the free radical source is preferably present in an amount greater than about 0.5 pph. In another embodiment, the free radical source is present in an amount greater than or equal to about 2 pph when the reaction product contains greater than about 0.05 pph antioxidant. In another embodiment, the free radical source is present in an amount greater than about 2.5 pph when the antioxidant is present in an amount greater than about 0.05 pph.

Other Additives Additional materials normally included in golf ball compositions can be added to the polybutadiene reaction product of the present invention. These additional materials include, but are not limited to, density control fillers, colorants, reaction accelerators, crosslinking agents, whitening agents, UV absorbers, hindered amine light stabilizers, antifoaming agents, processing aids. , And other conventional additives. Stabilizers, softeners, plasticizers including internal and external plasticizers, impact modifiers, blowing agents, excipients, reinforcements and compatibilizers may also be added to any composition of the present invention. These materials are all well known in the art and are added in amounts typical for their normal purpose.
For example, the fillers described above in connection with the polyurethane and polyurea compositions of the present invention may be added to the polybutadiene reaction product to improve flow and mixing characteristics, specific gravity (ie, density modifying filler), modulus, tear strength. It can act on reinforcement and the like. Fillers can also be used to modify the mass of the core, for example, lower mass balls are preferred by players with low swing speeds.

Trans-isomer conversion As mentioned above, it may be preferable to convert the cis-isomer to the trans-isomer in the polybutadiene core material. That is, in one embodiment, the trans-isomer content after conversion is at least about 10% or more, and further about 12% or more. In another embodiment, the trans-isomer content is about 15% or more after conversion. In yet another embodiment, the trans-isomer content after conversion is about 20% or more, preferably about 25% or more. In yet another embodiment, the trans-isomer content after conversion is about 30% or more, preferably about 32% or more. Also, the amount of trans-isomer after conversion can be about 35% or more, about 38% or more, or even about 40% or more. In yet another embodiment, the amount of trans-isomer after conversion can be about 42% or more, or even about 45% or more.
The cured portion of the component comprising the reaction product of the present invention can include a first amount of trans-isomer polybutadiene at an internal location and a second amount of trans-isomer polybutadiene at an external surface location. In one embodiment, the amount of trans-isomer at the outer surface position is greater than the amount of trans-isomer at the inner position. As further illustrated in the examples below, the difference in trans-isomer content between the outer surface and the inner position after conversion may vary depending on the cure cycle and material ratio used in the conversion reaction. For example, it is possible that these differences represent a center with a greater amount of trans-isomer in the inner part than in the outer part.

  The outer part of the center is the amount already described above, such as up to about 45% above and above and including about 10%, about 12%, about 15% etc. Has trans-isomer content. For example, in one embodiment of the invention, the polybutadiene reaction product may contain about 35% to 60% trans-isomer at the outer surface of the central portion. Another embodiment comprises about 40% to 50% trans-isomer on the outer surface of the central portion. In one embodiment, the reaction product contains about 45% trans-isomer polybutadiene at the outer surface of the central portion. In one embodiment, the reaction product at the center of the solid center portion is then at least about 20% lower trans-isomer, preferably at least about 30% lower trans-isomer than is present on the outer surface, Or it may contain at least about 40% lower trans-isomers. In another embodiment, the amount of trans-isomer at the internal location is at least about 6% lower than present at the outer surface, preferably at least about 10% lower than the second amount.

  The slope between the central inner part and the central outer part can vary. In one embodiment, the difference in trans-isomer content after conversion between external and internal is about 3% or more, while in another embodiment, the difference is about 5% or more. obtain. In another embodiment, the difference between the outer surface and the inner position after conversion is about 10% or more, preferably about 20% or more. In yet another embodiment, the difference in trans-isomer content after conversion between the outer surface and the inner position can be about 5% or less, about 4% or less, even about 3% or less. In yet another embodiment, the difference between the outer surface and the inner location after conversion is less than about 1%.

Reaction Product Properties The polybutadiene reaction product material preferably has a hardness of at least about 15 Shore A, more preferably from about 30 Shore A to 80 Shore D, and even more preferably from about 50 Shore A to 60 Shore D. In addition, the specific gravity is typically greater than about 0.7, preferably greater than about 1, in the golf ball polybutadiene material. Furthermore, the flexural modulus of about 500 psi to 300,000 psi (about 3.45 × 10 ³ kPa to 2.07 × 10 ⁶ kPa), preferably about 2,000 psi to about 200,000 psi (about 1.38 × 104 to about 1.38 × 10 ⁶ kPa). Have.
The desired loss tangent in the polybutadiene reaction product should be less than about 0.15 at −60 ° C. and less than about 0.05 at 30 ° C. when measured at a frequency of 1 Hz and 1% strain. In one embodiment, the polybutadiene reaction product material preferably has a tangent loss of less than about 0.1 at −50 ° C., more preferably less than about 0.07 at −50 ° C.

In order to produce a golf ball having the desired compression stiffness, the dynamic stiffness of the polybutadiene reaction product material should be less than about 50,000 N / m at -50 ° C. Preferably, the dynamic stiffness should be about 10,000-40,000 N / m at −50 ° C., more preferably the dynamic stiffness should be about 20,000-30,000 N / m at −50 ° C.
In one embodiment, the reaction product has a first dynamic stiffness measured at −50 ° C. that is less than about 130% of the second dynamic stiffness measured at 0 ° C. In another embodiment, the first dynamic stiffness is less than about 125% of the second dynamic stiffness. In yet another embodiment, the first dynamic stiffness is less than about 110% of the second dynamic stiffness.

Golf Ball Intermediate Layer When the golf ball of the present invention includes an intermediate layer, such as an inner cover layer or an outer core layer, ie, any layer placed between the inner core and outer cover of the golf ball, Any material known to those skilled in the art, such as plastic and thermoset materials, can be included. In one embodiment, the intermediate layer is formed from at least a portion of any of the polyureas, polyurethanes, and polybutadienes described above. In one embodiment, the intermediate layer is formed from at least one of the polyurea / urea composition, polyurea / urethane composition, polyurethane / urethane composition, or polyurethane / urea composition of the present invention. In another embodiment, the intermediate layer is formed from the polybutadiene reaction product described above.

Similarly, the intermediate layer can also include one or more homopolymer or copolymer materials as follows:
(1) Vinyl resins prepared by polymerization of vinyl chloride or by copolymerization of vinyl chloride with vinyl acetate, acrylic esters or vinylidene chloride;
(2) Polyolefins such as polyethylene, polypropylene, polybutylene; 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 catalysts Or copolymers and homopolymers prepared using metallocene catalysts;
(3) polyurethanes, such as polyurethanes prepared from polyols and diisocyanates or polyisocyanates and the polyurethanes disclosed in US Pat. No. 5,334,673;
(4) polyureas such as the polyureas disclosed in US Pat. No. 5,484,870;
(5) Poly (hexamethylene adipamide), other polyamides prepared from diamines and dibasic acids, and polyamides such as polyamides from amino acids such as poly (caprolactam); and polyamides And SURLYN, polyethylene, ethylene copolymers, ethyl-propylene-nonconjugated diene terpolymers and the like.

(6) Acrylic resins and blends of these resins with polyvinyl chloride, elastomers, etc .;
(7) Thermoplastic materials such as urethanes; Olefin-based thermoplastic rubbers such as blends of polyolefins and ethylene-propylene-nonconjugated diene terpolymers; Blocks of styrene and butadiene, isoprene or ethylene-butylene rubber Copolymers; or a copoly (ether-amide) such as PEBAX commercially available from Atofina Chemicals, Philadelphia, Pennsylvania;
(8) Polyphenylene oxide resins, or blends of polyphenylene oxide and high impact polystyrene such as that marketed by General Electric Company of Pittsfield, Mass. Under the trade name NORYL;
(9) thermoplastic polyesters, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / glycol modified; elastomers commercially available under the trade name HYTREL from EI DuPont de Nemours & Co., Wilmington, Delaware; and LOMOD from General Electric in Pittsfield, Massachusetts;

(10) Polycarbonate and acrylonitrile butadiene styrene, polybutylene terephthalate, polyethylene terephthalate, styrene maleic anhydride, polyethylene, elastomers, etc., and blends of polyvinyl chloride with acrylonitrile butadiene styrene, ethylene vinyl acetate or other elastomers Or alloys; and
(11) Blends of thermoplastic rubbers with polyethylene, propylene, polyacetal, nylon, polyesters, cellulose esters and the like.
In one embodiment, the intermediate layer comprises an ethylene, propylene, butene-1, or hexene-1 based homopolymer comprising a functional monomer such as acrylic acid or methacrylic acid and a fully or partially neutralized ionomer resin or Copolymers and blends thereof; methyl acrylate, methyl methacrylate homopolymers and copolymers; imidized amino group-containing polymers; polycarbonate, reinforced polyamides, 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 (fluoroethylene ) And copolymers comprising these functional comonomers; and polymers such as blends thereof.

Ionomer As mentioned briefly above, the intermediate layer may comprise ionomer materials such as ionic copolymers of ethylene and unsaturated monocarboxylic acids, these materials being EI DuPont, Wilmington, Delaware. It is available from de Nemours & Co. under the trade name SURLYN®, or Exxon's IOTEK® or ESCOR®. These are copolymers of ethylene and methacrylic acid or acrylic acid completely or partially neutralized with salts such as zinc, sodium, lithium, magnesium, potassium, calcium, manganese or nickel, ie, about 1 to about 100% neutralized. Or a terpolymer. In one embodiment, the carboxylic acid group is neutralized from about 10% to about 100%. The carboxylic acid group may also be methacrylic acid, corotonic acid, maleic acid, fumaric acid or itaconic acid. The salts are reaction products of olefins having 2 to 10 carbon atoms and unsaturated monocarboxylic acids having 3 to 8 carbon atoms.

The intermediate layer is an E / X / Y terpolymer (E is ethylene, X is an acrylate or methacrylate-based softening comonomer present at about 0 to 50% by mass, and Y is about 5 to 35% by mass. At least one ionomer, such as acid-containing ethylene copolymer ionomers, including acrylic acid or methacrylic acid present in%. In another embodiment, the acrylic acid or methacrylic acid is present at about 8-35 wt%, more preferably 8-25 wt%, most preferably 8-20 wt%.
The ionomers may include so-called “low acid” and “high acid” ionomers, and mixtures thereof. In general, ionic copolymers containing up to about 15% acid are considered “low acid” ionomers, and copolymers containing more than about 15% acid are considered “high acid” ionomers. For example, US Pat. Nos. 6,506,130 and 6,503,156 define low acid ionomers as containing an acid content of 16% by weight or less, while high acid ionomers contain more than about 16% by weight acid. It is defined as

  Low acid ionomers are believed to give high spin. That is, in one embodiment, the intermediate layer comprises a softer terpolymer having an acid present at about 10-15% by weight and optionally comprising a softening comonomer such as iso- or n-butyl acrylate. Contains low acid ionomers that form polymers. The softening comonomer is a vinyl ester of an aliphatic carboxylic acid having an acid of 2 to 10 carbon atoms, a vinyl ether having an alkyl group of 1 to 10 carbon atoms, and an alkyl group of 1 to 10 It may be selected from the group consisting of alkyl acrylates or methacrylates containing 1 carbon atom. Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate or butyl methacrylate.

  In another embodiment, the intermediate layer comprises at least one high acid ionomer for low spin speed and maximum distance. In this aspect, acrylic acid or methacrylic acid is present at about 15 to about 35% by weight, making the ionomer a high modulus ionomer. In one embodiment, the high modulus ionomer comprises about 16% by weight carboxylic acid, preferably about 17% to about 25% by weight carboxylic acid, more preferably about 18.5% to about 21.5% by weight carboxylic acid. Contains acid. In some situations, additional comonomers such as acrylate esters (ie, iso- or n-butyl acrylate, etc.) can also be included to prepare softer terpolymers. Additional comonomers include vinyl esters of aliphatic carboxylic acids where the acid has 2 to 10 carbon atoms, vinyl ethers where the alkyl group contains 1 to 10 carbon atoms, and 1 to 10 alkyl groups. It may be selected from the group consisting of alkyl acrylates or methacrylates containing carbon atoms. Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate or butyl methacrylate.

Thus, examples of many suitable copolymers used to prepare high modulus ionomers include, but are not limited to, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / itaconic acid copolymers, ethylene There are high acid embodiments such as ethylene / maleic acid copolymer, ethylene / methacrylic acid / vinyl acetate copolymer, ethylene / acrylic acid / vinyl alcohol copolymer.
In one embodiment, the intermediate layer may be formed from at least one polymer containing α, β-unsaturated carboxylic acid groups, or a salt thereof 100% neutralized with an organic fatty acid. The organic acid is an aliphatic monofunctional (saturated, unsaturated or polyunsaturated) organic acid. These organic acid salts may also be used. Examples of the organic acid salt of the present invention include barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin or calcium. Salts; salts of fatty acids, especially stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid or dimerized derivatives thereof. The organic acids and salts of the present invention are preferably relatively non-migratory (does not bloom on the polymer surface at ambient temperature) and are non-volatile (does not volatilize at the temperature required in melt mixing).

The acid component of the highly neutralized polymers ("HNP"), typically ethylene-based ionomers, is preferably greater than about 70%, more preferably greater than about 90%, and most preferably at least about 100%. Neutralize. HNPs can also be blended with a second polymer component, which can be neutralized with organic fatty acids, or both, in the usual manner if it contains acid groups. The second polymer component can be partially or fully neutralized, preferably ionomer copolymers and terpolymers, ionomer precursors, thermoplastics, polyamides, polycarbonates, polyesters, polyurethanes, polyureas, Including thermoplastic elastomers, polybutadiene rubber, balata, metallocene catalyzed polymers (grafted and non-grafted), single site polymers, highly crystalline acid polymers, cationic ionomers and the like.
In this embodiment, the acid copolymers may be described as E / X / Y copolymers, where E is ethylene, X is an α, β-ethylenically unsaturated carboxylic acid, and Y is a softening comonomer. It is. In a preferred embodiment, X is acrylic acid or methacrylic acid, Y is C ₁ -C ₁₈ alkyl acrylate or methacrylate ester. X is preferably present in an amount of about 1 to about 35% by weight of the polymer, more preferably about 5 to about 30% by weight of the polymer, and most preferably about 10 to about 20% by weight of the polymer. Y is preferably present in an amount of about 0 to about 50% by weight of the polymer, more preferably about 5 to about 25% by weight of the polymer, and most preferably about 10 to about 20% by weight of the polymer.

The organic acid is an aliphatic monofunctional (saturated, unsaturated or polyunsaturated) organic acid. These organic acid salts may also be used. Examples of the organic acid salt of the present invention include barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin or calcium. Salts; salts of fatty acids, especially stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid or dimerized derivatives thereof. The organic acids and salts of the present invention are preferably relatively non-migratory (does not bloom on the polymer surface at ambient temperature) and are non-volatile (does not volatilize at the temperature required in melt mixing).
Copolyetheresters, copolyesteresters, copolyetheramides, elastic polyolefins, styrene diene block copolymers and their hydrogenated derivatives, copolyesteramides; copolyetherurethanes, copolyesterurethanes, copolyureaurethanes Thermoplastic polyurethane components such as epoxy-based polyurethanes, polycarbonate-based polyurethanes; polyureas; and thermoplastic polymer components such as polycarbonate-based polyurethane fillers, and other components, if included, the acid component It can be blended either before, during or after neutralization.
Examples of these materials are disclosed in US Patent Application Publications 2001/0018375 and 2001/0019971, which are hereby incorporated by reference in their entirety.

The ionomer composition may also include at least one grafted metallocene catalyzed polymer. The blend of this embodiment comprises from about 1 pph to about 100 pph of at least one grafted metallocene catalyzed polymer and from about 99 pph to 0 pph of at least one ionomer, preferably from about 5 pph to about 90 pph of at least one graft. A metallocene-catalyzed polymer and at least one ionomer from about 95 pph to about 10 pph, more preferably at least one grafted metallocene-catalyzed polymer from about 10 pph to about 75 pph and at least one ionomer from about 90 pph to about 25 pph. Most preferably from about 10 pph to about 50 pph of at least one grafted metallocene catalyzed polymer and from about 90 pph to about 50 pph of at least one ionomer. When forming a layer, the grafted metallocene-catalyzed polymer blend can be foamed during molding by any conventional foaming or blowing agent.
Furthermore, the polyamides described in more detail below can also be blended with ionomers.

Non-ionomeric thermoplastic material In another embodiment, the intermediate layer comprises at least one predominantly or fully non-ionomeric thermoplastic material. Suitable non-ionomer materials include polyamides and polyamide blends, grafted and non-grafted metallocene catalyzed polyolefins or polyamides, polyamide / ionomer blends, polyamide / non-ionomer blends, polyphenylene ether / ionomer blends, and There are mixtures of these. Examples of grafted and ungrafted metallocene catalyzed polyolefins or polyamides, polyamide / ionomer blends, polyamide / nonionomer blends were filed on May 6, 2002, “Golf Ball Incorporating Grafted Metallocene Catalyzed Polymer Blends” Pending US patent application Ser. No. 10 / 138,304, which is hereby incorporated by reference in its entirety.

  In one embodiment, polyamide homopolymers such as polyamide 6,18 and polyamide 6,36 are used alone or in combination with other polyamide homopolymers. In another embodiment, polyamide copolymers such as polyamide 6,10 / 6,36 are used alone or in combination with other polyamide copolymers. Other examples of suitable polyamide homopolymers and copolymers include polyamide 4, polyamide 6, polyamide 7, polyamide 11, polyamide 12 (manufactured by Atofina Chemicals of Philadelphia, PA as Rilsan AMNO), polyamide 13, polyamide 4,6 , Polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 6,36, polyamide 12,12, polyamide 13,13, polyamide 6 / 6,6, polyamide 6,6 / 6, 10, Polyamide 6/6, T (T indicates terephthalic acid), Polyamide 6 / 6,6 / 6,10, Polyamide 6,10 / 6,36, Polyamide 66,6,18, Polyamide 66,6,36 , Polyamide 6 / 6,18, Polyamide 6 / 6,36, Polyamide 6 / 6,10 / 6,18, Polyamide 6 / 6,10 / 6,36, Polyamide 6,10 / 6,18, Polyamide 6,12 / 6,18, polyamide 6,12 / 6,36, polyamide 6/66 / 6,18, polyamide 6/66 / 6,36, polyamide 66 / 6,10 / 6,18, polyamide 66 / 6,10 / 6,36, Polyamide 6 / 6,12 / 6,18, polyamide 6 / 6,12 / 6, 36, and mixtures thereof.

As noted above, any of the polyamide homopolymers, copolymers and homopolymer / copolymer blends described above may be used as non-ionomer thermoplastic polymers, non-ionomer thermoplastic copolymers, non-ionomer TPEs, and mixtures thereof. It can be blended with non-ionomer polymers if desired.
One particular example of a polyamide-nonionomer blend is a polyamide-metallocene catalyzed polymer blend. The blend composition includes grafted and / or non-grafted metallocene catalyzed polymers. Grafted metallocene catalyzed polymers functionalized with pendant groups such as maleic anhydride are available in experimental quantities from DuPont. Grafted metallocene-catalyzed polymers can also be obtained by subjecting a commercially available non-grafted metallocene-catalyzed polymer to a post-polymerization reaction comprising a monomer and an organic peroxide and having one or more desired pendant groups. It can also be obtained by preparing a metallocene catalyzed polymer.
Another example of a polyamide-nonionomer blend is a nonionic polymer prepared using a polyamide and a nonmetallocene single-site catalyst. As used herein, the term “nonmetallocene catalyst” or “nonmetallocene single site catalyst” refers to a single site catalyst other than a metallocene catalyst. Examples of suitable single site catalyzed polymers are disclosed in pending US patent application Ser. No. 09 / 677,871, the entire disclosure of which is incorporated herein by reference.

Non-ionomers suitable for blending with polyamide include, but are not limited to, block copoly (ester) copolymers, block copoly (amide) copolymers, block copoly (urethane) copolymers, styrenic block copolymers, thermal Blends of plastics and elastomers (no elastomer vulcanized) (TEB), and blends of thermoplastics and elastomers or rubbers (elastomer dynamically vulcanized) (TED) . Other non-ionomers suitable for blending with polyamide to prepare interlayer compositions include, but are not limited to, polycarbonate, polyphenylene oxide, imidized amino group containing polymers, high impact polystyrene (HIPS), poly Ether ketone, polysulfone, poly (phenylene sulfide), reinforced plastics, acrylic acid-styrene-acrylonitrile, poly (tetrafluoroethylene), poly (butyl acrylate), poly (4-cyanobutyl acrylate), poly (2-ethyl) Butyl acrylate), poly (heptyl acrylate), poly (2-methyl butyl acrylate), poly (3-methyl butyl acrylate), poly (N-octadecyl acrylamide), poly (octadecyl methacrylate), poly (4-dodecyl styrene), Poly (4-tetradecylstyrene), poly (Ethylene oxide), poly (oxymethylene), poly (silazane), poly (furantetracarboxylic acid diimide), poly (acrylonitrile), poly (methylstyrene), silicones; and the polymers to which these polymers belong And copolymers containing their functional comonomers; and mixtures thereof.
In one embodiment, the non-ionomer material has a hardness of about 60 Shore D or higher and a flexural modulus of about 30,000 psi (about 2.07 × 10 ⁵ kPa) or higher.

Elastic polymer / reinforcing polymer blend The intermediate layer comprises an elastic polymer component (which is preferably used as a large proportion of polymer in the intermediate layer to provide elasticity in the cured state) and a reinforcing polymer component. Include as a blend.
Resilient polymers suitable for use in the intermediate layer preferably include polybutadiene, polyisoprene, styrene-butadiene, styrene-propylene-diene rubber, ethylene-propylene-diene having a high molecular weight of at least about 50,000 to about 1,000,000 ( EPDM), and mixtures thereof. In one embodiment, the molecular weight is from about 250,000 to about 750,000, more preferably from about 200,000 to about 400,000.
The reinforcing polymer component has a crystal melting temperature (T _g ) that is low enough to allow mixing without initiating crosslinking, preferably from about −35 ° C. to 120 ° C. Furthermore, the reinforcing polymer component has a sufficiently low viscosity at the mixing temperature when mixing with the resilient polymer component to allow for proper mixing of the two polymer components. The amount of the reinforcing polymer relative to the total composition for forming the intermediate layer is generally about 5-25% by weight, preferably about 10-20% by weight.

Examples of polymers suitable for use in the reinforcing polymer component include the following: trans-polyisoprene, block copolymer ether / ester, acrylic polyol, polyethylene, polyethylene copolymer, 1,2-polybutadiene (Sindi Tactic), ethylene-vinyl acetate copolymer, trans-polycyclooctenenamer, trans-isomer polybutadiene, and mixtures thereof. Particularly suitable reinforcing polymers are HYTREL 3078, a block copolymer ether / ester commercially available from DuPont, Wilmington, Del .; trade name FUREN 88 from Asahi Chemicals, Yakko, Kawasaki, Japan. Trans-isomeric polybutadienes such as those obtained as: trans-polyisoprene commercially available under the trade name KURRARAY TP251 from KURRARAY; commercially available under the trade name LEVAPREN 700HV from Bayer-Rubber Division of Akron, Ohio There are ethylene-vinyl acetate copolymers that are possible; and trans-polycyclooctanemers that are commercially available under the trade name VESTENAME® 8012 from Huls America, Inc., Talmage, Ohio. Some suitable reinforcing polymer components are shown in Table 1 below together with T _c and glass transition temperature (T _g ).

Another polymer that is particularly suitable for use in the reinforcing polymer component is a hardening polybutadiene component, which typically includes at least about 80% trans-isomer content, with the balance being cis- Isomer 1,4-polybutadiene and vinyl-isomer 1,2-polybutadiene. That is, the component can be distinguished from the cis-isomer polybutadiene used to form the golf ball core of the present invention or a polybutadiene having a low, ie, trans-isomer content of typically less than 80%. , "High trans-isomer polybutadiene" or "hardening polybutadiene". The vinyl content of the stiffening component is preferably no more than about 15% of the polybutadiene isomer, preferably less than about 10%, more preferably less than about 5%, most preferably less than about 3%. It is.
When used in the golf ball of the present invention, the hardening polybutadiene component has a polydispersity not higher than about 4, preferably not higher than about 3, more preferably not higher than about 2.5. Polydispersity (P _d ) is the ratio of the weight average molecular weight (M _w ) to the number average molecular weight (M _n ) of the polymer.

Further, the hardening component, when used in the golf balls of the present invention, typically has a high M _w defined as at least about 100,000, preferably from about 200,000 to 1,000,000. In one embodiment, the absolute average molecular weight is about 230,000-750,000. In another embodiment, the molecular weight is from about 275,000 to 700,000. In embodiments where the vinyl content is greater than about 10%, the absolute average molecular weight is preferably greater than about 200,000.
When included in the reinforcing polymer, trans-polyisoprene or high trans-isomer polybutadiene is a polymer blend, i.e., about 10-40%, preferably about 15-30% by weight of the elastic and reinforcing polymer component. More preferably, it is present in an amount of less than about 15-25% by weight.

The same crosslinkers described in connection with the core can also be used in this embodiment to achieve the desired modulus in the elastic polymer (reinforcing polymer blend). In one embodiment, the crosslinking agent is about 1 to about 50 parts per 100 parts of the polymer blend, preferably about 20 to about 45 parts per 100 parts of the polymer blend, more preferably about 30 to about 100 parts. Add in an amount of about 40 parts.
The elastic polymer component, the reinforcing polymer component, the free radical initiator, and any other components used to form the intermediate layer of the golf ball core according to the present invention may be any type of mixing known to those skilled in the art. Can be mixed by law.
The intermediate layer can also be formed from the compositions disclosed in US Pat. No. 5,688,191, and these compositions are listed in Table 2 below (the description of the US patent is hereby incorporated by reference in its entirety). As incorporated herein).

Golf ball cover The cover provides a ball-club interface. Desirable properties in the cover are, inter alia, good moldability, high wear resistance, high impact resistance, high tear strength, high elasticity, and good mold release.
The cover layer may be formed at least in part from the polyurea / urea composition, polyurea / urethane composition, polyurethane / urethane composition or polyurethane / urea composition of the present invention. For example, in one embodiment, the at least one cover layer comprises from about 1% to about 100% by weight of the polyurea / urea composition of the present invention. In another embodiment, the at least one cover layer comprises from about 1% to about 100% by weight of the polyurea / urethane composition of the present invention. In particular, the cover may be formed from the reaction product of an isocyanate and an amine-terminated compound that is cured with a hydroxy-terminated or amine-terminated curing agent. The curing agent can be incorporated into a modified curing agent blend that includes a freezing point depressant.

In another embodiment, the polyurethane composition of the present invention may be used to form at least one cover layer of the golf ball of the present invention. For example, the cover layer can be formed by a reaction product of an isocyanate and a polyol that can be cured with a curing agent or modified curing agent blend prepared from a hydroxy-terminated curing agent, an amine-terminated curing agent, or a mixture thereof. In one embodiment, the cover layer is formed from a polyurethane / urethane composition. In another embodiment, the cover layer is formed from a polyurethane / urea composition. In yet another embodiment, the curing agent is a blend that includes a freezing point depressant.
The cover layer (one or more layers) can also be formed from a blend of compositions as described above. For example, in one embodiment, at least one cover layer is comprised of about 10% to about 90% of preferably saturated polyurea and about 90% to about 10 other polymers and / or other materials. Formed from the composition blend. In another embodiment, the at least one cover layer is a composition of from about 10% to about 90%, preferably saturated polyurethane, and from about 90% to about 10 other polymers and / or other materials. Form from blend. In yet another embodiment, the cover composition comprises from about 10% to about 75% polyurea or polyurethane and from about 90% to about 25% other polymers such as those listed below and / or Includes other materials.

In an embodiment with the polyurea or polyurethane composition of the present invention, the cover composition includes one or more homopolymer or copolymer materials as described below, as well as the core or intermediate / inner cover layer. obtain:
(1) Vinyl resins prepared by polymerization of vinyl chloride or by copolymerization of vinyl chloride with vinyl acetate, acrylic esters or vinylidene chloride;
(2) Polyolefins such as polyethylene, polypropylene, polybutylene; 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 catalysts Copolymers and homopolymers prepared using them;
(3) Thermoplastic or thermosetting, such as polyurethanes prepared from polyols or amines and diisocyanates or polyisocyanates and the polyurethanes disclosed in US Pat. No. 5,334,673 and US Patent Application No. 10 / 072,395 Saturated, unsaturated or unsaturated aliphatic or aromatic acid functionalized polyurethanes;
(4) Thermoplastic or thermosetting saturated or unsaturated aliphatic or aromatic acid functionalized polyureas, such as the polyureas disclosed in US Pat. No. 5,484,870 and US Patent Application No. 10 / 072,395 Kind;

(5) Poly (hexamethylene adipamide), other polyamides prepared from diamines and dibasic acids, and polyamides from amino acids such as poly (caprolactam), polyamides such as reinforced polyamides And blends of polyamides with ionomers, polyethylene, ethylene copolymers, ethyl-propylene-nonconjugated diene terpolymers, and the like.
(6) Acrylic resins and blends of these resins with polyvinyl chloride, elastomers, etc .;
(7) Thermoplastic materials such as urethanes; Olefin-based thermoplastic rubbers such as blends of polyolefins and ethylene-propylene-nonconjugated diene terpolymers; Blocks of styrene and butadiene, isoprene or ethylene-butylene rubber Copolymers; or a copoly (ether-amide) such as PEBAX commercially available from Atofina Chemicals, Philadelphia, Pennsylvania;
(8) Polyphenylene oxide resins or blends of polyphenylene oxide and high impact polystyrene such as that marketed by General Electric Company of Pittsfield, Massachusetts under the trade name NORYL.
(9) thermoplastic polyesters, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / glycol modified; elastomers commercially available under the trade name HYTREL from EI DuPont de Nemours & Co., Wilmington, Delaware; and LOMOD from General Electric in Pittsfield, Massachusetts;

(10) Ethylene, propylene, 1-butene, 1-hexene homopolymers; copolymers containing functional monomers such as acrylic acid or methacrylic acid or fully or partially neutralized ionomer resins, and blends thereof; methyl acrylate Methyl methacrylate homopolymers or copolymers; low acid ionomers; high acid ionomers; and blends thereof;
(11) Polycarbonate and acrylonitrile butadiene styrene, polybutylene terephthalate, polyethylene terephthalate, styrene maleic anhydride, polyethylene, elastomers, etc., and blends of polyvinyl chloride with acrylonitrile butadiene styrene, ethylene vinyl acetate or other elastomers Or alloys; and
(12) Blends of thermoplastic rubbers with polyethylene, propylene, polyacetal, nylon, polyesters, cellulose esters and the like.
The cover may also be at least partially formed from the polybutadiene reaction product described above with respect to the core.
As described elsewhere herein, the composition may be formed on a golf ball in any known manner, such as by casting, compression molding, injection molding or reaction injection molding. One skilled in the art will know that the molding method used can be determined, at least in part, by the properties of the composition. For example, casting is preferred when the material is thermoset, whereas compression molding or injection molding may be preferred in thermoplastic compositions.

Golf Ball Structure The composition of the present invention can be used in any type of ball structure, including but not limited to one piece, two piece, three piece and four piece designs, double core, double cover, intermediate The layers (one or more), the multi-layer core, and / or the multi-layer cover depend on the desired performance type of the ball. That is, the composition of the present invention can be used in the core, intermediate layer, and / or cover of a golf ball, each of which can have a single layer or multiple layers. As used herein, the term “multilayer” means at least two layers.
As explained in the core section, the core can be a one-piece core or a multi-layer core, both of which can be solid, semi-solid, hollow, fluid-filled or powder-filled. A multi-layer core is a core having a deepest component having one or more additional core layers disposed thereon. For example, FIG. 1 shows a golf ball 1 having a core 2 and a cover 3. In one embodiment, the golf ball of FIG. 1 shows a cover 2 comprising a core 2 of polybutadiene reactive material or a number of conventional materials and a polyurea composition of the present invention. In another embodiment, the golf ball of FIG. 1 shows a core 2 formed from a polybutadiene reactive material and a cover 3 comprising the saturated polyurea composition of the present invention. In yet another embodiment, the golf ball 1 may include a core 2 of conventional material and a cover 3 formed from at least one water resistant polyurea or polyurethane composition.

Further, when the golf ball of the present invention includes an intermediate layer, this layer may be combined with a single or multi-layer cover, a single or multi-element core, both a single layer cover and a core, or both a multi-layer cover and a multi-layer core. . The intermediate layer can be an inner cover layer or outer core layer, or any other layer (one or more) disposed between the inner core and outer cover of the golf ball. As in the core, the intermediate layer may also include multiple layers. It should be understood that any number or type of intermediate layers may be used as desired.
FIG. 2 illustrates a multi-layer golf ball 12 that includes a cover 13, at least one intermediate layer 14, and a core 12. In one embodiment, the golf ball 11 of FIG. 2 includes a core 12 of polybutadiene reactive material, an intermediate layer 14, and a cover 13 formed from a polyurea composition of the present invention that is preferably saturated with polyurea. obtain. In addition, the golf ball 21 of FIG. 3 has a core 22 of polybutadiene reactive material or other conventional core material, at least one ionomer intermediate layer 24, and a cover 23 comprising at least one peaceful polyurea.

In another embodiment, the multi-layer golf ball 11 can include a cover 13, a core 12, and an intermediate layer 14, which is formed from at least one water resistant polyurea or polyurethane composition of the present invention. ing. In yet another embodiment, both the intermediate layer 14 and the cover 13 are formed from a water resistant polyurea or polyurethane composition. In yet another embodiment, the intermediate layer 14 is formed from an ionomer material, the core 12 is formed from a polybutadiene reaction product, and the cover 13 is formed from a water resistant polyurea or polyurethane composition.
The intermediate layer can also be a tensioned elastomeric material wrapped around a solid, semi-solid, hollow, fluid filled, or powder filled center. As used herein, the term “fluid” refers to a liquid or gas, and the term “semi-solid” refers to a paste, gel, or the like. The winding layer may be described as a core layer or an intermediate layer for the purposes of the present invention. For example, the golf ball 31 of FIG. 4 may include a core layer 32, a tension type elastomer layer 34 wound thereon, and a cover layer 33. In particular, the golf ball 31 of FIG. 4 may have a core 32 formed from a polybutadiene reaction product, an intermediate layer 34 comprising a tensile elastomeric material, and a cover 33 comprising at least one saturated polyurea or polyurethane. In this aspect of the invention, the saturated polyurea or polyurethane composition is prepared using an amine-terminated compound having a hydrophobic backbone or a polyol having a hydrophobic backbone, respectively, and is more water resistant golf. A ball can be formed. The tensile elastomeric material may be formed from any suitable material known to those skilled in the art.

In yet another embodiment, the wound liquid center golf ball 41 of FIG. 5 includes a hollow spherical core shell 42 having a hollow interior filled with a liquid 43, a thread rubber 44 layer including a tension type elastomer material, and at least one type. And a cover 45 containing a saturated polyurea or polyurethane composition. The saturated polyurea or polyurethane composition can also be water resistant elastomers as described above.
In one embodiment, the tensile elastomeric material can include the polybutadiene reaction product described above. Also, the tension type elastomeric material can be prepared from ordinary polyisoprene. In another embodiment, the polyurea composition of the present invention may be used to form a tensioned elastomeric material. In yet another embodiment, a tensioned form using solvent-spun polyether urea as disclosed in US Pat. No. 6,149,535, which is hereby incorporated by reference in its entirety. An elastomeric material is formed to achieve a smaller cross-sectional area with multiple strands.

In addition, the winding layer was filed on April 27, 2001, as disclosed in pending US patent application Ser. No. 09 / 842,829 entitled “All Rubber Golf Ball with Hoop-Stress Layer” It can also be a high tensile filament having a tensile modulus greater than about 10,000 kpsi (about 6.90 × 10 ⁷ kPa), the contents of which are incorporated herein by reference in their entirety. In another embodiment, the tensioned elastomer layer is coated with a binding material that adheres to the core and itself when activated to swell the strands of the tensioned elastomer layer and cause the cross-sectional area of the layer to swell. Increase by at least about 5%. An example of such a golf ball structure is presented in pending US patent application Ser. No. 09 / 841,910, the entire disclosure of which is incorporated herein by reference.
The intermediate layer can also be formed from a bonding material and a gap material distributed in the bonding material. The effective material property of the intermediate layer is that the force applied tangential to the ball surface is perpendicular to the ball surface. It differs specifically in the force applied to it. An example of this type of intermediate layer was filed on Dec. 28, 2001, and is disclosed in US patent application Ser. No. 10 / 028,826 entitled “Golf Ball with a Radially Oriented Transversely Isotropic Layer and Manufacture of Same”. The entire disclosure of the US patent application is incorporated herein by reference. In one embodiment of the invention, the interstitial material can reach the core from the intermediate layer. In another embodiment, the gap material can be embedded in the cover, brought into contact with the inner surface of the cover, or embedded only in the cover.

The at least one intermediate layer can also be a moisture barrier layer such as those described in US Pat. No. 5,820,488, which is hereby incorporated by reference. Any suitable film-forming material that has a lower water vapor transmission rate than the other layers may be inserted between the core and the outer surface of the ball, i.e., the cover, primer, and clearcoat. Examples include, but are not limited to, polybutadiene reaction products including polyvinylidene chloride, aragonite, and fluorine gas. In one embodiment, the moisture barrier layer comprises the same type of core and cover without the moisture barrier when the golf ball is stored at 100 ° F. (37.8 ° C.) and 70% relative humidity for 6 weeks. It has a water vapor transmission rate low enough to reduce the COR loss of the golf ball by at least 5% when compared to the loss of the COR of the golf ball having and stored under substantially the same conditions.
Prior to forming the cover layer, the inner ball, ie, the core and any intermediate layer positioned thereon, may be surface treated to increase the adhesion between the outer surface of the inner ball and the cover. Examples of such surface treatments include mechanically or chemically scraping the outer surface of the subassembly. In addition, the internal balls can be subjected to corona discharge, plasma treatment, silane dipping, or other chemical treatment known to those skilled in the art before the cover is formed around them. Other layers of the ball, such as the core and each cover layer, can also be surface treated. Examples of these and other surface treatment methods can be found in US Pat. No. 6,315,915, which is hereby incorporated by reference.

  Similarly, the cover may include a plurality of layers, for example, an inner cover layer disposed around the goal center and an outer cover layer disposed thereon. For example, FIG. 6 shows a golf ball 51 having a core 52, a thin inner cover layer 54, and a thin outer cover layer 53 disposed thereon. In particular, the core 51 may be formed from a polybutadiene reactant, the inner cover layer 54 from an ionomer blend, and the outer cover layer 53 from a polyurea composition. Further, FIG. 7 may show a golf ball 61 having a core 62, an outer core layer 65, a thin inner cover layer 64, and a thin outer cover layer 63 disposed thereon. In one embodiment, core 62 and outer core layer 65 are formed from a polybutadiene reactant but differ in hardness, inner cover layer 64 is formed from an ionomer blend, and outer cover layer 63 is formed from a polyurea composition. I am letting. Furthermore, the composition of the present invention can be used to form a golf ball 71 having a large core 72 and a thin outer cover layer 73 as shown in FIG. In one embodiment, the large core 72 is formed from a polybutadiene reactant and the thin outer cover layer 73 is preferably formed from a polyurea composition that is acid functionalized and whose acid groups are at least partially neutralized. ing.

Although golf balls typically use hardness gradients to obtain certain properties, the present invention has essentially the same hardness as the compositions of the present invention, and at least one of these layers is It is also contemplated for use in golf balls having a plurality of cover layers that have been modified in some way that alters properties that affect the performance of the golf ball. Such a golf ball structure was filed on June 13, 2002 and is disclosed in pending US patent application Ser. No. 10 / 167,744 entitled “Golf Ball with Multiple Cover Layers,” All disclosures are incorporated herein by reference.
In one such embodiment, each cover layer can be made of the same material and have essentially the same hardness, but each layer is designed to have a different coefficient of friction value. In another embodiment, the composition of the present invention is used in a golf ball having a plurality of cover layers having essentially the same hardness but different flow characteristics under high deformation. Another aspect of the present invention relates to a golf ball having a plurality of cover layers that have essentially the same hardness but different thicknesses to mimic a soft outer cover on a hard inner coverball.

In another aspect of this concept, each cover layer of a golf ball has essentially the same hardness, but has characteristics that are different at high or low temperatures compared to ambient temperature. Specifically, this aspect of the present invention is that the outer cover layer composition has a lower flexural modulus at lower temperatures than the inner cover layer, while each layer retains the same hardness at ambient and lower temperatures, Relates to a golf ball having a plurality of cover layers that produce a pseudo-soft outer cover layer on the feel of the hard inner cover layer. Certain polyureas have a much more stable flexural modulus at different temperatures than ionomer resins, thus creating an effective “softer” layer at ambient or lower temperatures than at elevated temperatures. Can be used to form.
Yet another aspect of this concept relates to a golf ball having a plurality of cover layers that have essentially the same hardness but have different properties in wet conditions when compared to dry conditions. The wettability of a golf ball layer can be affected by, inter alia, surface roughness, scientific heterogeneity, molecular orientation, swellability, and interfacial tension. That is, a non-destructive surface treatment of a golf ball layer can help increase the hydrophilicity of the layer, while a high degree of polishing or smoothing of the golf ball layer surface can reduce wettability. US Pat. Nos. 5,403,453 and 5,456,972 disclose methods of surface treating polymeric materials to modify their wettability, the disclosures of which are hereby incorporated by reference in their entirety. In addition, plasma etching, corona treatment and flame treatment are also useful surface treatments that modify wettability to the desired state. A wetting agent can also be added to the golf ball layer composition to modify the surface tension of the layer.

Thus, the difference in wettability of each cover layer according to the present invention can be measured by the difference in contact angle. The contact angle to the layer can be from about 1 ° (low wettability) to about 180 ° (very high wettability). In one embodiment, each cover layer has a contact angle that varies by about 1 ° or more. In another embodiment, the contact angle of the cover layer varies by about 3 ° or more. In yet another embodiment, the contact angle of each cover layer varies by about 5 ° or more.
Other non-limiting examples of suitable types of ball structures that can be used in the present invention include U.S. Patent Nos. 6,056,842, 5,688,191, 5,713,801, 5,803,831, 5,803,831, 5,885,172, Some are described in 5,919,100, 5,965,669, 5,981,654, 5,981,658, and 6,149,535, and advertisements US2001 / 0009310 A1, US2002 / 0025862, and US2002 / 0028885. The disclosures of these patents and published patent applications are all incorporated herein by reference.

Formation method of each layerThe golf ball of the present invention is compression molding, flip molding, injection molding, elastic pin injection molding, reaction injection molding (RIM), liquid injection molding (LIM), casting, vacuum molding, powder coating, It can be formed using various application methods such as flow coating, spin coating, dipping, spraying, and the like. An injection molding method using a split vent pin was filed on Dec. 22, 2000 and found in pending US patent application Ser. No. 09 / 742,435 entitled “Split Vent Pin for Injection Molding”. Can be done. Examples of retractable pin injection molding can be found in US Pat. Nos. 6,129,881, 6,235,230 and 6,379,138. These molding reference examples are incorporated herein by reference in their entirety. In addition, cooling chambers, i.e., cooling jackets, such as those disclosed in US patent application Ser. No. 09 / 717,136 filed Nov. 22, 2000 and entitled “Method of Making Golf Balls”, are cast. When used, it can be used to cool the composition and also allows the addition of higher amounts of catalyst into the system.

Usually compression molding and injection molding apply to thermoplastic materials, while RIM, liquid injection molding, and casting are used in thermosetting materials. These and other manufacturing methods are disclosed in US Pat. Nos. 6,207,784 and 5,484,870, the disclosures of which are hereby incorporated by reference in their entirety.
The cores of the present invention may be formed by any suitable method known to those skilled in the art. When the cores are formed from a thermosetting material, compression molding is a particularly suitable method of forming the core. On the other hand, in the thermoplastic core embodiment, the cores may be injection molded.
For example, methods for converting a cis-isomer of a polybutadiene elastic polymer core component to a trans-isomer during a molding cycle are known to those skilled in the art. Suitable methods include single pass mixing (each component added sequentially), multiple pass mixing, and the like. The crosslinker and any other additive used to modify the properties of the golf ball center or additional layers (one or more) may be similarly mixed by any type of mixing method. Suitable mixing equipment is well known to those skilled in the art, and such equipment includes a Banbury mixer, a two roll mill or a twin screw extruder. Appropriate mixing rates and temperatures are well known to those skilled in the art and can be readily determined without undue experimentation.

The mixture can be subjected to, for example, a compression or injection molding process, and the molding cycle can have a single step of molding the mixture at a single temperature for a period of time. In one embodiment, a single step cure cycle is used. While the curing time depends on the various materials selected, a suitable curing time is about 5 to about 18 minutes, preferably about 8 to about 15 minutes, more preferably about 10 to about 12 minutes. An example of a single step molding cycle is to hold the polymer mixture at 171 ° C. (340 ° F.) for 15 minutes in a mixture containing dicumyl peroxide. An example of a two-step molding cycle is to hold the mold at 143 ° C. (290 ° F.) for 40 minutes and then raise the mold to 171 ° C. (340 ° F.) where it is held for 20 minutes. One skilled in the art can readily adjust the cure time based on the particular material used and the description herein.
Furthermore, U.S. Pat. Nos. 6,180,040 and 6,180,722 disclose a method of manufacturing a dual core golf ball. The disclosures of these US patents are incorporated herein by reference in their entirety.

The intermediate layer may also be formed using any suitable method known to those skilled in the art. For example, the intermediate layer may be formed by blow molding and covered with a dimpled cover layer formed by injection molding, compression molding, casting, vacuum forming, powder coating, or the like.
The castable reactive liquid polyurea material of the present invention uses various application methods such as spraying, compression molding, dipping, spin coating, casting, or flow coating methods well known in the art. Can be applied on the inner ball. In one embodiment, the castable reactive polyurea material is formed on the core using a combination of casting and compression molding. Usually compression molding and injection molding are applied to thermoplastic cover materials, while RIM, liquid injection molding and casting are used in thermosetting cover materials.
US Pat. No. 5,733,428 discloses a method of forming a polyurethane cover on a golf ball core (the disclosure of the US patent is hereby incorporated by reference in its entirety). This method relates to the use of casting of both thermosetting and thermoplastic materials as a golf ball cover, since the cover is formed around the core by mixing and introducing the above materials into the mold half. Polyurea compositions can also be used using the same casting method.

For example, as soon as the polyurea composition is mixed, an exothermic reaction begins and continues until the material solidifies around the core. Viscosity is measured over time, filling each mold half, introducing the core into one half, and properly timing each subsequent step of closing the mold to achieve centering of the core cover half fusion. It is important to be able to obtain overall uniformity. A suitable viscosity range for the urea mixture during curing to introduce the core into the mold half is estimated to be approximately from about 2,000 cP to about 30,000 cP, with a range of about 8,000 cP to about 15,000 cP being preferred.
To begin forming the cover, the prepolymer and curing agent are mixed by metering the amount of curing agent and prepolymer through the supply line in a power mixer inside the mixing head. Fill the preheated upper mold halves and place them in the fixture using centering pins that move into the openings in each mold. Thereafter, the cavities of the lower mold half, or each cavity of a series of lower mold halves, are filled with a mixture amount similar to that used in the upper mold half. After holding the reacting material in the upper mold half for about 40 to about 100 seconds, preferably about 70 to about 80 seconds, the core is lowered into the mixture during the gelling reaction at a controlled rate.

The ball cup holds the ball core by reduced pressure (ie, partial vacuum). After about 4 to about 12 seconds of gelation, the vacuum is released to release the core on the location of the core in each half of the mold. In one embodiment, the vacuum is released and the core is released after about 5-10 seconds. The mold half, including the core and the solidified cover half on it, is removed from the centering fixture and inverted, containing the introduced polyurea prepolymer and curing agent starting to gel in the selected amount of reaction at the appropriate time earlier Integrate with second mold half.
Similarly, two of US Pat. Nos. 5,006,297 and 5,334,673 disclose suitable molding methods that can be used to apply the castable reactive liquid used in the present invention. However, the methods of the present invention are not limited to the use of these methods; other methods known to those skilled in the art can also be used. For example, other methods may be used instead of partial vacuum to hold the ball core.

Dimple Use of various dimple patterns and shapes is a relatively effective way to modify the aerodynamic characteristics of a golf ball. Therefore, the method of arranging the dimples on the ball surface can be any available method. For example, the ball may have a 20-sided pattern as described in US Pat. No. 4,560,168 or an 8-sided dimple pattern as described in US Pat. No. 4,960,281.
In one embodiment of the present invention, the golf ball includes 20 triangles formed from about 362 dimples, and does not have a large circle that does not intersect any dimples, except possibly in the mold separation gland. It has an icosahedron dimple pattern. Each of the large triangles preferably has an odd number of dimples (seven) along each side, and the small triangle has an even number of dimples (four) along each side. In order to properly pack the dimples, the large triangle has nine more dimples than the small triangle. In another embodiment, the ball has a total of five different dimple sizes. Each side of the large triangle has four types of dimple sizes, and the small triangle has two types of dimple sizes.

In another embodiment of the present invention, the golf ball has a icosahedron dimple pattern having a plurality of small triangles with one large triangle containing three different dimples and one diameter dimple. In the preferred embodiment, there are 392 dimples and one large circle that does not intersect any dimples. In another embodiment, more than five alternate dimple diameters are used.
In one embodiment of the present invention, a golf ball has an octahedral dimple pattern that includes eight triangles formed from about 440 dimples and three large circles that do not intersect any dimples. In an octahedral pattern, the pattern includes a third group of dimples formed in a smallest triangle adjacent to it in a small triangle. To properly pack the dimples, the large triangle has nine more dimples than the small triangle, and the small triangle has nine more dimples than the smallest triangle. In this embodiment, the ball has six different dimple series distributed over the ball surface. The large triangle has five different dimple series, the small triangle has three different dimple series, and the smallest triangle has two different dimple series.

The dimple pattern can also be arranged according to a phyllotactic pattern as described in US Pat. No. 6,338,684, which is hereby incorporated by reference in its entirety.
The dimple pattern is also an Archimedes pattern such as a truncated octahedron, a large rhomboid 20/12 plane, a truncated dodecahedron, and a large oblique cube octahedron, as disclosed in US patent application Ser. No. 10 / 078,417. The pattern has a non-linear separation line (the US patent application is hereby incorporated by reference in its entirety).
The golf ball of the present invention can also be covered by non-circular dimples, i.e., amorphous dimples, as disclosed in U.S. Pat. No. 6,409,615 (which is hereby incorporated by reference in its entirety). Incorporated into the book).

Dimple patterns that provide a high percentage of surface coverage are preferred and are well known in the art. For example, US Pat. Nos. 5,562,552, 5,575,477, 5,957,787, 5,249,804 and 4,925,193 disclose geometric patterns for positioning dimples on a golf ball. In one embodiment, the golf ball of the present invention has a dimple coverage of at least about 60%, preferably at least about 65%, more preferably at least 70% or more of the cover surface area. Dimple patterns having slightly higher dimple coverage values than those described above can also be used in the present invention. That is, the golf ball of the present invention may have a dimple coverage of at least about 75% or more, about 80% or more, or even about 85% or more.
Further, tubular lattice patterns such as those disclosed in US Pat. No. 6,290,615 may also be used in the golf ball of the present invention, which is hereby incorporated by reference in its entirety. The golf ball of the present invention may also have a number of pyramidal protrusions disposed on the intermediate layer of the ball as disclosed in US Pat. No. 6,383,092, which is hereby incorporated by reference in its entirety. Incorporated herein). A number of pyramidal protrusions on the golf ball cover about 20% to about 80% of the intermediate layer surface.

In another embodiment, the golf ball may have non-planar separation lines that allow some of the multiple pyramidal protrusions to be placed around the equator. Such a golf ball is manufactured using a mold such as that disclosed in pending US patent application Ser. No. 09 / 442,845 filed Nov. 18, 1999 and entitled “Mold For A Golf Ball”. The U.S. patent application is hereby incorporated by reference in its entirety. This embodiment provides higher uniformity of the pyramidal projections.
Some further non-limiting examples of dimple patterns with varying dimple sizes are also filed on September 27, 1999, and are filed in US patent application Ser. No. 09 / 404,164 entitled “Golf Ball Dimple Patterns” and US Pat. No. 6,213,898 (the disclosures of the US patent application and US patent are hereby incorporated by reference in their entirety).

The total number of dimples on the ball, that is, the number of dimples, varies depending on factors such as the selected dimple size and pattern. Generally, the total number of dimples on the ball is preferably about 100 to about 1000 dimples, but those skilled in the art can significantly improve the flight performance of the ball by varying the number of dimples within this range. You will recognize that it can change. In one embodiment, the number of dimples is about 380 or more, more preferably about 400 or more, and even more preferably about 420 or more. In one embodiment, the number of dimples on the ball is about 422 dimples. In some cases, it may be desirable to have a lower dimple number on the ball. That is, one embodiment of the present invention has a dimple number of about 380 or less, more preferably about 350 dimples.
The dimple shape that rotates the suspension curve around the symmetry axis increases the aerodynamic efficiency, provides a convenient way to adjust ball performance without changing the dimple pattern by changing the number of dimples, and has all swing speeds Uniformly increased flight distance can occur in golfers. That is, the suspension curve dimple shape as disclosed in US patent application Ser. No. 09 / 989,191 filed on Nov. 21, 2001 and entitled “Golf Ball Dimples with a Catenary Curve Profile” Intended for use with balls (the US patent application is hereby incorporated by reference in its entirety).

Golf Ball Post Treatment The golf balls of the present invention can be painted, coated, or surface treated for additional advantages.
For example, golf ball covers frequently contain fluorescent materials and / or dyes or pigments to obtain desired color characteristics. The golf ball of the present invention can also be treated with the base resin paint composition. Further, the golf ball can be treated with a composition containing a whitening agent. For example, U.S. Patent Publication No. 2002/0082358 uses 7-triazinylamino-3-phenylcoumarin derivatives as fluorescent whitening agents to provide improved weatherability and gloss (see U.S. Pat. The disclosure of the publication is incorporated herein by reference in its entirety.
In one embodiment, the golf ball of the present invention can be UV cured. Suitable UV curing methods are disclosed in US Pat. Nos. 6,500,495, 6,248,804, and 6,099,415, the disclosures of which are hereby incorporated by reference in their entirety. In one embodiment, the topcoat is UV curable. In another embodiment, the ink is UV curable and can be used as a paint layer or as a marking means for a separate logo or indicium.

In addition, trademarks or other indicia can also be stamped, i.e. pad printed, on the outer surface of the ball cover, after which the stamped outer surface is treated with at least one Korea coat to give the ball a glossy finish. Give and protect the stamp indicia on the cover.
Also, the golf ball of the present invention can be subjected to dye sublimation, and at least one golf ball component is subjected to at least one sublimable ink that migrates deep into the outer surface to form indicia. The at least one sublimable ink preferably comprises at least one of an azo dye, a nitroarylamine dye or an anthraquinone dye. US patent application Ser. No. 10 / 012,538 filed Dec. 12, 2001 and entitled “Method of Forming Indicia on a Golf Ball” is hereby incorporated by reference in its entirety.
Laser marking of selected surface portions of a golf ball that cause a color change in the laser light irradiated portion is also contemplated for use in the present invention. US Pat. Nos. 5,248,878 and 6,075,223 generally disclose such methods, the disclosures of which are incorporated herein by reference in their entirety. Further, the golf ball can be subjected to ablation, i.e. the laser irradiation beam is directed to one part of the cover, the cover part is irradiated, and the irradiation cover part is ablated to form a detectable mark. No significant discoloration of the part occurs. Ablation is filed on December 18, 2002 and is described in US patent application Ser. No. 09 / 739,469 entitled “Laser Marking of Golf Balls,” which is hereby incorporated by reference in its entirety. Embedded in the book.

Protective and decorative coating materials and methods for applying such materials to golf ball cover surfaces are well known in the golf ball art. In general, such coating materials include urethanes, urethane hybrids, epoxies, polyesters and acrylics. If desired, more than one coating layer may be used. The coating layer (one or more layers) may be applied by any suitable method known to those skilled in the art. In one embodiment, the coating layer (one or more) is applied on a golf ball cover by an in-mold coating method as described in US Pat. No. 5,849,168 (which is the entirety of the US patent). Are incorporated herein by reference).
The use of the saturated polyurea and polyurethane compositions of the present invention in golf equipment eliminates the need for golf ball coating with typical post-treatments such as pigmented coating prior to applying a clear top coat to the ball. To do. Unlike compositions that do not have light-stable properties, the compositions used to form the golf equipment of the present invention do not change color upon exposure to light (especially for long-term exposure). Also, by reducing at least one coating process, manufacturers realize economic benefits in terms of reduced processing time and resulting improved work efficiency. In addition, significant weight loss of volatile organic compounds (“VOCs”) that are constituents of typical paints can also be realized by use of the present invention, providing significant environmental benefits.

  Thus, although it is not necessary to use a pigmented coating on the golf ball of the present invention when formed with the above-described saturated composition, the golf ball of the present invention provides paint application, Can be coated or surface treated. For example, as a price for golf balls manufactured and painted in accordance with the present invention, enhanced color stability is provided when surface paint degradation occurs during normal play. The mainstream technology currently used to enhance whiteness is to form a white-toned cover with titanium dioxide, which can be applied to corona treatment, plasma treatment, UV treatment, flame treatment or electron beam treatment. For surface treatment, one or more layers of clear paint that can contain a fluorescent whitening agent are applied. This method is protective and cost effective.

Golf Ball Properties Properties such as hardness, modulus, core diameter, intermediate layer thickness and cover layer thickness of the golf ball of the present invention are effective for play characteristics such as spin, initial speed and feel of the golf ball of the present invention. It has been found. For example, it is believed that the bending and / or tensile modulus of the intermediate layer has an effect on the “feel” of the golf ball of the present invention. It should be understood that the ranges herein are congested with each other, i.e., the lower limit of one range may overlap with the upper limit of another range.

Component Dimensions The dimensions, i.e., thickness and diameter, of each component of a golf ball can vary depending on the properties desired. Any layer thickness may be used for the purposes of the present invention. Non-limiting examples of the various embodiments outlined above are presented below for layer dimensions.
The present invention relates to a golf ball of any size. Although the USGA standard defines the size of a competitive golf ball to be 1.68 inches (4.267 cm) in diameter, golf balls of any size can be used for leisure golf play. The preferred diameter of the golf ball is about 1.68 inches to about 1.8 inches (about 4.267 cm to about 4.572 cm). A more preferred diameter is from about 1.68 inches to about 1.76 inches (about 4.267 cm to about 4.470 cm). A diameter of about 1.68 inches to about 1.74 inches (about 4.267 cm to about 4.420 cm) is most preferred, but any diameter in the range of 1.7 to about 1.95 inches (4.318 to 4.953 cm) may be used. Preferably, the overall diameter of the core and all intermediate layers is about 80% to about 98% of the overall diameter of the final ball.

The core has a diameter ranging from about 0.09 inch to about 1.65 inch (about 0.229 cm to about 4.191 cm). In one embodiment, the core of the present invention has a diameter of about 1.2 inches to about 1.630 inches (about 3.048 cm to about 4.140 cm). In another embodiment, the core has a diameter of about 1.3 inches to about 1.6 inches (about 3.302 cm to about 4.064 cm), preferably about 1.39 inches to about 1.6 inches (about 3.531 cm to about 4.064 cm), and more. Preferably, it is about 1.5 inches to about 1.6 inches (about 3.810 cm to about 4.064 cm). In yet another embodiment, the core has a diameter of about 1.55 inches to about 1.65 inches (about 3.937 cm to about 4.191 cm).
Also, the core of the golf ball can be very large relative to the remainder of the ball. For example, in one embodiment, the core comprises about 90% to about 98% of the ball, preferably about 94% to about 96% of the ball. In this embodiment, the core diameter is preferably about 1.54 inches or more, more preferably about 1.55 inches or more. In one embodiment, the core diameter is about 1.59 inches or greater. In another embodiment, the core diameter is about 1.64 inches or greater.

  Where the core includes an inner core layer and an outer core layer, the inner core layer is preferably about 0.9 inches (about 2.286 cm) or greater, and the outer core layer is preferably about 0.1 inches (about 0.254 cm) or greater in thickness. Have In one embodiment, the inner core layer has a diameter of about 0.09 inches to about 1.2 inches (0.229 cm to about 3.048 cm) and the outer core layer is about 0.1 inches to about 0.8 inches (about 0.254 cm to about 2.032 cm). cm). In yet another embodiment, the inner core layer diameter is about 0.095 inches to about 1.1 inches (about 0.241 cm to about 2.794 cm) and the outer core layer is about 0.20 inches to about 0.03 inches (about 0.508 cm to about 0.58 cm). 0.076 cm) in thickness.

  The cover has a thickness that provides sufficient strength, good performance characteristics and durability. In one embodiment, the cover thickness is about 0.02 inches to about 0.35 inches (about 0.051 cm to about 0.889 cm). The cover preferably has a thickness of about 0.02 inches to about 0.12 inches (about 0.051 cm to about 0.305 cm), more preferably less than about 0.1 inches (about 0.254 cm). When the composition of the present invention is used to form the outer cover of a golf ball, the cover has a thickness of about 0.1 inches or less, preferably about 0.07 inches or less. obtain. In one embodiment, the outer cover may have a thickness of about 0.02 inches to about 0.07 inches (about 0.051 cm to about 0.178 cm). In another embodiment, the cover thickness is about 0.05 inches or less, preferably about 0.02 inches to about 0.05 inches (about 0.051 cm to about 0.127 cm). In yet another embodiment, the outer cover layer of such a golf ball is about 0.02 inches to about 0.045 inches (about 0.051 cm to about 0.114 cm). In yet another embodiment, the outer cover layer is about 0.025 inches to about 0.04 inches (about 0.064 cm to about 0.102 cm) thick. In another embodiment, the outer cover layer is about 0.03 inches (about 0.076 cm) thick.

  The thickness range in the intermediate layer of a golf ball is large because of the great potential when using the intermediate layer, i.e., as an outer core layer, inner cover layer, winding layer, moisture / vapor barrier layer. When used in the golf balls of the present invention, the intermediate layer or inner cover layer may have a thickness of about 0.3 inches or less. In one embodiment, the thickness of the intermediate layer is about 0.002 inches to about 0.1 inches (about 0.051 mm to about 0.254 cm), preferably about 0.01 inches (about 0.254 mm) or more. In one embodiment, the intermediate layer has a thickness of about 0.09 inches or less, preferably about 0.06 inches or less. In another embodiment, the intermediate layer thickness is about 0.05 inches or less, more preferably about 0.01 inches to about 0.045 inches (about 0.254 mm to about 1.143 mm). In one embodiment, the intermediate layer thickness is about 0.02 inches to about 0.04 inches (about 0.508 mm to about 1.016 mm). In another embodiment, the intermediate layer thickness is from about 0.025 inches to about 0.035 inches (about 0.635 mm to about 0.889 mm). In yet another embodiment, the thickness of the intermediate layer is about 0.035 inches (about 0.889 mm) thick. In yet another embodiment, the inner cover layer is about 0.03 inches to about 0.035 inches (about 0.762 mm to about 0.889 mm) thick. Various combinations of these ranges in intermediate and outer cover layer thicknesses may be used in other embodiments.

  The thickness ratio of the intermediate layer to the outer cover layer is preferably about 10 or less, more preferably about 3 or less. In another embodiment, the ratio of the thickness of the intermediate layer to the outer cover layer is about 1 or less. The core and intermediate layer (one or more layers) together form an inner ball having a diameter of preferably about 1.48 inches (about 3.759 cm) or more for 1.68 inch (4.267 cm) balls. In one embodiment, the internal ball of a 1.68 inch (4.267 cm) ball has a diameter greater than or equal to about 1.52 inch (about 3.861 cm). In another embodiment, the internal ball of a 1.68 inch (4.267 cm) ball has a diameter of about 1.66 inch (about 4.216 cm) or less. In yet another embodiment, a 1.72 inch (or larger) ball has an internal ball diameter of greater than or equal to about 1.50 inch. In yet another embodiment, the diameter of the inner ball for a 1.72 inch (4.369 cm) ball is about 1.70 inch (4.318 cm) or less.

Hardness Most golf balls consist of layers with different hardnesses, eg, hardness gradients, to achieve the desired performance characteristics. The present invention contemplates a golf ball having a hardness gradient between each layer, as well as a golf ball having each layer having the same hardness.
In particular, those skilled in the art should understand that there is a fundamental difference between “material hardness” and “hardness as measured directly on a golf ball”. Material hardness is defined by the procedure described in ASTM-D2240 and generally involves measuring the hardness of a flat “slab” or “button” formed from the material whose hardness is to be measured. Hardness when measured directly on a golf ball (or other sphere surface) is a completely different measurement, thus producing different hardness values. This difference includes, but is not limited to, many factors such as ball structure (i.e., core type, number of core and / or cover layers, etc.), ball (or sphere) diameter, and material composition of each adjacent layer. Derived from. It should also be understood that the two measurement methods do not correlate linearly and therefore one hardness value cannot be easily correlated with the other hardness value.

The core of the present invention can have various hardnesses depending on the particular golf ball structure. In one embodiment, the core hardness is at least about 15 Shore A, preferably about 30 Shore A, as measured in the formed sphere. In another embodiment, the core has a hardness of about 50 Shore A to about 90 Shore D. In yet another embodiment, the core has a hardness of about 80 Shore D or less. Preferably, the core has a hardness of about 30 to about 65 Shore D, more preferably the core has a hardness of about 35 to about 60 Shore D.
The intermediate layer (one or more layers) of the present invention also varies in hardness depending on the specific structure of the ball. In one embodiment, the intermediate layer has a hardness of about 30 Shore D or greater. In another embodiment, the intermediate layer has a hardness of about 90 Shore D or less, preferably about 80 Shore D or less, more preferably about 70 Shore D or less. In yet another embodiment, the intermediate layer has a hardness of about 50 Shore D or greater, preferably about 55 Shore D or greater. In one embodiment, the interlayer hardness is from about 55 Shore D to about 65 Shore D. The intermediate layer can also be about 65 Shore D or greater.

If it is desired that the intermediate layer be harder than the core layer, the ratio of intermediate layer hardness to core hardness is preferably about 2 or less. In one embodiment, the ratio is about 1.8 or less. In yet another embodiment, the ratio is about 1.3 or less.
As with the core and intermediate layer, the cover hardness can vary depending on the structure and desired properties of the golf ball. The ratio of cover hardness to internal ball hardness is a fundamental variable factor for adjusting the aerodynamics of the ball, especially the spin of the ball. In general, the harder the inner ball, the greater the driver spin, and the softer the cover, the greater the driver spin.
For example, if the intermediate layer is intended to be the hardest point in the ball, e.g., about 50 Shore D to about 75 Shore D, the cover material is about 20 Shore D or more, preferably about 20 when measured on a slab. It has a hardness of 25 Shore D or greater, more preferably about 30 Shore D or greater. In another embodiment, the cover itself has a hardness of about 30 Shore D or greater. In particular, the cover can be from about 30 Shore D to about 70 Shore D. In one embodiment, the cover has a hardness of about 40 Shore D to about 65 Shore D, and in another embodiment, about 40 Shore D to about 55 Shore D. In another aspect of the invention, the cover has a hardness of less than about 45 Shore D, preferably less than about 40 Shore D, more preferably from about 25 Shore D to about 40 Shore D. In one embodiment, the cover has a hardness of about 30 Shore D to about 40 Shore D.

In this embodiment, if the outer cover layer is softer than the intermediate layer or inner cover layer, the ratio of the Shore D hardness of the outer cover material to the intermediate layer material is about 0.8 or less, preferably about 0.75 or less, more preferably Is about 0.7 or less. In another embodiment, the ratio is about 0.5 or less, preferably about 0.45 or less.
In yet another embodiment, the ratio is about 0.1 or less when the cover and the interlayer material have a hardness that is substantially the same. If the different hardness between the cover layer and the intermediate layer is not intended to be significant, the cover can have a hardness of about 55 Shore D to about 65 Shore D. In this embodiment, the outer cover to intermediate layer Shore D hardness ratio is about 1.0 or less, preferably about 0.9 or less.
The cover hardness can also be defined from the point of Shore C. For example, the cover has a hardness of about 70 Shore C or higher, preferably about 80 Shore C or higher. In another embodiment, the cover has a hardness of about 95 Shore C or less, preferably about 90 Shore C or less.

In another embodiment, the cover layer is harder than the intermediate layer. In this design, the ratio of the Shore D hardness of the cover layer to the intermediate layer is about 1.33 or less, preferably about 1.14 or less.
When building a two-piece ball, the core may be softer than the outer cover. For example, the core hardness can range from about 30 Shore D to about 50 Shore D, and the cover hardness can be from about 50 Shore D to about 80 Shore D. In this type of structure, the ratio between cover hardness and core hardness is preferably about 1.75 or less. In another embodiment, the ratio is about 1.55 or less. Depending on the material, for example, if the composition of the present invention is acid functionalized and the acid groups are at least partially neutralized, the cover to core hardness ratio is preferably about 1.25 or less.

The compression value depends on the diameter of the component being measured. The Atti compression of a golf ball core or part of a core made in accordance with the present invention is preferably less than about 80, more preferably less than about 75. As used herein, the term “Atti compression” or “compression” contrasts with the deflection of the calibration spring as measured by the Atti Compression Gauge, commercially available from Atti Engineering, Union City, NJ. Defined as the deflection of the target object or material. Atti compression is typically used to measure the compression of a golf ball. In another embodiment, the core compression is from about 40 to about 80, preferably from about 50 to about 70. In yet another embodiment, the core compression is preferably less than about 50, more preferably less than about 25.
In another low compression embodiment, the core has a compression of less than about 20, more preferably less than about 10, and most preferably zero. However, as is known to those skilled in the art, a core formed in accordance with the present invention may be below the Atti Compression Gauge measurement.
The core of the present invention also has a Soft Center Deflection Index (SCDI) compression of less than about 160, preferably from about 40 to about 160, and most preferably from about 60 to about 120.
In one embodiment, the golf ball of the present invention has an Atti compression of about 55 or greater, preferably about 60 to about 120. In another embodiment, the Atti compression of the golf ball of the present invention is at least about 40, preferably about 50-120, more preferably about 60-100. In yet another embodiment, the golf ball of the present invention has a compression of about 75 or more and about 95 or less. For example, preferred golf balls of the present invention can have a compression of about 80 to about 95.

Initial speed and COR
Although there is currently no USGA regulation on golf ball COR, the initial velocity of a golf ball cannot exceed 250 ± 5 ft / s (76.2 ± 1.524 m / s). That is, in one embodiment, the initial velocity is about 245 ft / s (about 74.7 m / sec) or more, about 255 ft / s (77.7 m / sec) or more. In another embodiment, the initial speed is about 250 ft / s (about 76.2 m / sec) or greater. In one embodiment, the initial velocity is from about 253 ft / s (about 77.1 m / sec) to about 254 ft / s (about 77.4 m / sec). In yet another embodiment, the initial velocity is about 255 ft / s (about 77.7 m / sec). Although current regulations on initial speed require golf ball manufacturers to remain within the above regulations, those skilled in the art will readily recognize that the golf ball of the present invention is a golf ball having an initial speed outside the above range. You will recognize that it can be replaced.

As a result of the initial speed regulation set forth by the USGA, the objective is to minimize the COR without violating the 255 ft / s limit described above. The ball's COR is measured by taking the ratio of outbound or rebound speed to income or inbound speed. In one-piece solid golf balls, the COR depends on various characteristics of the ball such as composition and hardness. For a given composition, the COR generally increases with increasing altitude. In two-piece solid golf balls, such as the core and cover, one purpose of the cover is to produce a COR acquisition that exceeds the core COR acquisition. If the core's contribution to the high COR is substantial, the cover will only require a small contribution. Similarly, if the cover contributes substantially to the high COR of the ball, only a small contribution is required from the core.
The present invention contemplates a golf ball having a COR of about 0.700 to about 0.850 at an inbound speed of about 125 ft / s (about 38.1 m / sec). In one embodiment, the COR is about 0.750 or more, preferably about 0.780 or more. In another embodiment, the ball has a COR of about 0.800 or greater. In yet another embodiment, the COR of the ball of the present invention is from about 0.800 to about 0.815.
In addition, the inner ball also preferably has a COR of about 0.780 or greater. In one embodiment, the COR is about 0.790 or greater.

Spin Speed As is known to those skilled in the art, the spin speed of a golf ball varies depending on the golf ball structure. In multi-layer balls, such as the core, intermediate layer and cover, where the cover is formed from the polyurea or polyurethane composition of the present invention, the spin rate of the ball away from the driver ("driver spin rate") is preferably about More than 2700 rpm. In one embodiment, the driver spin speed is from about 2800 rpm to about 3500 rpm. In another embodiment, the driver spin speed is from about 2900 rpm to about 3400 rpm. In yet another embodiment, the driver spin speed is less than about 2700 rpm.
A two-piece ball made in accordance with the present invention may also have a driver spin speed of 2700 rpm or higher. In one embodiment, the driver spin speed is from about 2700 rpm to about 3300 rpm. A wound ball made in accordance with the present invention may have a similar spin rate.
Those skilled in the art should understand how to measure the spin rate. Examples of methods for measuring spin rate are disclosed in US Pat. Nos. 6,500,073, 6,488,591, 6,286,364, and 6,241,622, which are hereby incorporated by reference in their entirety.

Flexural Modulus Accordingly, the golf ball of the present invention preferably has an intermediate layer having a flexural modulus of about 500 psi to about 500,000 psi (about 3.447 × 10 ³ kPa to about 3.447 × 10 ⁶ kPa). More preferably, the flexural modulus of the intermediate layer is from about 1,000 psi to about 250,000 psi (about 6.895 × 10 ³ kPa to about 1.724 × 10 ⁶ kPa). Most preferably, the flexural modulus of the intermediate layer is from about 2,000 psi to about 200,000 psi (about 1.379 × 10 ⁴ kPa to about 1.379 × 10 ⁶ kPa).
The flexural modulus of the cover layer is preferably about 2,000 psi (about 1.379 × 10 ⁴ kPa) or more, more preferably about 5,000 psi (about 3.447 × 10 ⁴ kPa) or more. In one embodiment, the cover has a flexural modulus of about 10,000 psi to about 150,000 psi (about 6.895 × 10 ⁴ kPa to about 1.034 × 10 ⁶ kPa). More preferably, the flexural modulus of the cover layer is about 15,000psi~ about 120,000 (about 1.034 × 10 ⁵ kPa to about 8.274 × 10 ⁵ kPa). Most preferably, the flexural modulus of the cover layer is about 18,000psi~ about 110,000 psi (about 1.241 × 10 ⁵ kPa to about 7.584 × 10 ⁵ kPa). In another embodiment, the cover layer has a flexural modulus of about 100,000 psi (about 6.895 × 10 ⁵ kPa) or less, preferably about 80,000 psi (about 5.516 × 10 ⁵ kPa) or less, more preferably about 70,000 psi. (About 4.826 × 10 ⁵ kPa) or less. For example, the flexural modulus of the cover layer is about 10,000 psi to about 70,000 psi (about 6.895 × 10 ⁴ kPa to about 4.826 × 10 ⁵ kPa), about 12,000 psi to about 60,000 psi (about 8.274 × 10 ⁴ kPa to about 4.137). × 10 ⁵ kPa), or about 14,000 psi to about 50,000 psi (about 9.653 × 10 ⁴ kPa to about 3.447 × 10 ⁵ kPa).

In one embodiment, when the cover layer has a hardness of about 50 Shore D to about 60 Shore D, the cover layer is preferably about 55,000 psi to about 65,000 psi (about 3.792 × 10 ⁵ kPa to about 4.482 × 10 ^It has a flexural modulus of ⁵ kPa).
In one embodiment, the ratio of flexural modulus of the intermediate layer to the cover layer is from about 0.003 to about 50. In another embodiment, the flexural modulus ratio of the intermediate layer to the cover layer is from about 0.006 to about 4.5. In yet another embodiment, the ratio of flexural modulus of the intermediate layer to the cover layer is from about 0.11 to about 4.5.
In one embodiment, the compositions of the present invention are used in golf balls having multiple cover layers that have essentially the same hardness but differ in flexural modulus. In this aspect of the invention, the difference between the flexural moduli of the two cover layers is preferably about 5,000 psi (about 3.447 × 10 ⁴ kPa) or less. In another embodiment, the difference in flexural modulus is about 500 psi (about 3.447 × 10 ³ kPa) or greater. In yet another embodiment, the difference in flexural modulus between two layers reinforced with at least one layer is between about 500 psi and about 10,000 psi (about 3.447 × 10 ³ kPa to about 6.895 × 10 ⁴ kPa). About 500 psi to about 5,000 psi (about 3.447 × 10 ³ kPa to about 3.447 × 10 ⁴ kPa). In one embodiment, the difference in flexural modulus between two cover layers formed from unreinforced or unmodified material is about 1,000 to about 2,500 (about 6.894 × 10 ³ kPa to about 1.724 × 10 ⁴ kPa). is there.

The specific gravity of the specific gravity cover or intermediate layer is preferably at least about 0.7. In one embodiment, the specific gravity of the intermediate layer or cover is about 0.8 or higher, preferably about 0.9 or higher. For example, in one embodiment, a golf ball has an intermediate layer having a specific gravity of about 0.9 or greater and a cover having a specific gravity of about 0.95 or greater. In another embodiment, the intermediate layer or cover has a specific gravity of about 1.00 or greater. In yet another embodiment, the intermediate layer or cover has a specific gravity of about 1.05, preferably about 1.10 or greater.
The cover may have a specific gravity of about 1.00 or higher, preferably 1.05 or higher. For example, the golf ball of the present invention may have a core having a specific gravity of about 1.10 or higher and a cover having a specific gravity of about 0.95 or higher.

Bond i.e. peel strength of polyurethane and polyurea compositions of the bonding strength present invention is preferably about 5 lb _f / in (about 0.565 N / m) or more. In one embodiment, the adhesive strength is less than or equal to about 25 lb _f / in (about 2.825 N / m). For example, the adhesive strength is preferably about 10 lb _f / in (about 1.130 N / m) or more at about 20 lb _f / in (about 2.260 N / m) or less. In another embodiment, the adhesive strength is about 20 lb _f / in (about 2.260 N / m) or greater, preferably about 24 lb _f / in (about 2.712 N / m) or more. In yet another embodiment, the adhesive strength is about 26 lb _f / in (about 2.938 N / m) or more. In yet another embodiment, the adhesive strength is about 20 lb _f / in~ about 30 lb _f / in (about 2.260 N / m to about 3.390 N / m).
A skilled engineer knows how to measure the bond strength. For example, the cross hatch test and the repeated ball impact test are useful for measuring the adhesion strength of a specific layer of a golf ball. The cross-hatch test consists of cutting the material perpendicularly to each other into small pieces, applying an adhesive cellophane tape piece over the material, rapidly peeling the tape, and counting the number of pieces removed. The repeated impact test consists of subjecting the final golf ball to repeated impacts and visually inspecting the coating film for peeling from the golf ball. Examples of these methods are presented in US Pat. No. 5,316,730, which is hereby incorporated by reference.

Water Resistance The water resistance of a golf ball portion formed from the composition of the present invention can be expressed in terms of weight gain over time. For example, the change in mass of a golf ball part monitored over 7 weeks at 100% relative humidity and 72 ° F. (22.2 ° C.) helps to demonstrate which ball has good water resistance. In one embodiment, the golf ball portion of the present invention has a mass gain of about 0.15 grams or less after 7 weeks. In another embodiment, the golf ball of the present invention has a mass gain of about 0.13 grams or less after a 7 week storage period. In yet another embodiment, the weight gain of the golf balls of the present invention is less than about 0.09 grams after 7 weeks. In yet another embodiment, the mass gain is about 0.06 grams or less after 7 weeks. The golf balls of the present invention preferably have a mass gain of no more than about 0.03 grams over a 7 week storage period.
Size increase can also be used as an indicator of water resistance. That is, the more moisture the golf ball takes in, the larger the golf ball becomes due to the moisture enclosed under the outermost layer of the golf ball portion. Thus, the golf ball of the present invention preferably has no appreciable size increase. In one embodiment, the golf ball size increase after 7 weeks of the present invention is about 0.001 inch (25.4 microns) or less.

Shear / Cut Resistance The cut resistance of a golf ball cover can be measured using a shear test having a scale of 1-9 to assess breakage and appearance. In one embodiment, the failure rating is preferably about 3 or less, more preferably about 2 or less. In another embodiment, the degradation grade is about 1 or less. The appearance grade of the golf ball of the present invention is preferably about 3 or less. In one embodiment, the appearance grade is about 2 or less, preferably about 1 or less.
The light stability of the light-stable cover can be quantified by the yellowness index difference (ΔYI), ie the yellowness measured after a given exposure time minus the yellowness before storm. In one embodiment, ΔYI is about 10 or less after 5 days (120 hours) of exposure, preferably about 6 or less after 5 days of exposure, more preferably about 4 or less after 5 days of exposure. In one embodiment, ΔYI is about 2 or less after 5 days of exposure, preferably about 1 or less after 5 days of exposure. b Difference in chromaticity range (Δb *, yellow to blue) is also one method for quantifying the light stability of the cover. In one embodiment, Δb * is about 4 or less after 5 days (120 hours) of exposure, preferably about 3 or less after 5 days of exposure, more preferably about 2 or less after 5 days of exposure. is there. In one embodiment, Δb * is about 1 or less after 5 days of exposure.

  The following non-limiting examples are merely illustrative of preferred embodiments of the invention and are not to be construed as limiting the scope defined in the invention and the claims. Parts are by mass unless otherwise noted.

Saturated Polyurethane Golf Ball Cover Table 3 illustrates the components used to prepare the saturated polyurethane golf ball cover composition.

*プレポリマーは、4,4'-ジシクロヘキシルメタンジイソシアネートとポリテトラメチレンエーテルグリコールとの反応生成物である。
** HCC-19584は、PolyOne Corporation社(前Harwick Chemical Corporation社)製の白色-青色カラー分散物。
上記組成物から形成させたカバーを有するゴルフボールを、米国特許第5,733,428号の教示に従い製造した。物性およびボール性能を表４に示す。

* Prepolymer is the reaction product of 4,4'-dicyclohexylmethane diisocyanate and polytetramethylene ether glycol.
** HCC-19584 is a white-blue color dispersion manufactured by PolyOne Corporation (formerly Harwick Chemical Corporation).
A golf ball having a cover formed from the above composition was made according to the teachings of US Pat. No. 5,733,428. Table 4 shows the physical properties and ball performance.

表４に示す上記組成物からの成型ボールを下記に述べるようなQUV試験にさらに供した。

Molded balls from the above compositions shown in Table 4 were further subjected to a QUV test as described below.

Method
ASTM G53-88 “Standard Practice for Operating Light and Water-Exposure Apparatus (Fluorescent UV-Condensation Type) for Exposure of Nonmetallic Materials” was reworked with some modifications:
Six different balls for evaluation were placed in a custom-made golf ball holder and inserted into a sample rack of a Q-Panel model OUV / SER accelerated weathering tester manufactured by Q-Panel Lab Productd of Cleveland, Ohio. Each sample holder was constructed so that each ball was approximately 1.75 inches (4.445 cm) from the UVA-340 bulb at its closest point. The weathering tester was then cycled every 4 hours between the following two groups of conditions (specific time lengths of 24 hours, 48 hours and 120 hours):
Condition # 1: A water bath temperature of about 50 ° C. with a UV lamp set to ON and adjusted to an irradiation output of 1.00 W / m ² / nm.
Condition # 2: Water bath temperature of about 40 ° C with UV lamp off.
Color was measured using a BYK-Gardner Model TCS II sphere-type spectrophotometer with a 25-mm port before weathering and after each time cycle. D65 / 10 ° illuminance was used in the specular reflection containing mode.
The test results for molded balls 24 hours after UB exposure are shown in Table 5, where ΔL * is equal to the L range difference (bright to dark); Δa * is the a chromaticity range difference (red to Δb * is equal to b chromaticity range difference (yellow to blue); ΔC * is equal to the combined chromaticity difference (a * and b * scale), hue and saturation; ΔH * is ΔE * is equal to the total hue difference; ΔWI is equal to the whiteness index difference; ΔYI is the yellowness index difference, excluding the saturation and luminescence effects.

Table 6 shows the test results for the molded balls after 48 hours of UV exposure.

Table 7 shows the test results for the molded balls after 120 hours of UV exposure.

H ₁₂ MDI polyether urea cured with diol
A golf ball having a cover formed from a composition cured with 1,4-butanediol containing a prepolymer prepared from H ₁₂ MDI and a polyoxyalkylene having a molecular weight of about 2000 was prepared. Table 8 shows the physical properties and ball performance results. The same light stable aliphatic polyurethane golf ball as in Example 1 was used for comparison purposes.

*剪断試験の格付け：１〜9の尺度による、１が最良、９が最悪

* Shear test rating: 1 to 9 on a scale of 1-9, 9 is worst

H ₁₂ MDI polyether urea cured with a diamine
Formed from a composition cured with 4,4'-bis- (sec-butylamino) -dicyclohexylmethane (Clearlink 1000), containing a prepolymer prepared from H ₁₂ MDI and polyoxyalkylene having a molecular weight of about 2000 A golf ball having a covered cover was produced. Table 9 shows the physical properties and ball performance results. The same light stable aliphatic polyurethane golf ball as in Example 1 was used for comparison purposes.

*剪断試験の格付け：１〜9の尺度による、１が最良、９が最悪

* Shear test rating: 1 to 9 on a scale of 1-9, 9 is worst

H ₁₂ MDI amine-terminated compound urea cured with a diamine
Contains prepolymers prepared from H ₁₂ MDI and amine-terminated compounds such as amine-terminated polybutadiene and cured with N, N′-diisopropyl-isophoronediamine (JEFFLINK® 754 available from Huntsman Corporation) Golf balls according to the present invention having a cover formed from the composition can be produced. Table 9 shows the physical properties and ball performance results. A light stable aliphatic polyurethane reference golf ball similar to Example 1 can be used for comparison purposes. The golf balls of the present invention preferably have good breakage and appearance ratings, as well as improved light stability after a 5-day QUV test when compared to the control balls, while still maintaining a high COR. .

Moisture Resistance of the Golf Ball of the Invention The moisture resistance of the golf ball of the invention was measured relative to a control golf ball. The golf ball cover of the present invention comprises a prepolymer of MDI and a hydroxy-terminated polybutadiene prepolymer and is 4,4-bis- (sec-butylamino) diphenylmethane (UNILINK® 4200 available from Huntsman Corporation). Formed from the composition cured in
The cover was molded on a 1.580 inch (4.0132 cm) wrapping ball and finished by ordinary coating. Each ball was incubated for 1 week in an environmental room at 50% relative humidity and 72 ° F. (22.2 ° C.), then weighed and measured. Thereafter, the golf balls of the present invention thus conditioned were subjected to an environmental chamber of 100% relative humidity and 72 ° F. (22.2 ° C.). Mass and size changes were monitored over 7 weeks. The test results are shown in the table below (Tables 10 and 11) and graphically in FIGS.

Water Resistant Polyurea Cover Golf Ball Golf balls can be made according to the present invention using a cover formed from a solid core, an intermediate layer, and a water resistant polyurea composition. In particular, the cover may be formed from the reaction product of a polyurea prepolymer and a curing agent.
The polyurea prepolymer can be prepared from isocyanates such as H ₁₂ MDI and amine-terminated compounds having a hydrophobic backbone, such as amine-terminated polybutadiene. Curing agents are 4,4′-bis- (sec-butylamino) dicyclohexylmethane (UNILINK® 4200 available from Huntsman Corporation), N, N′-diisopropyl-isophoronediamine (obtained from Huntsman Corporation) Secondary diamines such as JEFFLINK® 754), or mixtures thereof.
The control ball preferably uses the same core and interlayer material, but uses a polyurethane composition comprising a polyol that does not have a hydrophobic backbone. Both the golf ball of the present invention and the control golf ball can be incubated for 1 week in an environmental room at 50% relative humidity and 72 ° F. (22.2 ° C.) and then weighed and measured. These balls can then be subjected to an environmental chamber at 100% relative humidity and 72 ° F. (22.2 ° C.). Mass and size changes can be monitored over 7 weeks.
The water resistant polyurea cover golf ball has good water resistance when compared to the control ball. For example, a golf ball of the present invention may have a mass gain after about 7 weeks that is about 75% less than the control golf ball, preferably about 80% less than the control ball. Similarly, the golf balls of the present invention preferably do not show an increase in size after 7 weeks, whereas the control golf ball shows an increase in size of 0.001 inch (25.4 μm) as shown in Example 5, Table 11. Have.

  The invention described and claimed herein is not to be limited in scope by the specific embodiments disclosed herein. This is because these embodiments are intended as illustrations of some aspects of the present invention. Any equivalent embodiment may be contemplated within the scope of the present invention. For example, the compositions of the present invention may also be used in golf equipment such as putter inserts, golf grab heads and parts thereof, golf shoe parts, and golf bag parts. Indeed, various modifications of the invention in addition to those shown and described herein will be apparent to those skilled in the art from the foregoing description. Such modifications are also within the scope of the claims. All patents and patent applications cited above are incorporated herein by reference for purposes of illustration.

1 is a cross-sectional view of a two-piece golf ball in which a cover is formed from a composition comprising at least one polyurea. 1 is a cross-sectional view of a multi-component golf ball in which at least one cover is formed from a composition that includes at least one polyurea. 1 is a cross-sectional view of a multi-component golf ball in which a cover is formed from a composition that includes at least one polyurea and an intermediate layer is formed from a composition that includes at least one ionomer resin. 1 is a cross-sectional view of a multi-component golf ball that includes a core and a cover, wherein the core is surrounded by a tensile elastomeric material and the cover is formed from a composition that includes at least one polyurea. 1 is a cross-sectional view of a liquid center golf ball in which a liquid core is surrounded by a tensioned elastomeric material and a cover is formed from a composition that includes at least one polyurea. A cross-sectional view of a multi-component golf ball comprising a core, a thin inner cover layer, and a thin outer cover layer disposed on the inner cover layer, wherein the cover is formed from a composition comprising at least one polyurea. It is. A multi-component golf comprising a core, an outer core layer, a thin inner cover layer, and a thin outer cover layer disposed on the inner cover layer, wherein the cover is formed from a composition comprising at least one polyurea It is sectional drawing of a ball | bowl. 1 is a cross-sectional view of a multi-component golf ball that includes a large core and a thin outer cover layer disposed thereon, the cover being formed from a composition that includes at least one polyurea. 6 is a graph showing the change in mass of a golf ball subjected to temperature and humidity controlled over a specific amount of time. 6 is a graph showing the change in size of a golf ball subjected to temperature and humidity controlled over a specific amount of time.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Golf ball 2 Core 3 Cover 11 Golf ball 12 Core 13 Cover 14 Intermediate layer 21 Golf ball 22 Core 23 Cover 24 Intermediate layer 31 Golf ball 32 Core layer 33 Cover 34 Intermediate layer 41 Liquid center golf ball 42 Hollow spherical core shell 43 Liquid 44 Thread rubber 45 Cover 51 Golf ball 52 Core 53 Outer cover layer 54 Inner cover layer 61 Golf ball 62 Core 63 Outer cover layer 64 Inner cover layer 65 Outer core layer 71 Golf ball 72 Large core 72 Outer cover layer

Claims (21)

A golf ball comprising a core and a cover, wherein at least a portion of the golf ball is formed from a water resistant polyurea composition comprising a polyurea prepolymer and a curing agent , wherein the polyurea prepolymer comprises an isocyanate and A golf ball comprising a reaction product with an amine-terminated compound containing a hydrophobic main chain. The golf ball of claim 1, wherein the amine-terminated compound comprises at least one of an unsaturated amine-terminated hydrocarbon, a saturated amine-terminated hydrocarbon, or a mixture thereof. The golf ball of claim 1, wherein the curing agent is selected from the group consisting of a hydroxy terminal curing agent, an amine terminal curing agent, and a mixture thereof. The golf ball according to claim 1, wherein the curing agent is selected from the group consisting of a primary diamine curing agent, a secondary diamine curing agent, triamines, and a mixture thereof. The golf ball of claim 1, wherein the amine terminal curing agent is a secondary diamine curing agent. The golf ball of claim 1, wherein the golf ball has a mass gain of 0.15 grams or less after 7 weeks storage at 72 ° F. (22.2 ° C.) in 100% humidity. The golf ball of claim 1, wherein the golf ball has a mass gain of 0.09 grams or less after 7 weeks storage at 72 ° F. (22.2 ° C.) in 100% humidity. The golf ball according to claim 1, wherein the water-resistant polyurea composition comprises a urea bond. The golf ball of claim 1, wherein the water resistant polyurea composition further comprises at least one density adjusting filler. A core having a diameter of 1.55 inches (3.937 cm) or greater; an intermediate layer placed around the core to form a center; and 0.02 inches to 0.035 inches (0.508 mm to 0.889 mm) placed around the center includes a cover having a thickness, the cover is seen containing a water-resistant polyurea composition comprising a polyurea prepolymer and a curing agent, wherein the polyurea prepolymer, amine-terminated compound comprising a hydrophobic backbone of at least one And a reaction product of at least one isocyanate with a golf ball. The golf ball of claim 10, wherein the amine-terminated compound comprises at least one amine-terminated hydrocarbon. The golf ball according to claim 10, wherein the cover has a first hardness, and the intermediate layer has a second hardness greater than the first hardness. The golf ball according to claim 12, wherein the first hardness is 40 Shore D to 55 Shore D, and the second hardness is 60 Shore D or more. The golf ball according to claim 10, wherein the core includes a first layer and a second layer. The golf ball according to claim 10, wherein the core hardness is 60 Shore D or less. The golf ball of claim 10, wherein the golf ball has a mass gain of no more than 0.05 grams after 7 weeks storage at 72 ° F. (22.2 ° C.) in 100% humidity. A golf ball comprising a water resistant polyurea composition comprising a polyurea prepolymer and a curing agent , wherein the polyurea prepolymer comprises at least one amine-terminated compound comprising at least one hydrophobic backbone and an isocyanate. Formed from a reaction product, the golf ball has a mass increase of less than 0.15 grams and a size increase of less than 0.001 inches (25.4 microns) after 7 weeks storage at 72 ° F. (22.2 ° C.) in 100% humidity. A featured golf ball. The curing agent is ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine; 4,4′-bis. -(sec-butylamino) -dicyclohexylmethane and its derivatives; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (sec-butylamino) -cyclohexane; 4,4'-dicyclohexyl 1,4-cyclohexane-bis- (methylamine); 1,3-cyclohexane-bis- (methylamine); diethylene glycol bis- (aminopropyl) ether; 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine Triethylenetetramine; tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamino; Imide-bis-propylamine; monoethanolamine; diethanolamine; triethanolamine; monoisopropanolamine; diisopropanolamine; isophoronediamine; 4,4'-methylenebis- (2-chloroaniline); 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'-dialkyl Amino-diphenylmethane; trimethylene glycol-di-p-aminobenzoate; polytetramethylene oxide-di-p-aminobenzoate; 4,4'-methylenebis- (3-chloro-2,6-diethyleneaniline); '-Mech Bis- (2,6-diethylaniline); meta-phenylenediamine; paraphenylenediamine; cyclohexyldimetol; N, N'-diisopropyl-isophoronediamine;polyoxypropylenediamine; propylene oxide triamine; 3,3'-dimethyl The golf ball of claim 17 , selected from the group consisting of: -4,4′-diaminocyclohexylmethane; and mixtures thereof. The golf ball of claim 17, wherein the golf ball has a polybutadiene core. The polyurea prepolymer has the following general formula:

(Wherein x is 1 or greater; R and R ₁ are straight or branched hydrocarbon chains having 1 to 20 carbons)
The golf ball of claim 1, 10 or 17, comprising a bond having The water resistant polyurea composition has the following general formula:

(Wherein x is 1 or more; R and R ₁ are straight or branched hydrocarbon chains having 1 to 20 carbons)
21. A golf ball according to claim 1, 10, 17 or 20, comprising a bond having:

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