JP3964843B2 - Golf ball containing light-stable substance and method for producing the same - Google Patents

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part application of U.S. patent application Ser. No. 09 / 466,434 which is a currently pending December 17, 1999 application is currently pending, 2001, September 13 This is a continuation-in-part of US patent application Ser. No. 09 / 951,963, filed Aug. 6, 2002, and claims the priority of US provisional application No. 60 / 401,047 filed on Aug. 6, 2002. The entire disclosure of which is incorporated herein by reference to these applications.
TECHNICAL FIELD OF THE INVENTION The present invention relates to golf equipment comprising a polyurea composition. In particular, the present invention is directed to a golf equipment including a composition produced by crosslinking a polyurea prepolymer of polyetheramine and isocyanate with a curing agent, and a method for producing the same. Preferably, the components of the composition are saturated, i.e. substantially free of unsaturated carbon-carbon bonds or aromatic groups, to produce a light stable composition.

Golf equipment, i.e. clubs and balls, are manufactured from various compositions. For example, golf ball covers are manufactured from a variety of materials including balata and ionomer resins. Balata is a natural or synthetic trans-polyisoprene rubber. Balla-covered balls are preferred by golfers who are skilled in many techniques, because the cover is soft, which allows the player to more accurately control the direction and distance of the ball, especially for short shots. This is because a sufficient rotational speed can be achieved. However, balls covered with balata are easily damaged and thus lack the durability required by average golfers. Accordingly, cover compositions that replace balata have been developed with the intention of giving the ball a rotational speed and sensation close to that of a ball covered with balata, while also providing higher durability and overall flight distance. It was.
Ionomer resins have replaced balata as a cover material to a considerable extent. Chemically, the ionomer resin is an α, β-ethylenically unsaturated compound in which 10 to 90% of carboxylic acid groups are neutralized with metal ions as disclosed in US Pat. No. 3,264,272. It is a copolymer of carboxylic acid and olefin. Commercially available ionomer resins include, for example, copolymers of methacrylic acid or acrylic acid and ethylene neutralized with metal ions. Examples of commercially available ionomer resins include but are not limited to: DuPont de Neumours SURLYN®, and Exxon ESCOR® and IOTEK® Trademark). 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 are all golf ball covers It relates to the one using the composition of SURLYN (registered trademark) type. However, as described in the previous patent, the golf ball covered with SURLYN (registered trademark) actually has a cut-resistant cover, and has a rotation and a feeling compared with the ball covered with balata. Inferior.
Since around 1960, polyurethane has also been recognized as a useful material for golf ball covers. U.S. Pat. No. 3,147,324 is directed to a method of manufacturing a golf ball having a polyurethane cover. The resulting golf ball is durable, while at the same time maintaining the “feel” of the balata ball.
Many companies are studying the usefulness of polyurethane as a cover material for golf balls. U.S. Pat. No. 4,123,061 teaches golf balls made from polyurethane prepolymers made from polyethers having diisocyanates that are cured by either polyols or amine-type curing agents. US Pat. No. 5,334,673 discloses two commercially available polyurethanes for making golf ball covers, namely thermoset and thermoplastic polyurethanes, in particular polyurethane prepolymers and retarders. A golf ball covered with a thermosetting polyurethane made from a composition of reactive amine curing agent and / or bifunctional glycol is disclosed.

Unlike a golf ball covered with SURLYN (registered trademark), it is possible to have a soft “feel” of a golf ball covered with balata by disposing a polyurethane golf ball cover. However, golf ball covers made from polyurethane are currently not completely comparable to SURLYN® golf balls with respect to the resilience and rebound of the golf ball cover, which is It is a function of the initial velocity of the golf ball.
In addition, because the polyurethanes used to make these golf ball covers generally contain aromatic components such as aromatic diisocyanates, polyols or polyamines, they are exposed to light, particularly ultraviolet (UV) light. It is believed to fade. Light and UV stabilizers such as Tinuvin 770, 765 and 328 are added to these aromatic polymer materials to retard the fade. However, to ensure that the cover made from aromatic polyurethane does not show a fading color, the cover is painted with a white paint and then covered with a clear coating to maintain the white color of the golf ball. Applying a coating containing a non-uniform white pigment to the surface of a golf ball having dimples is a difficult process, which adds time and expense to the manufacture of the golf ball.

  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 the reaction product of an organic diisocyanate and an organic amine, both having at least two functional groups. Combining these two components forms a polyurea, thus limiting the possibility of changing the physical properties of the composition. Like polyurethane, polyurea is not completely comparable to SURLYN® golf balls in the resilience or rebound or braking action of golf ball covers.

  Thus, sustained golf equipment having a soft component that provides improved resilience, increased cut, scratch and peel resistance, and enhanced adhesion without adversely affecting the overall operational characteristics of the golf ball. There is a request. In addition, it would be advantageous to provide a composition that combines cut and scratch resistance with fade resistance, which is appropriate for golf balls and other golf-related equipment.

The present invention is directed to golf equipment having at least one portion made from a polyurea composition. In one aspect, the present invention is directed to a one-piece golf ball comprising polyurea. In another embodiment, the compositions of the present invention are used in two-piece and multicomponent, including three-piece, four-piece golf balls, comprising at least one cover layer and a core, wherein at least one cover layer is at least one polyurea. In a multi-component golf ball comprising a core and / or a cover having two or more layers, at least one of these layers is made from at least one polyurea.
More particularly, in a first aspect, the present invention is directed to a golf ball comprising at least one cover and at least one core layer, wherein the cover is a diisocyanate and polyetheramine cured with a curing agent. Made from a composition comprising at least one polyurea composition made from a polyurea prepolymer.
The present invention is further directed, in the second aspect, 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 is a curing agent. Made from a composition comprising a diisocyanate cured with a polyurea prepolymer of polyetheramine.

The present invention is further directed, in the third aspect, 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 Both are made from a composition comprising a diisocyanate cured with a curing agent and a polyurea prepolymer of polyetheramine.
In embodiments of the golf ball cover of the present invention, the polyurea preferably comprises from about 1 to about 100 weight percent cover and, if present, the remainder of the cover, the cover being one or more compatible materials known to those skilled in the art. Contains a polymer having rebound resilience.
The present invention is further directed to a golf ball comprising at least one light-stable cover layer made from a composition comprising at least one polyurea made from a polyurea prepolymer and a curing agent. In some embodiments, the polyurea prepolymer comprises at least one diisocyanate and at least one polyetheramine.

  In the context of the present invention, the diisocyanate is saturated and is selected from the group consisting of: ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene diisocyanate; tetramethylene-1, 4-diisocyanate; 1,6-hexamethylene-diisocyanate; octamethylene diisocyanate; decamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexa Methylene diisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate Cyclohexane-1,4-diiso Anato; methyl-cyclohexylene 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-isocyanatomethylcyclohexane; isocyanate ethylcyclohexane isocyanate; bis (isocyanate methyl) ) -Cyclohexane diisocyanate; 4,4′-bis (isocyanatomethyl) dicyclohexane; 2,4′-bis (isocyanatomethyl) dicyclohexane; isophorone diisocyanate; HDI Triisocyanate; triisocyanate of 2,2,4-trimethyl-1,6-hexanediisocyanate; 4,4′-dicyclohexylmethane diisocyanate; 2,4-hexahydrotoluene diisocyanate; Hexahydrotoluene diisocyanate; and mixtures thereof. 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 other embodiments, the diisocyanate is an araliphatic isocyanate and is selected from the group consisting of: meta-tetramethylxylene diisocyanate; para-tetramethylxylene diisocyanate; trimerization of polyisocyanate Diisocyanates of polyisocyanates; modified polyisocyanates; and mixtures thereof.
The polyether amine can be selected from the group consisting of: polytetramethylene ether diamine, polyoxypropylene diamine, poly (oxypropylene terminated ethylene oxide) ether diamine, triethylene glycol diamine, propylene oxide based triamine, Trimethylolpropane-based triamine, glycerin-based triamine, and mixtures thereof. In some embodiments, the polyetheramine has a molecular weight of about 1000 to 3000.
The curing agent can be selected from the group consisting of: hydroxy-terminated curing agents, amine-terminated curing agents, and mixtures thereof, preferably having a molecular weight of about 250-3900.

  In some embodiments, the hydroxy-terminated curing agent is selected from the group consisting of: 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; Cyclohexyl dimethylol; triisopropanolamine; tetra- (2-hydroxypropyl) -ethylenediamine; diethylene glycol di- (aminopropyl) ether; 1,5-pentanediol; 1,6-hexanediol; (2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol; 1,3-bis- [2- (2-hydroxyethoxy) ethoxy] cyclohexane; 1,3-bis- {2- [2- (2- Hydroxyethoxy) ethoxy] ethoxy} cyclohexane; trimethylolpropane; preferably polytetramethylene ether glycol having a molecular weight of about 250-3900; and mixtures thereof.

  The amine-terminated curing agent can be selected from the group consisting of: ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; tetrahydroxypropyleneethylenediamine; 2,2,4- and 2,4,4. 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 derivatives; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis- (methylamine); , 3-cyclohexane-bis- (methylamine); diethylene glycol di- (aminopropyl) 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamine; imido-bis-propylamine; Monoethanolamine, diethanolamine; triethanolamine; monoisopropanolamine, diisopropanolamine; isophoronediamine; and mixtures thereof.

In some embodiments, the composition further comprises a catalyst selected from the group consisting of: bismuth catalyst, zinc octoate, di-butyltin dilaurate, di-butyltin diacetate, tin (II) chloride, tin (IV) chloride, di- -Butyltin dimethoxide, dimethyl-bis- [1-oxonedecyl) oxy] tin, di-n-octyltin bis-isooctyl mercaptoacetate, triethylenediamine, triethylamine, tributylamine, oleic acid, acetic acid; delayed catalysts, and these blend. The catalyst can be present from about 0.005% to about 1% by weight of the composition.
In other embodiments, the cover layer has a yellowness difference of about 12 or less after 5 days exposure to ultraviolet light. In yet another aspect, the cover layer has a b color dimension difference of about 6 or less after 5 days exposure to ultraviolet light.
In the aspect of the present invention, the cover layer can be manufactured by casting, injection molding or reaction injection molding.

The present invention is further directed to a golf ball comprising a core, a layer disposed around the core forming the center, and a cover cast into the center, the cover comprising at least one diisocyanate, at least one diisocyanate. A light-stable polyurea material comprising a polyetheramine and at least one of a hydroxy-terminated curing agent, an amine-terminated curing agent or mixtures thereof.
In some embodiments, the layer comprises: ionomer, polyamide, highly neutralized polymer, polyester, polycarbonate, polyimide, polyolefin, acid copolymer, polyurethane, vinyl resin, acrylic resin, polyphenylene oxide resin, metallocene catalyzed polymer. , And mixtures thereof. In other embodiments, the layer is a moisture barrier.
In other embodiments, the cover has a thickness of from about 0.02 inches to about 0.35 inches. Further, the layer preferably has a first Shore D hardness and the cover has a second Shore D hardness, and the ratio of the second Shore D hardness to the first Shore D hardness is about 0.7 or Smaller than that.

The core may comprise polybutadiene and may have a diameter of about 1.55 inches or greater. In some embodiments, the core includes a cis-trans transfer catalyst, a rebound elastic polymer component, and a free radical source. The cis-trans transfer catalyst can include an organic sulfur component, a VIA group component, an inorganic sulfide component, an aromatic organic compound, or a mixture thereof.
In some embodiments, at least one of the core, layer, cover, or combination thereof includes a density adjusting filler.

The present invention further provides the center of goulballs to produce a castable reactive polyurea liquid material by mixing a polyurea prepolymer and at least one curing agent, with one half of the first mold being the first Filling with an amount of material, and after a predetermined first time, sink the center in half of the first set of molds, wherein the second predetermined time center is held in a vacuum and the second predetermined time The time is sufficient to complete the exothermic reaction of the first amount of material, removing the vacuum from the center to provide a partially covered center, and halving the second set of molds to the second Filled with an amount of material, where the first and second amounts are substantially the same, and a second amount of exothermic reaction has begun, partially halving the second set of molds. In this case, the second amount of exothermic reaction is terminated. To, it is directed to a method of manufacturing a golf ball comprising the step.
In some embodiments, the first predetermined time is about 40 seconds to about 100 seconds. In other aspects, the second predetermined time is from about 4 seconds to about 12 seconds.

The polyurea prepolymer comprises at least one diisocyanate and at least one polyetheramine. In some embodiments, the step of mixing the polyurea prepolymer and at least one curing agent further includes mixing at least one triol or at least one tetraol, or a mixture thereof. In other embodiments, the step of mixing the polyurea prepolymer and at least one curing agent further comprises at least one catalyst, at least one light stabilizer, at least one antifoaming agent, at least one acid functionalized moiety, or Mixing these combinations.
In yet another aspect, preparing the golf ball includes preparing a golf ball core and forming a layer disposed about the golf ball core. In other embodiments, the golf ball core includes a polybutadiene reaction product, where the core diameter is equal to or greater than about 1.55 inches and the layer thickness is about 0.0508 cm ( 0.02 inches) to about 0.035 inches.
Additional features and advantages of the present invention can be ascertained from the following detailed description, taken in conjunction with the accompanying drawings.

The present invention contemplates improved compositions for use in golf equipment such as golf balls, golf clubs, and the like. Specifically, the compositions of the present invention are based on polyurea and are included in various golf ball structures, ie, one-piece, two-piece, or multi-layer balls, and golf club members, such as club head inserts.
The compositions of the present invention are preferably light stable or saturated. Light stability can be achieved in various ways for the purposes of the present invention. For example, the compositions of the present invention can contain only saturated components, i.e., saturated prepolymers and saturated curing agents, or light stabilizers to improve light stability when using aromatic compounds. Can be included.

Polyurea Compositions Conventional aromatic polyurethane / urethane elastomers and polyurethane / urea elastomers are generally obtained by curing a diisocyanate and polyol prepolymer with at least one diol curing agent or at least one diamine curing agent, respectively. It is manufactured. Without being bound by any particular theory, by replacing the long chain polyol segment in the polyurethane prepolymer with a long chain polyetherdiamine oligomer soft segment ("polyetheramine"), a polyurea prepolymer is formed. It is currently believed that shear, cut, and impact resilience will be improved, and adhesion to other components will be improved.
For example, the polyurea elastomer composition of the present invention can be made from at least one isocyanate, at least one polyetheramine, and at least one curing agent. The polyurea composition can preferably be prepared from at least one isocyanate, at least one polyetheramine, and at least one diol curing agent and at least one diamine curing agent. The composition of the present invention can also be referred to as a castable reactive liquid material, which can be used to cast a layer around an inner member, as described in more detail below. To do.

The polyurea composition of the present invention is produced by crosslinking an isocyanate and a polyetheramine prepolymer with a curing agent. The curing agent is preferably a second diamine curing agent.
All polyetheramines available to those skilled in the art are suitable for use according to the present invention. As used herein, “polyetheramine” means at least a polyoxyalkyleneamine containing a primary amino group attached to the end of the polyether backbone. However, the choice of diamines and polyetheramines is limited to those that allow the formation of polyurea prepolymers because of the rapid reaction of isocyanates with amines and the insolubility of many urea products. In some embodiments, the polyether backbone is predominantly tetramethylene, propylene, ethylene, trimethylolpropane, glycerin, and mixtures thereof.
Suitable polyether amines include, but are not limited to: polytetramethylene ether diamine, polyoxypropylene diamine, poly (ethylene oxide terminated oxypropylene) ether diamine, triethylene glycol diamine, propylene oxide based triamine, Triamines based on methylolpropane, triamines based on glycerin, and mixtures thereof. In one embodiment, the polyetheramine used to make the prepolymer is Jeffamine D2000 (Huntsman, Austin, Texas).

  The molecular weight of the polyetheramine used in the present invention is in the range of about 100 to about 5000. The term “about” as used herein with respect to one or more numerical values or numerical ranges should be understood to include all numerical values within the range and mean all those numerical values. In some embodiments, the molecular weight of the polyetheramine is about 230 or greater. In other embodiments, the molecular weight of the polyetheramine is about 4000 or less. In yet another aspect, the molecular weight of the polyetheramine is about 600 or greater. In other embodiments, the molecular weight of the polyetheramine is about 3000 or less. In other variations, the molecular weight of the polyetheramine is from about 1000 to about 3000, more preferably from about 1500 to about 2500. A low molecular weight polyetheramine tends to form solid polyurea, so a high molecular weight oligomer such as Jeffamine D2000 is preferred.

式中、繰り返し単位の数ｘは約１〜約７０の範囲の値を有する。より好ましくは、繰り返し単位は約５〜約５０であり、さらに好ましくは約１２〜約３５である。 In some embodiments, the polyetheramine has the following general structure:

Wherein the number of repeating units x has a value in the range of about 1 to about 70. More preferably, the repeat unit is about 5 to about 50, and more preferably about 12 to about 35.

式中、繰り返し単位の数ｘ及びｚは組み合わせて約３．６〜約８の値を有し、繰り返し単位ｙは約９〜約５０の範囲の値を有し、Ｒは−(ＣＨ₂)_a−であり、式中ａは約１〜約１０の繰り返し単位であってもよい。 In other embodiments, the polyetheramine has the following general structure:

Wherein the number of repeating units x and z in combination has a value of about 3.6 to about 8, the repeating unit y has a value in the range of about 9 to about 50, and R is — (CH ₂ ). _a , wherein a may be from about 1 to about 10 repeating units.

式中、Ｒは−(ＣＨ₂)_a−であり、式中ａは約１〜約１０の繰り返し単位であってもよい。 In yet another embodiment, the polyetheramine has the following general structure:

Wherein R is — (CH ₂ ) _a —, where a may be about 1 to about 10 repeating units.

As mentioned briefly above, many amines are unsuitable for reaction with isocyanates due to the rapid reaction of amines with isocyanates. In particular, short-chain amines react quickly. However, in certain embodiments, sterically hindered secondary diamines may be suitable for use in the prepolymer. Without being bound by any particular theory, amines with a high degree of steric hindrance, such as amines having a tertiary butyl group attached to the nitrogen atom, are more kinetic than amines with no or less hindrance. Is thought to be slow. For example, 4,4′-bis- (sec-butylamino) -dicyclohexylmethane (Clearlink 1000) may be suitable for making a polyurea prepolymer in combination with an isocyanate.
Any isocyanate available to one skilled in the art is suitable for use in accordance with the present invention. The isocyanates used in the present invention are aliphatic, cycloaliphatic, araliphatic, aromatic, any of these derivatives, and derivatives of these compounds having two or more isocyanate (NCO) groups per molecule. Includes combinations. The isocyanate can be an organic polyisocyanate-terminated prepolymer, a lower free isocyanate, and mixtures thereof. The reactive component comprising the isocyanate may comprise any isocyanate functional monomer, dimer, trimer, or multimeric adduct, prepolymer, pseudoprepolymer, or mixture thereof. it can. The isocyanate functional compound can include a monoisocyanate or a polyisocyanate containing two or more isocyanate functional groups.

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

Examples of diisocyanates that can be used in the present invention include, but are not limited to: 2,2′-, 2,4′-, and 4,4′-diphenylmethane diisocyanate (MDI). Substituted and isomer mixtures including; 3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI); toluene diisocyanate (TDI); polymer MDI; carbodiimide-modified liquid 4,4′-diphenylmethane di Isocyanate; 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; Limethylene polyisocyanate (PMDI); MDI and PMDI mixture; PMDI and TDI mixture; Ethylene diisocyanate; Propylene-1,2-diisocyanate; Tetramethylene-1,2-diisocyanate; 1,3-diisocyanate; tetramethylene-1,4-diisocyanate; 1,6-hexamethylene diisocyanate (HDI); octamethylene diisocyanate; decamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1, 2-diisocyanate; Cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methyl-cyclohexylene diisocyanate (HTDI); 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate 4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanate methylcyclohexane isocyanate; 1-isocyanate-3,3,5- Trimethyl-5-isocyanatomethylcyclohexane; isocyanate ethylcyclohexane isocyanate; bis (isocyanatomethyl) -cyclohexanediisocyanate; 4,4′-bis (isocyanatomethyl) dicyclohexane; 2,4 ′ Bis (isocyanatomethyl) dicyclohexane; isophorone diisocyanate (IPDI); triisocyanate of HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexanediisocyanate (TMDI); '-Dicyclohexylmethane diisocyanate (H ₁₂ MDI); 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; 1,2-, 1,3-, and 1,4- Phenylene diisocyanates; aromatic aliphatic isocyanates such as 1,2-, 1,3- and 1,4-xylene diisocyanates; meta-tetramethylxylene diisocyanate (m-TMXDI); para-tetra Methyl xylene diisocyanate (p-TMXDI); any of the polyisocyanates Trimerized isocyanurates such as isocyanurates of toluene diisocyanate, trimers of diphenylmethane diisocyanate, trimers of tetramethylxylene diisocyanate, isocyanurates of hexamethylene diisocyanate, and mixtures thereof; Dimerized ureas of any of the polyisocyanates, such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, and mixtures thereof; modified polyisocyanates derived from the above isocyanates and polyisocyanates; and A mixture of these.

By changing the number of unreacted NCO groups in the isocyanate and polyetheramine polyurea prepolymers, factors such as the rate of reaction and the hardness of the resulting composition can be controlled. For example, the number of unreacted NCO groups in the polyurea prepolymer of isocyanate and polyetheramine can be less than about 14%. In some embodiments, 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 some embodiments, the proportion of unreacted NCO groups is from about 3% to about 9%. In other cases, the proportion of unreacted NCO groups is about 7.5% or lower, more preferably about 7% or lower. In other embodiments, the proportion of unreacted NCO groups is from about 2.5% to about 7.5%, more preferably from about 4% to about 6.5%.
Polyurea compositions can be made by cross-linking a polyurea prepolymer with a blend or mixture of curing agents. Curing agents used in the present invention include, but are not limited to: hydroxy-terminated curing agents, amine-terminated curing agents, and mixtures thereof. In certain preferred embodiments, the curing agent is an amine-terminated curing agent, more preferably a second diamine curing agent. However, if desired, the polyurea composition can be made with a single curing agent. Polyurea prepolymers cured with a secondary diamine at a stoichiometric amount of 1: 1 in the absence of humidity are inherently thermoplastic, while thermosetting polyurea prepolymers are generally generally primary diamines. Or made from polyurea prepolymer cured with multifunctional glycols.

Those skilled in the art that various properties of golf balls and golf ball members, such as hardness, can be controlled by adjusting the ratio of prepolymer to hardener (which is a function of the prepolymer's NCO content and hardener molecular weight). I know. For example, when a polyurea prepolymer having 6% unreacted NCO groups is cured with 1,4-butanediol, this ratio is 15.6: 1, while the same prepolymer is converted to 4,4′-bis- ( When cured with sec-butylamino) -dicyclohexylmethane (Clearlink 1000), this ratio is 4.36: 1. For the purposes of the present invention, the ratio of prepolymer to curing agent is preferably from about 0.5: 1 to about 16: 1.
The composition of the present invention can be selected from both castable thermosets and thermoplastics, which is determined at least in part by the curing agent used to cure the prepolymer and their ratio. . For example, the castable thermoplastic composition of the present invention comprises a linear polymer and is typically made by curing a prepolymer with a diol or a secondary diamine. On the other hand, the thermosetting composition of the present invention is a crosslinked polymer and is typically prepared from the reaction of a diisocyanate cured with a primary diamine or a polyfunctional glycol and a polyol.

Both types of curing agents, namely hydroxy-terminated curing agents and amine-terminated curing agents, can contain one or more saturated, unsaturated, aromatic, and cyclic groups. In addition, the hydroxy-terminated curing agent and the amine-terminated curing agent can contain one or more halogen groups.
Furthermore, the composition of the present invention can be used to produce thermoplastic pellets, which can be formed on balls by other molding methods such as injection molding or compression molding. The thermoplastic or thermosetting composition of the present invention can further be formed around the core using reaction injection molding (RIM) techniques.

  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; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; trimethylol Propane; cyclohexyldimethylol; triisopropanolamine; tetra- (2-hydroxypropyl) -ethylenediamine; diethylene glycol di- (aminopropyl) ether; 1,5-pentanediol; 1,6-hexanediol; ( -Hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol; 1,3-bis- [2- (2-hydroxyethoxy) ethoxy] cyclohexane; 1,3-bis- {2- [2- (2-hydroxyethoxy) ) Ethoxy] ethoxy} cyclohexane; trimethylolpropane; polytetramethylene ether glycol; resorcinol-di- (β-hydroxyethyl) ether and its derivatives; hydroquinone-di- (β-hydroxyethyl) ether and its derivatives; -Bis- (2-hydroxyethoxy) benzene; 1,3-bis- [2- (2-hydroxyethoxy) ethoxy] benzene; N, N-bis- (β-hydroxypropyl) aniline; 2-propanol-1, 1'-phenylaminobis; and mixtures thereof.

  In some embodiments, the hydroxy-terminal curing agent has a molecular weight of at least about 50. In other embodiments, the molecular weight of the hydroxy-terminated curing agent is about 2000 or less. In yet another aspect, the hydroxy-terminated curing agent is polytetramethylene ether glycol, which preferably has a molecular weight of about 250 to about 3900. The molecular weights used herein are absolute mass average molecular weights and should be understood as understood by those skilled in the art.

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

In some embodiments, the molecular weight of the amine-terminated curing agent is about 64 or greater. In other embodiments, the molecular weight of the amine-terminated curing agent is about 2000 or less.
A catalyst can be used to promote the reaction between the curing agent and the prepolymer. Suitable catalysts include, but are not limited to: zinc octoate, tin catalyst such as di-butyltin dilaurate (DBACO®-T12 manufactured by Air Products and Chemicals); Butyltin diacetate (DBACO®-T1); tin (II) chloride; tin (IV) chloride; di-butyltin dimethoxide (FASCAT®-4211); dimethyl-bis- [1-oxonedecyl) oxy Tin (FORMEZ® UL-28); di-n-octyltin bis-isooctyl mercaptoacetate (FORMEZ® UL-29); amine catalysts such as triethylenediamine (DBACO®-33LV) ), Triethylamine, and tributylamine; organic acids such as oleic acid and acetic acid; delayed catalysts such as POLYCAT® SA-1, POL YCAT (registered trademark) SA-2, POLYCAT (registered trademark), etc., and mixtures thereof. In some embodiments, the catalyst is di-butyltin dilaurate.

The catalyst is preferably added in an amount that sufficiently catalyzes the reaction of the components in the reaction mixture. In some embodiments, 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 di-butyltin dilaurate, the catalyst is preferably present in an amount from about 0.005% to about 1%. In other embodiments, the catalyst is present in an amount of about 0.5% by weight or greater.
The use of small amounts of tin catalyst, typically in the amount of about 0 to about 0.04% by weight of the total polyurea composition, requires high temperatures to obtain a suitable reaction rate, The result may be degradation of the polyurea prepolymer. Increasing the amount of catalyst to a higher level that is not normally used allows the processing temperature to be lowered while maintaining a temperature comparable to the curing step. The use of high levels of catalyst can also reduce the mixing rate. Thus, in some embodiments, the tin catalyst is present in an amount from about 0.01% to about 0.55% by weight of the composition. In other embodiments, from about 0.05% to about 0.4% tin catalyst is present in the composition. In yet other embodiments, the tin catalyst is present in an amount from about 0.1% to about 0.25%.

Various additional components can also be added to the polyurea composition of the present invention. These are not limited to, but include the following: White pigments such as TiO _2, ZnO, optical brighteners, surfactants, processing aids, blowing agents, UV stabilizers, and light stabilizers. In some embodiments, the polyurea composition includes at least one light-stable component to prevent the component that includes the unsaturated component from significantly yellowing. By adding light stabilizers, these materials can have certain advantages. The use of light stabilizers or UV absorbers is preferred for compositions having, for example, a difference in yellowing degree (ΔYI) of about 15 or greater.
Use of the light-stable component can assist in preventing damage to the cover surface due to photolysis. Suitable UV absorbers and light stabilizers include, but are not limited to: TINUVIN (R) 292, TINUVIN (R) 328, TINUVIN (R) 213, TINUVIN (R) 765, TINUVIN (R) Trademark) 770 and TINUVIN® 622. A preferred UV absorber for aromatic compounds is TINUVIN® 328 and a preferred sterically hindered amine light stabilizer is TINUVIN® 765. A preferred light stabilizer for saturated (aliphatic) compounds is TINUVIN® 292. TINUVIN® products are available from Ciba-Geigy. Dyes, optical brighteners and fluorescent pigments can be included in golf ball covers made with polymers made in accordance with the present invention. These additional ingredients can be added in any amount that achieves their desired purpose.
In order to further improve the shear resistance of the resulting polyurea elastomer, a trifunctional curing agent can be used to help improve the crosslinking. For example, a hydroxy-terminal curing agent can be used. Preferably, a triol, such as trimethylolpropane or tetraol, such as N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine can be added to the formulation.

Saturated polyurea compositions In addition, compositions and obtainables by using polyetheramines in place of conventional polyols and active saturated curing agents in place of aromatic curing agents in combination with saturated isocyanates. It has been found to provide light stability and improved shear resistance and impact resilience to the resulting golf equipment. As used herein, the term “saturated” means a composition having saturated aliphatic and alicyclic polymer backbones, ie, no carbon-carbon double bonds.
Accordingly, one aspect of the present invention is a saturated polyurea composition for use in golf equipment, particularly golf balls, wherein the saturated prepolymer is a product made from the reaction of at least one polyetheramine and at least one saturated diisocyanate. Oriented to things. The polyether amines listed above are also suitable for use with saturated prepolymers. The prepolymer is then cured with at least one saturated diol or diamine curing agent to provide a light stable polyurea / urethane or polyurea / urea elastomer, respectively.

Examples of saturated diisocyanates that can be used in the present invention include, but are not limited to: ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene-diisocyanate; tetramethylene-1 1,6-hexamethylene diisocyanate (HDI); octamethylene diisocyanate; decamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; -Trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,2-diisocyanate; cyclohexane-1,3- Diisocyanate; cyclohexane-1 4-diisocyanate; methyl-cyclohexylene diisocyanate (HTDI); 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4′-dicyclohexyl diisocyanate; '-Dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanate methylcyclohexane isocyanate; 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; isocyanate ethylcyclohexane isocyanate Bis (isocyanatomethyl) -cyclohexanediisocyanate; 4,4′-bis (isocyanatomethyl) dicyclohexane; 2,4′-bis (isocyanatomethyl) dicyclohexane; isophorone Isocyanate (IPDI); HDI of triisocyanate; 2,2,4-trimethyl-1,6-hexanediamine triisocyanate diisocyanate (TMDI); 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI ); 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; and mixtures thereof. Aromatic aliphatic isocyanates can also be used to produce light stable materials. Examples of these isocyanates include: 1,2-, 1,3-, and 1,4-xylene diisocyanates; meta-tetramethylxylene diisocyanate (m-TMXDI); para-tetramethyloxy Diisocyanate (p-TMXDI); trimerized isocyanurate of any polyisocyanate, such as isocyanurate of toluene diisocyanate, trimer of diphenylmethane diisocyanate, trimer of tetramethylxylene diisocyanate An isocyanurate of hexamethylene diisocyanate, and mixtures thereof; a dimerized ureasione of any polyisocyanate, such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, and mixtures thereof; Isocyan Over preparative and modified polyisocyanates derived from polyisocyanate; and mixtures thereof. Furthermore, aromatic aliphatic isocyanates can be mixed with any of the saturated isocyanates listed above for the purposes of the present invention.

  Saturated polyurea compositions can be made with blends or mixtures of curing agents. Saturated curing agents used in the present invention include, but are not limited to: hydroxy-terminated curing agents, amine-terminated curing agents, and mixtures thereof. However, if desired, the polyurea composition can be made with a single curing agent. As noted above, polyurea prepolymers cured in the absence of humidity at a 1: 1 stoichiometric amount with a diol or secondary diamine are inherently thermoplastic. On the other hand, thermosetting polyureas are generally made from polyurea prepolymers cured with primary diamines or multifunctional glycols.

  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 Dipropylene glycol; polypropylene glycol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; Cyclohexyl dimethylol; triisopropanolamine; tetra- (2-hydroxypropyl) -ethylenediamine; diethylene glycol di- (aminopropyl) ether; 1,5-pentanediol; 1,6-hexanediol; (2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol; 1,3-bis- [2- (2-hydroxyethoxy) ethoxy] cyclohexane; 1,3-bis- {2- [2- (2- Hydroxyethoxy) ethoxy] ethoxy} cyclohexane; trimethylolpropane; polytetramethylene ether glycol having a molecular weight of about 250-3900; and mixtures thereof. In some embodiments, the hydroxy-terminated-curing agent has a molecular weight of at least about 50. In other embodiments, the molecular weight of the hydroxy-terminated curing agent is about 2000 or less.

  Suitable saturated amine-terminated curing agents include, but are not limited to: ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; tetrahydroxypropyleneethylenediamine; 2,2,4- and 2,4 , 4-trimethyl-1,6-hexanediamine; 4,4′-bis- (sec-butylamino) -dicyclohexylmethane; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (Sec-butylamino) -cyclohexane; 4,4′-bis- (sec-butylamino) -dicyclohexylmethane derivative; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis- (methylamine); 1,3-cyclohexane-bis- (methylamine); diethylene glycol di- (aminopropylene 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamine; imido-bis-propylamine Monoethanolamine, diethanolamine; triethanolamine; monoisopropanolamine, diisopropanolamine; isophoronediamine; and mixtures thereof. In some embodiments, the amine-curing agent has a molecular weight of about 64 or greater. In other embodiments, the molecular weight of the amine-curing agent is about 2000 or less. In addition, any of the above polyether amines can be used as a curing agent to react with the polyurea prepolymer.

Saturated polyetheramine can be blended with additional polyol to form a copolymer that can be reacted with excess isocyanate to produce a polyurea prepolymer. In some embodiments, less than about 30% by weight of the copolymer is blended with saturated polyetheramine. In other embodiments, less than about 20% by weight of the copolymer, preferably less than about 15% by weight of the copolymer is blended with the saturated polyetheramine. Any saturated polyol available to those skilled in the art, such as polyether polyols, polycaprolactone polyols, polyester polyols, polycarbonate polyols, hydrocarbon polyols, other polyols, and mixtures thereof are suitable for blending in accordance with the present invention. Yes. The molecular weight of these polymers can be from about 200 to about 4000, but can be from about 1000 to about 3000, more preferably from about 1500 to about 2500.
Saturated polyether polyols suitable for blending with polyurea prepolymers include, but are not limited to: polytetramethylene ether glycol (PTMEG); PTG-L; poly (oxyethylene) glycol; poly (oxypropylene) Glycols; poly (ethylene oxide terminated oxypropylene) glycols; and mixtures thereof.

Saturated 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 glycol initiated polycaprolactone; 1 , 6-hexanediol initiated polycaprolactone; polytetramethylene ether glycol (PTMEG) initiated polycaprolactone; and mixtures thereof.
Suitable saturated 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; blend.

Examples of saturated polycarbonate polyols for use in the present invention include, but are not limited to: poly (phthalate carbonate) glycol, poly (hexamethylene carbonate) glycol, polycarbonate polyol containing bisphenol A, and mixtures thereof. Hydrocarbon polyols include, but are not limited to, hydroxy-terminated liquid isoprene rubber (LIR), hydroxy-terminated polybutadiene polyols, and mixtures thereof.
Other aliphatic polyols that can be used to make the prepolymers of the present invention include, but are not limited to: glycerol; castor oil and its derivatives; saturated hydroxy-terminated hydrocarbon polyols; Polytail H; HA; Kraton polyol; acrylic polyol; acid functionalized polyol based on carboxylic acid, sulfonic acid, or phosphoric acid group; dimer alcohol converted from saturated dimerized fatty acid; and mixtures thereof.

As noted above, a catalyst can be used to promote the reaction between the saturated curing agent and the saturated prepolymer. The above-described catalyst is suitable for use in the saturated composition of the present invention.
Saturated polyureas are typically resistant to discoloration. However, they are not resistant to degradation of their mechanical properties when exposed to outside air. The addition of UV absorbers and light stabilizers to any of the polyurea compositions described above helps maintain tensile strength, elongation, and color stability. Therefore, UV absorbers and light stabilizers as described above can also be included in the saturated composition of the present invention. Preferably, these components can be added not only to compositions having a yellowness difference of about 15 or greater, but can also be added to compositions having a yellowness difference of about 12 to about 15. .

Composition Blend The polyurea composition preferably comprises from about 1% to about 100% polyurea, although the polyurea composition may be blended with other materials. In some embodiments, the composition comprises about 10% to about 90% polyurea, preferably about 10% to about 75% polyurea, and about 90% to 10%, more preferably about 90%. Up to about 25% other polymers and / or other materials described below.
Other polymeric materials suitable for blending with the compositions of the present invention include, but are not limited to: castable thermoplastic or thermoset polyurethanes (eg, US Pat. No. 5,334,673), Cationic and anionic ionomers (eg, US Pat. No. 5,692,974) and urethane epoxides, polyurethane / polyurea ionomers, epoxy resins, polyethylene, polyamides and polyesters, polycarbonates, polyacrylins, and mixtures thereof. Examples of suitable polyureas used to produce the above polyurea ionomers are described in US Pat. No. 5,484,870, which is reacted with a polyisocyanate and a polyamine curing agent. Get. The polyurea compound of the '870 patent differs from the polyurea of the present invention, which is made from a polyurea prepolymer and a curing agent. Examples of suitable polyurethanes cured with epoxy group containing curing agents are disclosed in US Pat. No. 5,908,358. The entire disclosure is incorporated herein by reference to the above patents.

For example, the polyurea composition of the present invention can be blended with a reaction product between a thermosetting or thermoplastic polyurethane, ie, at least one polyurethane prepolymer (isocyanate and polyol) and at least one curing agent. .
As noted above, the main difference between the polyurea composition of the present invention and the polyurethane composition is that the polyetheramine is replaced with a prepolymer. Accordingly, any of the isocyanates and curing agents described above for the polyurea composition are suitable for use in the present invention. In addition, any polyol available to those skilled in the art, such as polyether polyols, polycaprolactone polyols, polyester polyols, polycarbonate polyols, hydrocarbon polyols, other polyols, and mixtures thereof are suitable for the polyurethane prepolymer.

In one embodiment, a saturated polyurea composition is blended with a saturated polyurethane, the polyurethane made from a saturated isocyanate and a saturated polyol and cured with a saturated curing agent. Any of the saturated isocyanates, saturated hardeners, and saturated polyols described above with respect to the saturated polyurea composition are suitable for use in the saturated polyurethane composition. In addition, a catalyst can be used to promote the reaction between the curing agent and the isocyanate and the polyol. Any of the catalysts described above with respect to the polyurea composition are suitable for use in the polyurethane composition.
Before blending with the polyurea composition, the polyurethane may be made of other materials such as ionic or nonionic polyurethanes, cationic and nonionic urethane ionomers and urethane epoxies, epoxy resins, polyethylene, polyamides and polyesters, ionic and nonionic. Polyurea and blends thereof can also be blended. When blended with other materials, the polyurethane composition preferably comprises from about 90% to about 10%, more preferably from about 90% to about 25%, of one or more polymers and / or other materials as described above.

Acid Functionalization of Compositions The present invention also contemplates acid functionalization of the polyurea and polyurethane compositions of the present invention, which is a “new acid functional polyurethane, polyurea filed on Feb. 5, 2002. Or a golf ball composition comprising these copolymers, disclosed in US patent application Ser. No. 10 / 072,395, which is hereby incorporated by reference in its entirety. Without being bound by any particular theory, it is believed that polyureas and polyurethanes containing acid functional moieties or groups have improved adhesion to other components or layers. The acid functional group is preferably mainly composed of a sulfonic acid group (HSO ₃ ), a carboxyl group (HCO ₂ ), a phosphoric acid group (H ₂ PO ₃ ), or a combination thereof. More than one type of acid functional group can be incorporated into the polyurea or polyurethane.
In some embodiments, the acid functional polyurea or polyurethane is made from a prepolymer having an acid functional moiety. Acid groups can be introduced into the isocyanate moiety, or each of the polyurea or polyether amine or polyol components of the polyurethane.

  In US Pat. Nos. 5,661,207 and 6,103,822, acid functional polyols are disclosed in detail along with reagents and methods used to derive the acid functional polyols. All of that disclosure is incorporated herein by reference and the polyol is suitable when using acid functional polyurethane compositions. In some embodiments, the acid functional polyol used in the polyurethane prepolymer comprises a derivative of a carboxylated, sulfonated, or phosphonated polyester polyol. Suitable acid-functional polyols have an acid number (calculated by dividing 56,100 by the acid equivalent weight) of at least about 10, preferably from about 20 to about 420, more preferably from about 25 to about 150, most preferably about 30 to about 75. Furthermore, the polyol has a hydroxyl number (calculated by dividing 56,100 by the hydroxyl equivalent number) of at least about 10, preferably from about 20 to about 840, more preferably from about 20 to about 175, and most preferably from about 50 to about 175. 150. Further, the hydroxyl functionality (average number of hydroxyl groups per polyol molecule) of the polyol is at least about 1.8, preferably from about 2 to about 4.

In other cases, the acid functionality can be further bound to the isocyanate or isocyanate component of the polyurea or polyurethane. Suitable acid functional isocyanates include conventional isocyanates having acid functional groups that can be prepared by reacting an isocyanate with a compound containing acid functional groups, which are disclosed in US Pat. No. 4,956,438. And 5,071,578, the entire disclosure of which is hereby incorporated by reference.
In other embodiments, acid groups are incorporated during post-polymerization reactions where acid functional groups are introduced or attached to the polyurea or polyurethane. Further, additional acid functional groups can be further incorporated into the acid-functional polyurea or polyurethane produced by the above-described copolymerization means by such post-polymerization reaction. Suitable reagents and methods for making acid urea groups into polyureas or polyurethanes are described in US Pat. No. 6,207,784, the disclosure of which is hereby incorporated by reference in its entirety. take in.

Those skilled in the art are aware of other methods of producing acid functional polyureas or polyurethanes. For example, combinations of the above aspects can be used as described in US Pat. No. 5,661,207, the entire disclosure of which is incorporated herein by reference.
Acid functional polyureas or polyurethanes can be partially or fully neutralized with organic or inorganic metal bases and / or tertiary amines to produce anionic polyurethane / polyurea ionomers. In the production of the prepolymer, a base can be added as a separate neutralization step of the already polymerized acid-functional polyurea or polyurethane or in the dispersion of the polyurea or polyurethane. These bases can be added anywhere in these stages, or if these stages occur simultaneously, the base is present in all stages.

  Suitable metal bases used for partial or complete neutralization can include compounds such as metal oxides, metal hydroxides, metal carbonates, metal bicarbonates and metal acetates. Metal ions 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 these bases include: lithium, sodium, potassium, magnesium, zinc, calcium, manganese, aluminum, tungsten, zirconium, titanium and hafnium. The amine is preferably a sterically hindered organic tertiary amine such as tributylamine, triethylamine, triethylenediamine, dimethylcetylamine and similar compounds. Only when the neutralization step occurs after polymer production, primary or secondary amines can preferably be used, since the hydrogen of the amine can immediately react with isocyanate groups, thereby polyurea or polyurethane polymerization. This is because it receives interference. Those skilled in the art are aware of additional suitable chemicals for neutralization.

Golf Ball Core Layer Materials Golf ball cores made in accordance with the present invention can be solid, semi-solid, hollow, liquid-filled or powder-filled, one-piece or multi-component cores. The term “semi-solid” is used herein to mean paste, gel, 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, and thermoplastic materials such as ionomer resins, polyamides or polyesters, and thermoplastic and thermosetting. Polyurethane elastomer. As described above, the polyurea composition of the present invention can be incorporated into all members of the golf ball including the core.

  In some embodiments, a golf ball core is made from a composition that includes a base rubber (natural, synthetic, or a combination thereof), a crosslinking agent, and a filler. In other embodiments, the golf ball core is made from a reaction product comprising a cis-trans catalyst, a rebound elastic polymer with polybutadiene, a free radical source, and optionally a crosslinker, filler, or both. Polymers, sic-trans catalysts, fillers, crosslinkers, and free radical sources such as those disclosed in co-pending and co-assigned US Patent Publication No. 2003/0119989, the disclosure of which is hereby incorporated by reference Various combinations of (incorporated in the specification) can be used to produce the reaction product. Although this polybutadiene reaction product has been discussed in the part relating to the core composition, the present invention further contemplates using the reaction product to produce at least some portion of any component of the golf ball. Yes. In some embodiments, the polybutadiene reaction product is substantially free of antioxidants. As used herein, the term “substantially free” generally means that the polybutadiene reaction product contains less than about 0.3 phr, preferably less than about 0.1 phr, more preferably about 0.05 phr of antioxidant. Means less, most preferably less than about 0.01 phr. In some embodiments, the ratio of free radical source to antioxidant is greater than about 10. In other embodiments, the ratio of free radical source to antioxidant is about 25, preferably greater than about 50. In yet other embodiments, the ratio of free radical source to antioxidant is about 100 or greater. In other embodiments, the ratio of free radical source to antioxidant is about 200 or greater, preferably about 250 or greater, more preferably about 300 or greater.

式中、Ｒ₁〜Ｒ₅はいずれの順序であってもよいＣ₁〜Ｃ₈アルキル基；ハロゲン基、チオール基（−ＳＨ）、カルボキシル化した基；スルホン化した基；及び水素であることができ；さらに以下のものであることができる：ペンタフルオロチオフェノール；２−フルオロチオフェノール；３−フルオロチオフェノール；４−フルオロチオフェノール；２，３−フルオロチオフェノール；２，４−フルオロチオフェノール；３，４−フルオロチオフェノール；３，５−フルオロチオフェノール；２，３，４−フルオロチオフェノール；３，４，５−フルオロチオフェノール；２，３，４，５−テトラフルオロチオフェノール；２，３，５，６−テトラフルオロチオフェノール；４−クロロテトラフルオロチオフェノール；ペンタクロロチオフェノール；２−クロロチオフェノール；３−クロロチオフェノール；４−クロロチオフェノール；２，３−クロロチオフェノール；２，４−クロロチオフェノール；３，４−クロロチオフェノール；３，５−クロロチオフェノール；２，３，４−クロロチオフェノール；３，４，５−クロロチオフェノール；２，３，４，５−テトラクロロチオフェノール；２，３，５，６−テトラクロロチオフェノール；ペンタブロモチオフェノール；２−ブロモチオフェノール；３−ブロモチオフェノール；４−ブロモチオフェノール；２，３−ブロモチオフェノール；２，４−ブロモチオフェノール；３，４−ブロモチオフェノール；３，５−ブロモチオフェノール；２，３，４−ブロモチオフェノール；３，４，５−ブロモチオフェノール；２，３，４，５−テトラブロモチオフェノール；２，３，５，６−テトラブロモチオフェノール；ペンタヨードチオフェノール；２−ヨードチオフェノール；３−ヨードチオフェノール；４−ヨードチオフェノール；２，３−ヨードチオフェノール；２，４−ヨードチオフェノール；３，４−ヨードチオフェノール；３，５−ヨードチオフェノール；２，３，４−ヨードチオフェノール；３，４，５−ヨードチオフェノール；２，３，４，５−テトラヨードチオフェノール；２，３，５，６−テトラヨードチオフェノール；及びこれらの亜鉛塩。好ましくはハロゲン化した有機硫黄化合物はペンタクロロチオフェノールであり、これは純粋な形態で又は商標名STRUKTOL（登録商標）（米国、ストウ、OH、のストラクトール（Struktol）社から市場を通じて入手可能である）の名称で市場から入手可能である。ある態様では、ハロゲン化した有機硫黄化合物はペンタクロロチオフェノールの亜鉛塩であり、これはサンフランシスコ、CA、のキナケム（Chinachem）社から市場を通じて入手可能である。 In another embodiment, the cis-trans transfer catalyst used is an organic sulfur component, preferably a halogenated organic sulfur having the general formula:

In the formula, R _{1 to} R ₅ may be in any order C _{1 to} C ₈ alkyl group; halogen group, thiol group (—SH), carboxylated group; sulfonated group; and hydrogen Can also be: pentafluorothiophenol; 2-fluorothiophenol; 3-fluorothiophenol; 4-fluorothiophenol; 2,3-fluorothiophenol; 2,4-fluorothio 3,4-fluorothiophenol; 3,3,4-fluorothiophenol; 3,3,4-fluorothiophenol; 3,4,5-fluorothiophenol; 2,3,4,5-tetrafluorothiophenol 2,3,5,6-tetrafluorothiophenol; 4-chlorotetrafluorothiophenol; pentachlorothiophene 2-chlorothiophenol; 3-chlorothiophenol; 4-chlorothiophenol; 2,3-chlorothiophenol; 2,4-chlorothiophenol; 3,4-chlorothiophenol; 3,5-chlorothio 2,3,4-chlorothiophenol; 3,3,4-chlorothiophenol; 2,3,4,5-tetrachlorothiophenol; 2,3,5,6-tetrachlorothiophenol; pentabromo 2-bromothiophenol; 3-bromothiophenol; 4-bromothiophenol; 2,3-bromothiophenol; 2,4-bromothiophenol; 3,4-bromothiophenol; 3,5-bromo Thiophenol; 2,3,4-bromothiophenol; 3,4,5-bromothiophenol; 2,3,4 2,3,5,6-tetrabromothiophenol; pentaiodothiophenol; 2-iodothiophenol; 3-iodothiophenol; 4-iodothiophenol; 2,3-iodothiophenol 2,4-iodothiophenol; 3,4-iodothiophenol; 3,5-iodothiophenol; 2,3,4-iodothiophenol; 3,4,5-iodothiophenol; , 5-tetraiodothiophenol; 2,3,5,6-tetraiodothiophenol; and zinc salts thereof. Preferably, the halogenated organosulfur compound is pentachlorothiophenol, which is available in the pure form or commercially available from Struktol, Inc., under the trade name STRUKTOL® (US, Stow, OH). Is available on the market under the name In some embodiments, the halogenated organosulfur compound is a zinc salt of pentachlorothiophenol, which is commercially available from Chinachem, San Francisco, CA.

Golf Ball Intermediate Material When the golf ball of the present invention includes an intermediate layer, such as an inner cover layer or an outer cover layer, i.e., any layer disposed between the inner core and outer cover of the golf ball, This layer can comprise any material known to those skilled in the art including thermoplastic and thermoset materials. For example, the intermediate layer can be made from any of the polyurea, polyurethane, and polybutadiene materials described above.
The intermediate layer may also contain one or more homopolymer or copolymer materials as follows:
(1) Vinyl resin, for example, produced by polymerization of vinyl chloride, or produced by copolymerization of vinyl chloride and vinyl acetate, acrylic ester or vinylidene chloride;
(2) Manufactured using polyolefins such as polyethylene, polypropylene, polybutadiene and copolymers such as ethylene methacrylate, ethylene ethyl acrylate, ethylene vinyl acetate, ethylene methacrylic acid or ethylene acrylic acid or propylene acrylic acid and single site or metallocene catalysts Copolymer or homopolymer;
(3) Polyurethanes, such as those made from polyols and diisocyanates or polyisocyanates and those disclosed in US Pat. No. 5,334,673;
(4) Polyureas such as those disclosed in US Pat. No. 5,484,870;
(5) polyamides such as poly (hexamethylenediadipamide) and others made from diamines and dibasic acids, and amino acids such as those made from poly (caprolactam), and SURLYN, polyethylene, ethylene copolymers, Blends of ethylene-propylene-nonconjugated diene terpolymers and polyamides, etc .;

(6) Acrylic resins and blends of these resins with polyvinyl chloride, elastomers, etc .;
(7) thermoplastics such as urethane; olefinic thermoplastic rubbers such as blends of ethylene-propylene-nonconjugated diene terpolymers and polyolefins; block copolymers of butadiene, isoprene or ethylene-butylene rubbers and styrene; or copoly (ethers) Amide), such as PEBAX available from ELF Atochem, Philadelphia, PA;
(8) Polyphenylene oxide resin or a blend of high impact polystyrene and polyphenylene oxide marketed under the trade name NORYL by General Electric, Pittsfield, MA;
(9) Thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / glycol modified, and Wilmington, DE, EI DuPont de Nemours & Co., marketed under the trade name HYTREL. An elastomer marketed under the name LOMOD by General Electric Company, Pittsfield, MA;
(10) Blends and alloys containing acrylonitrile butadiene styrene, polybutylene terephthalate, polyethylene terephthalate, styrene maleic anhydride, polyethylene, elastomers and polycarbonates, and acrylonitrile butadiene styrene or ethylene vinyl acetate or other elastomers and polyvinyl chloride, and (11) Blend of polyethylene, propylene, polyacetal, nylon, polyester, cellulose ester, etc. and thermoplastic rubber.

  In some embodiments, the intermediate layer comprises: a polymer, such as ethylene, propylene, butene-1, or a functional monomer such as acrylic acid and methacrylic acid and a fully or partially neutralized ionomer resin and blends thereof. Hexane-1-based homopolymers or copolymers, methyl acrylate, methyl methacrylate homopolymers and copolymers, imidized amino group-containing polymers, polycarbonate, reinforced polyamide, polyphenylene oxide, high impact polystyrene, polyether ketone, polysulfone, poly ( Phenylene sulfide), acrylonitrile-butadiene, acrylic-styrene-acrylonitrile, poly (ethylene terephthalate), poly (butylene terephthalate), poly (ethylene vinyl alcohol), Li (tetrafluoroethylene) and copolymers thereof containing functional comonomers, and blends thereof.

Ionomer As briefly mentioned above, the intermediate layer can include an ionomer material, such as an ionic copolymer of ethylene and an unsaturated monocarboxylic acid, which is manufactured by DuPont (EI) of Wilmington, DE. DuPont de Nemours & Co.) under the trade name SURLYN, Exxon IOTEK® or ESCOR®. These are completely or partially neutralized with salts of zinc, sodium, lithium, magnesium, potassium, calcium, manganese, nickel, etc., i.e. about 1 to about 100% neutralized methacrylic acid or acrylic acid and ethylene. Or a terpolymer. In some embodiments, the carboxylic acid group is neutralized from about 10 to about 100%. The carboxylic acid group can further comprise methacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid. These 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 further comprises at least one ionomer, for example an acid-containing ethylene copolymer ionomer comprising an E / X / Y terpolymer, wherein E is ethylene and X is an acrylate or methacrylate present from about 0 to 50% by weight. A softening comonomer based on which Y is acrylic acid or methacrylic acid present in about 5-35% by weight. In other embodiments, 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 can further include so-called “low acid” and “high acid” ionomers, and blends thereof. In general, ionic copolymers containing up to about 15% acid are considered "low acid" ionomers, while those containing more than about 15% acid are considered "high acid" ionomers.

  Low acid ionomers are believed to give high rotation. Thus, in certain embodiments, the intermediate layer comprises a low acid ionomer in which the acid is present at about 10-15% by weight, and optionally contains a softening comonomer, such as iso- or n-butyl acrylate, to produce a flexible terpolymer. Including. The softening comonomer can be selected from the group consisting of: a vinyl ester of an aliphatic carboxylic acid, where the acid has 2-10 carbon atoms, a vinyl ether where the alkyl group contains 1-10 carbon atoms, Alkyl acrylate or methacrylate, wherein the alkyl group contains 1 to 10 carbon atoms. Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and the like.

  In other embodiments, the intermediate layer includes at least one highly acidic ionomer for low rotational speed and maximum flight distance. In this respect, about 15 to about 35% by weight of acrylic acid or methacrylic acid is present to make the ionomer a high modulus ionomer. In some embodiments, 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%. Contains wt% carboxylic acid. In some situations, additional comonomers, such as acrylate esters (ie, iso- or n-butyl acrylate, etc.) can be further included to produce soft terpolymers. The additional comonomer can be selected from the group consisting of: 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 Alkyl acrylates or methacrylates containing 1 to 10 carbon atoms. Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and the like.

Accordingly, a number of copolymers suitable for use to produce high modulus ionomers include, but are not limited to: ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / itaconic acid copolymers, ethylene / maleic acid copolymers. Highly acidic embodiments such as ethylene / methacrylic acid / vinyl acetate copolymer and ethylene / acrylic acid / vinyl alcohol copolymer.
In some embodiments, the intermediate layer can be made from at least one polymer comprising these salts that are 100% neutralized by α, β-unsaturated carboxylic acid groups or organic fatty acids. The organic acid is an aliphatic, mono-functional (saturated, unsaturated, or polyunsaturated) organic acid. These organic acid salts can also be used. The salts of organic acids of the present invention include the following salts: barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, Tin, or calcium, salts of fatty acids, in particular salts of stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid or dimerized derivatives thereof. The organic acids and salts of the present invention must be relatively non-mobile (no bloom on the surface of the polymer at ambient temperature) and non-volatile (not volatile at the temperature required for melt blending). preferable.

  The acid portion of a highly neutralized polymer ("HNP"), typically an ethylene-based ionomer, is preferably more than about 70% neutralized, more preferably more than about 90%, most preferably at least about 100% neutralized. HNP can be further blended with a second polymer component and, if it contains acid groups, this component can be neutralized with organic fatty acids according to conventional methods, or both. The second polymer component, which may be partially or fully neutralized, preferably comprises: ionomer copolymers and terpolymers, ionomer precursors, thermoplastics, polyamides, polycarbonates, polyesters, polyurethanes, polyureas , Thermoplastic elastomers, polybutadiene rubber, balata, metallocene catalyzed polymers (grafted or ungrafted), single-site polymers, highly crystalline acid polymers, cationic ionomers, and the like.

In this embodiment, the acid copolymer can be described as an E / X / Y copolymer, where E is ethylene, X is an α, β-ethylenically unsaturated carboxylic acid, and Y is a soft comonomer. In a preferred embodiment, X is acrylic acid or methacrylic acid and Y is a C _1-8 alkyl acrylate or methacrylate ester. X is preferably present from about 1 to about 35% by weight of the polymer, more preferably from about 5 to about 30% by weight of the polymer, and most preferably from about 10 to about 20% by weight of the polymer. Y is preferably present from about 0 to about 50% by weight of the polymer, more preferably from about 5 to about 25% by weight of the polymer, and most preferably from about 10 to about 20% by weight of the polymer.
The organic acid is an aliphatic, mono-functional (saturated, unsaturated, or polyunsaturated) organic acid. These organic acid salts can also be used. The salts of organic acids of the present invention include the following salts: barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, Tin, or calcium, salts of fatty acids, in particular salts of stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid or dimerized derivatives thereof. The organic acids and salts of the present invention must be relatively non-mobile (no bloom on the surface of the polymer at ambient temperature) and non-volatile (not volatile at the temperature required for melt blending). preferable.

The following can be blended either before, during or after neutralization of the acid moiety: thermoplastic polymer components such as copolyetheresters, copolyesteresters, copolyetheramides, elastomers Polyolefins, styrene diene block copolymers and their hydrogenated derivatives, copolyesteramides, thermoplastic polyurethanes such as copolyether urethanes, copolyester urethanes, copolyurea urethanes, polyurethanes based on epoxy, polyurethanes based on polycaprolactone, Polyurea and polyurethane fillers based on polycarbonate, and other components, if included.
Examples of these materials are disclosed in US Patent Application Nos. 2001/0018375 and 2001/0019971, all of which are hereby expressly incorporated by reference.

The ionomer composition can further comprise a polymer made with at least one grafted metallocene catalyst. The blend of this embodiment can comprise from about 1 phr to about 100 phr of at least one grafted metallocene catalyst prepared polymer and from about 99 phr to 0 phr of at least one ionomer, preferably from about 5 phr to about 90 phr of at least one A polymer comprising a grafted metallocene catalyst and from about 95 phr to about 10 phr of at least one ionomer, more preferably from about 10 phr to about 75 phr of at least one grafted metallocene catalyst and from about 90 phr to about 25 phr of at least One ionomer, and most preferably from about 10 phr to about 50 phr of the polymer prepared with at least one grafted metallocene catalyst and from about 90 phr to about 50 phr of at least one ionomer. If the layer is foamed, the polymer blend produced with the grafted metallocene catalyst can be foamed with conventional foaming or blowing agents during molding.
In addition, the polyamides described in detail below can also be blended with ionomers.

Non-Ionomer Thermoplastic Material In other embodiments, the intermediate layer includes at least one inherently or completely non-ionomer thermoplastic material. Suitable non-ionomer materials include: polyamides and polyamide blends, polyolefins or polyamides made with grafted and ungrafted metallocene catalysts, polyamide / ionomer blends, polyamide / non-ionomer blends, polyphenylene ether / ionomer blends, and the like Mixture of. Polyolefins or polyamides made with grafted and ungrafted metallocene catalysts, polyamide / ionomer blends, polyamide / non-ionomer blends are co-pending applications filed May 6, 2002, made with “grafted metallocene catalysts” No. 10 / 138,304, entitled “Golf Balls Containing Polymer Blend”, the entire disclosure of which is incorporated herein by reference.

  In some embodiments, polyamide homopolymers such as polyamide 6,18 and polyamide 6,36 are used alone or in combination with other polyamide homopolymers. In other embodiments, 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 Polyamide 4, Polyamide 6, Polyamide 7, Polyamide 11, Polyamide 12 (Philadelphia, PA, Elf Atochem, manufactured by 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 represents terephthalic acid), polyamide 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, the polyamide homopolymers, copolymers, and homopolymer / copolymer blends described above are optionally combined with non-ionomers, such as non-ionomer thermoplastic polymers, non-ionomer thermoplastic copolymers, non-ionomer TPEs, and mixtures thereof. Can be blended.
A specific example of a polyamide-nonionomer blend is a blend of polymers made with a polyamide-metallocene catalyst. The blended composition can include polymers made with grafted and / or ungrafted metallocene catalysts. Polymers made with grafted metallocene catalysts, functionalized with branching groups such as maleic anhydride, are available in experimental quantities from DuPont. The polymer produced with the grafted metallocene catalyst is further subjected to a post-polymerization reaction of a polymer produced with a commercially available ungrafted metallocene catalyst containing a monomer and an organic peroxide to obtain a graft having one or more desired branching groups. It can also be obtained by providing a polymer made with a prepared metallocene catalyst.

Another example of a polyamide-nonionomer blend is a nonionic polymer made using a single site catalyst that is not based on polyamide and a metallocene system. As used herein, the term “non-metallocene based catalyst” or “non-metallocene based single site catalyst” means a single site catalyst other than a metallocene catalyst. Examples of polymers made with suitable single-site catalysts are disclosed in co-pending application US patent application 09 / 677,871, which is hereby incorporated by reference in its entirety.
Suitable non-ionomers for blending with polyamide include, but are not limited to: block copoly (ester) copolymers, block (amide) copolymers, block copoly (urethane) copolymers, styrene based block copolymers, elastomers vulcanized No thermoplastic and elastomer blends (TEB), and thermoplastic and elastomer or rubber blends (TED) where the elastomer is dynamically vulcanized. Other non-ionomers that are suitable for blending with the polyamide to produce an interlayer composition include, but are not limited to: polycarbonate, polyphenylene oxide, imidized, amino group-containing polymer, high impact polystyrene. (HIPS), polyetherketone, polysulfone, poly (phenylene sulfide), reinforced engineering plastics, acrylic-styrene-acrylonitrile, poly (tetrafluoroethylene), poly (butyl acrylate), poly (4-cyanobutyl acrylate), Poly (2-ethylbutyl acrylate), polyheptyl acrylate), poly (2-methylbutyl acrylate), poly (3-methylbutyl acrylate), poly (N-octadecylacrylamide), poly (octade) Methacrylate) poly (4-dodecylstyrene), poly (4-tetradecylstyrene), poly (ethylene oxide), poly (oxymethylene), poly (silazane), poly (furantetracarboxylic diimide), poly (acrylonitrile), Poly ("-methylstyrene), and copolymers thereof, and blends thereof, including the group of polymers and functional comonomers to which they belong.
In other embodiments, the non-ionomer material has a Shore D hardness of about 60 or greater and a flexural modulus of about 206.84 MPa (30,000 psi) or greater.

The reinforced intermediate layer of the rebound elastic polymer- polymer blend can include a rebound elastic polymer component, which preferably is used as a major portion of the polymer in the intermediate layer to impart rebound resilience in the cured state and the polymer component as a blend. To strengthen.
Rebound resilience polymers suitable for use in the interlayer include the following, preferably having a high molecular weight of at least about 50,000 to about 1,000,000: polybutadiene, polyisoprene, styrene-butadiene, styrene-propylene- Diene rubber, ethylene-propylene-diene (EPDM), mixtures thereof, and the like. In some embodiments, the molecular weight is from about 250,000 to about 750,000, more preferably from about 200,000 to about 400,000.
The toughening polymer component preferably has a glass transition temperature (T _G ) that is low enough to allow mixing without initiating crosslinking, preferably from about 35 ° C to 120 ° C. In addition, the toughening polymer component preferably sways a viscosity that is low enough to allow proper mixing of the two polymer components at the mixing temperature when mixed with the resilience polymer component. The weight of the reinforcing polymer is generally in the range of about 5 to 25% by weight, preferably about 10 to 20% by weight, based on the total composition forming the interlayer.

Examples of polymers suitable for use in the reinforced polymer component include: trans-polyisoprene, block copolymer ether / ester, acrylic polyol, polyethylene, polyethylene copolymer, 1,2-polybutadiene (syndiotactic), ethylene -Vinyl acetate copolymers, trans-polycyclooctenenamers, trans-isomer polybutadienes, and mixtures thereof. Particularly preferred toughening polymers include: HYTREL 3078, a block copolymer ether / ester commercially available from DuPont, Wilmington, DE; trans-isomer polybutadiene, such as Kawasaki-ku, Kawasaki, Japan FUREN 88 obtained from Asahi Chemicals, Yako, KURRARAY TP251, trans-polyisoprene available through the market from KURARARAY; Bayer-Rubber Division of LEVAPREN 700HV, Akron, OH ( Ethylene-vinyl acetate copolymer commercially available from Bayer-Rubber Division; and trans-polycyclooctanemer commercially available from Huls America Inc. of VESTENAME® 8012, Tallmadge, OH . Suitable reinforcing polymer components shown in Table 1 below listed along with the crystal during the melting (T _C) and / or T _G.

Another polymer that is particularly suitable for use in the reinforced polymer component is a polybutadiene component that enhances stiffness, which is typically at least about 80% trans-isomer component and the remainder cis-isomer. , 4-polybutadiene and vinyl-isomer 1,2-polybutadiene. Accordingly, this is referred to herein as “high trans-isomer polybutadiene” or “stiffness-enhanced polybutadiene”, which is derived from polybutadiene having a low cis-isomer polybutadiene or trans-isomer content, ie, typically less than 80%. Can be distinguished and used to form the golf ball core of the present invention. The vinyl content of the stiffness enhancing polybutadiene component is preferably no more than about 15% of the polybutadiene isomer, more preferably no more than about 10%, even more preferably no more than about 5%, most preferably about Present in an amount not exceeding 3%.
When the rigidity-enhancing polybutadiene is used in the golf ball of the present invention, its polydispersity preferably does not exceed about 4, more preferably does not exceed about 3, and even more preferably does not exceed about 2.5. Polydispersity or PDI is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer.

Further, when the rigidity enhancing polybutadiene component is used in the golf ball of the present invention, it typically has a high absolute average molecular weight as defined above, at least about 100,000, preferably about 200,000 to 1,000,000. . In some embodiments, the absolute average molecular weight is about 230,000 to 750,000. In other embodiments, the molecular weight is from about 275,000 to about 700,000. In either embodiment, the absolute molecular weight is preferably greater than about 200,000 when the vinyl component is present in greater than about 10%.
When trans-polyisoprene or high-trans-isomer polybutadiene is included in the reinforced polymer component, it is about 10-40% by weight, preferably about 15-30% by weight of the polymer blend, ie, the resilience and reinforced polymer component, More preferably it can be present in an amount not exceeding about 15-25% by weight.

The same cross-linking agents as described above for the core can be used in this embodiment to achieve the desired modulus of the resilience polymer-reinforced polymer blend. In some embodiments, the cross-linking agent is added in an amount of about 1 to about 50 parts per 100 parts polymer blend, preferably about 20 to about 45 parts, more preferably about 30 to about 40 parts per 100 parts polymer blend.
Rebound resilience polymer component, reinforcing polymer component, free radical initiator, and all other materials used to form the intermediate layer of the golf ball core according to the present invention can be obtained by any type of mixing known to those skilled in the art. Can be combined.
The intermediate layer can also be made from the composition disclosed in US Pat. No. 5,688,191, the disclosure of which is incorporated herein by reference and is set forth in Table 2 below. I will give you.

The golf ball cover material cover provides the ball and club interface. Desirable properties for the cover are in particular good moldability, high peel resistance, high tear strength, high impact resilience, and good release properties.
For embodiments having the polyurea composition of the present invention as a core or intermediate / inner cover layer, the cover composition can include one or more homopolymer or copolymer materials as described above for the intermediate layer material.
In some embodiments, at least one cover layer comprises the polyurea composition of the present invention. In another aspect of the invention, saturated polyurea is used to produce a cover layer, preferably an outer cover layer, which can be selected from both castable thermosetting and thermoplastic polyureas. . In this embodiment, the saturated polyurea is substantially free of aromatic groups or moieties, as described above.
Preferably, the cover composition comprises from about 1% to about 100% polyurea or saturated polyurea, which is the reaction product of at least one polyisocyanate, polyetheramine, and at least one curing agent. Manufacture from things. In some embodiments, the cover composition is made from a blend of about 10% to about 90% polyurea or saturated polyurea and about 90% to about 10% other polymers and / or other materials. In other embodiments, the cover composition comprises from about 10% to about 75% polyurea or saturated polyurea and from about 90% to about 25% other polymers and / or other materials, such as those listed above. Including.

Additional Materials Additional materials can be added to the compositions of the present invention and can be added to the conventional materials described for the manufacture of the core, interlayer and cover layer.
For example, fillers can be added to the compositions of the present invention to affect rheological and mixing properties, specific gravity (ie, density-modified filler), elastic modulus, tear strength, reinforcement, and the like. Fillers are generally inorganic and suitable fillers are numerous substances, metal oxides and salts such as zinc oxide and tin oxide, and barium sulfate, zinc sulfate, calcium carbonate, zinc carbonate, barium carbonate, clay, tungsten, tungsten carbide, Includes a series of silicas, reground products (recycled cores typically ground to about 30 mesh particles), high Mooney viscosity rubber reground materials, and mixtures thereof.

  The composition of the present invention can be further foamed by the addition of at least one physical or chemical blowing agent. By using a foamed polymer, a golf ball designer can adjust the density or mass dispersion of the ball to adjust the angular moment of inertia, thus adjusting the rotational speed and operation of the ball. Useful blowing agents include but are not limited to: organic blowing agents such as 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-toluene Sulphonyl semicarbide; barium azodicarboxylate; butylamine nitrile; nitrourea; trihydrazinotriazine; phenyl-methyl-uranium; p-sulfone hydrazide; Lium.

Furthermore, the foam composition of the present invention can be produced by blending the microspheres and the composition during or after the molding process. Polymer, ceramic, metal and glass microspheres are useful in the present invention and can be solid or hollow and filled or unfilled. In particular, microspheres having a diameter of up to about 1000 μm are useful.
Either injection molding or compression molding can be used to produce a layer or core containing foamed polymeric material.
Other materials conventionally included in golf ball compositions can be added to the compositions of the present invention, namely polyurea polyurethanes, ionomers, polybutadienes, and mixtures thereof. These additional materials include, but are not limited to: colorants, reaction enhancers, crosslinking agents, whitening agents, UV absorbers, sterically hindered amine light stabilizers, antifoaming agents, processing aids, and Conventional additives. Antioxidants, stabilizers, softeners, plasticizers including internal and external plasticizers, impact modifiers, excipients, reinforcing substances and admixtures can also be added to the compositions of the present invention. All these materials are known in the art and are added in typical amounts for their usual purposes.

Golf Ball Construction The composition of the present invention can be used in the construction of any type of ball. For example, depending on the type of desired operating characteristics of the ball, the ball may be a one-piece, two-piece, or three-piece design, a dual core, a double cover, one or more intermediate layers, a multilayer core, and / or A multilayer cover may be used. As used herein, the term “multilayer” means at least two layers. For example, the compositions of the present invention can be used in a golf ball core, in an intermediate layer, and / or in a cover, each of which can have a single layer or multiple layers.
As described above in the section of the core, the core can be a one-piece core or a multilayer core, both of which can be solid, semi-solid, hollow, fluid-filled or powder-filled. A multi-layer core is a core having an innermost component with one or more additional core layers disposed on the core. For example, FIG. 1 shows a golf ball having a core 2 and a cover 3. In one embodiment, the golf ball of FIG. 1 represents a cover 3 comprising a polybutadiene reactant or other conventional material core 2 and a polyurea composition of the present invention. In another embodiment, the golf ball of FIG. 1 represents a core 2 made from a polybutadiene reactant and a cover 3 comprising the saturated polyurea composition of the present invention.

Further, if the golf ball of the present invention includes an intermediate layer, such as an inner cover layer or an outer core layer, i.e. one or more layers disposed between the inner core and the outer cover of the golf ball, For example, it may be incorporated into a single layer or multilayer cover, a one-piece core or multilayer core, both a single layer cover and core, or both a multilayer cover and multilayer core. Similar to the core, the intermediate layer may further include a plurality of layers. It will be appreciated that any number or type of interlayer may be used as desired.
FIG. 2 shows a multi-layer golf ball 11 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 can include a polybutadiene reactant core 12, an intermediate layer 14, and a cover 13 made from the polyurea composition of the present invention, where the polyurea is saturated. It is preferable. Further, the golf ball 21 of FIG. 3 has a core 22 of polybutadiene reactive material or conventional core material, at least one ionomer intermediate layer 24, and a cover 23 containing at least one saturated polyurea.

The intermediate layer can also be a tensioned elastic material wrapped around a solid, semi-solid, hollow, fluid-filled, or powder-filled center. From the viewpoint of the present invention, the wound layer can also be referred to as a core layer or an intermediate layer. As an example, the golf ball 31 of FIG. 4 can include a core layer 32, a tensioned elastic layer 34 wound thereon, and a cover layer 33. In particular, the golf ball 31 of FIG. 4 may have a core 32 made from a polybutadiene reaction product, an intermediate layer 34 containing a tensioned elastic material, and a cover 33 containing at least one saturated polyurethane. The tensioned elastic material can be made from any suitable material known to those skilled in the art. In still another aspect, the wound liquid center golf ball 41 of FIG. 5 includes a hollow spherical core shell 42 filled with a liquid 43 inside a hollow, a rubber thread layer 44 including a tensioned elastic material, and at least one. It has a cover 45 containing two saturated polyureas.
In some embodiments, the tensioned elastic material incorporates the polybutadiene reaction product described above. The tensioned elastic material can also be produced from conventional polyisoprene. In other embodiments, the polyurea compositions of the present invention are used to produce tensioned elastic materials. A tensioned elastic material is further produced from the solvent-spun polyether urea described in US Pat. No. 6,149,535 or the high-tensile filament disclosed in co-pending US Patent Publication No. 2002/0160859. And the disclosure of which is incorporated herein in its entirety.

In certain embodiments, a tensioned elastic material is coated with a binding material, as described in US Patent Publication No. 2002/0160862, the entire disclosure of which is incorporated herein by reference.
The intermediate layer can also be made from a binding material and an interstitial material dispersed in the binding material, as described in US Patent Publication No. 2003/0125134, the disclosure of which is hereby incorporated by reference. Are incorporated herein in their entirety. As described in US Pat. No. 5,820,488, at least one of the intermediate layers can further be a moisture barrier layer, which is incorporated herein by reference.
Prior to forming the cover layer, the inner ball, i.e., the core and some intermediate layers disposed thereon, can 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 polishing the external surface of the subassembly. In addition, the inner ball can be corona discharged or plasma treated before the cover is formed around the core. Other layers of the ball, such as the core, may be surface treated. Examples of these and other surface treatment techniques can be found in US Pat. No. 6,315,915, which is hereby incorporated by reference in its entirety.

  Similarly, the cover can include a plurality of layers, such as an inner cover layer disposed around a golf ball center and an outer cover layer formed thereon. For example, FIG. 6 may represent 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 can be made of a polybutadiene reactant, the inner cover layer 54 can be made of an ionomer blend, and the outer cover layer 53 can be made of a polyurea composition. Further, FIG. 7 can represent a golf ball 61 having a core 62, an outer cover 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 made from polybutadiene reactants of different hardness, inner cover layer 64 is made from an ionomer blend, and outer cover layer 63 is made from a polyurea composition. Further, a golf ball 71 shown in FIG. 8 is manufactured using the composition of the present invention, and the ball has a large core 72 and a thin outer cover layer 73. In some embodiments, the large core 72 is made from a polybutadiene reactant and the thin outer cover layer 73 is made from a polyurea composition, preferably an acid functionalized, wherein the acid groups are at least partially neutralized. Yes.

While it is typical to use a hardness gradient in a golf ball to achieve certain properties, the composition of the present invention for use in a golf ball having multiple cover layers with essentially the same hardness is used. The present invention further considers, in which case at least one layer has been modified in some way in order to change the properties that affect the properties of the ball. The structure of these balls is described in co-pending application US patent application Ser. No. 10 / 167,744, filed Jun. 13, 2002, entitled “Golf Ball with Multiple Cover Layers”. The entire disclosure of which is incorporated herein by reference. In this embodiment, both cover layers can be manufactured from the same material and having essentially the same hardness, but the layers have different coefficients of friction, different thicknesses, different rheological properties under high deformation, and / or Or it is designed to have different wettability.
Examples of suitable types of ball configurations that can be used in the present invention include, but are not limited to, those described below: US Pat. Nos. 6,056,842, 5,688,191. No. 5,713,801, No. 5,803,831, No. 5,885,172, No. 5,919,100, No. 5,965,669, No. 5,981,654, Nos. 5,981,658 and 6,149,535 and published US 2001/0009310 A1, US 2002/0025862, and US 2002/0028885. The disclosures of all these patents and patent application publications are incorporated herein by reference thereto.

Layer Formation Method The golf ball of the present invention can be applied to various techniques such as compression molding, flip molding, injection molding, retractable pin injection molding, reaction injection molding (RIM), liquid injection molding (LIM), casting, and vacuum molding. , Powder coating, flow coating, spin coating, dipping, thermal spraying, and the like. An injection molding method using split vent pins can be found in co-pending US Patent Publication 2002/0079615, and examples of retractable pin injection molding are US Pat. Nos. 6,129,881, 6,235, 230, and 6,379,138. All of which are incorporated herein by reference to these molding literature.
Traditionally, compression molding and injection molding have been applied to thermoplastic materials, while RIM, liquid injection molding, and casting have been used for thermosetting materials. These and other manufacturing methods are described in US Pat. Nos. 6,207,784 and 5,484,870, the entire disclosures of which are incorporated herein by reference. For example, when the core is manufactured from a thermosetting material, compression molding is a particularly suitable method for manufacturing the core. On the other hand, in the embodiment of the thermoplastic core, the core can be injection molded. The intermediate layer can also be manufactured using any suitable method known to those skilled in the art. For example, the intermediate layer can be produced by blow molding and covered with a cover layer provided with dimples by injection molding, compression molding, casting, vacuum molding, powder coating or the like.

The castable reactive liquid polyurea material of the present invention is applied to the inner ball using various application techniques well known in the art such as spraying, compression molding, dipping, spin coating, or flow coating. can do. In some embodiments, the castable reactive polyurea is formed on the core using a combination of casting and compression molding. US Pat. No. 5,733,428 discloses a method of forming a polyurethane core on a golf ball core, the entire disclosure of which is incorporated herein by reference. This method relates to casting both thermoplastic and thermosetting materials as a golf ball cover. In this case, since the materials are mixed and introduced into the mold half, the same casting method is adopted. Polyurea compositions can be used.
For example, the polyurea composition is first mixed and the exothermic reaction begins and continues until the material solidifies around the core. It is important to measure the viscosity over time so that the subsequent steps of filling each half of the mold, introducing the core into one half, and closing the mold are performed in a timely manner. Half of the cover melt is centrally located and overall uniformity can be achieved. A suitable viscosity range for the curable urea mixture introduced into the mold half is about 2 Pa · sec (2,000 cP) to about 30 Pa · sec (30,000 cP), preferably about 8 Pa · sec (8,000 cP) to About 15 Pa · sec (15,000 cP).

To begin manufacturing the cover, the prepolymer and hardener are mixed by feeding metered amounts of hardener and prepolymer through the line in a mixing head fitted with a motor driven mixer. Place in the mounting unit using centering pins that fill the upper half of the preheated mold and move to the opening of each mold. Later, the lower mold cavity, or a series of lower mold cavities, is filled with the same amount of mixture as used for the upper mold. After the reaction material is present in the upper half mold for about 40 to about 100 seconds, preferably about 70 to about 80 seconds, the core is dropped to the reaction mixture being gelled at a controlled rate.
A ball cup holds the core of the ball by reduced pressure (or partial vacuum). After gelling for about 4 to about 12 seconds, place the core in half of the mold and release the vacuum to release the core. In some embodiments, after about 5 seconds to about 10 seconds, the vacuum is released to release the core. The mold half with the core and solidified cover half is removed from the centering fixture and inverted to fit the second mold half and the selected amount of reactivity introduced into the second mold The polyurea prepolymer and curing agent begin to gel at an appropriate time before being combined.
Similarly, both US Pat. No. 5,006,297 and US Pat. No. 5,334,673 are suitable for use in applying the castable reactive liquid used in the present invention. Disclosed is a molding technique. However, the method of the present invention is not limited to these techniques, and any other method known to those skilled in the art can be used. For example, other methods of holding the core of the ball can be used instead of using a partial vacuum.

Golf Ball Post-treatment The golf balls of the present invention can be painted, coated, or surface treated to obtain additional benefits. In addition, the outer surface of the ball cover can be marked or otherwise marked, i.e. the pad can be printed, then the marked outer surface is treated with at least one transparent coating to give the ball a gloss finish And protect the mark on the marked cover. The golf balls of the present invention may further be dye sublimated, such as the treatment disclosed in US Patent Publication No. 2003/0106442, laser marking (as disclosed in US Pat. Nos. 5,248,878 and 6,075,223). ), And / or ablation (US Patent Publication 2001/0047986), the entire disclosure of which is incorporated herein by reference.
The use of saturated polyurea and polyurethane in golf equipment can avoid the need for typical post-treatments, such as coating the ball with a coating containing pigments prior to applying the top coat to the golf ball. . Unlike compositions that are not light stable, the compositions used to make the golf equipment of the present invention do not fade when exposed to light, particularly when related or prolonged. Furthermore, by removing at least one coating step, the manufacturer understands the economic benefits in terms of reducing processing time and resulting labor efficiency. In addition, significant reductions in volatile organic compounds (“VOCs”), typically paint components, can be understood through the use of the present invention, which provides significant environmental benefits.
Thus, although it is not necessary to use a pigmented coating on the golf ball of the present invention when made with a saturated composition, the golf ball of the present invention is painted, coated, or surfaced for additional advantages. Can be processed. For example, golf balls manufactured and painted in accordance with the present invention exhibit enhanced color stability when the surface coating degrades during normal play. Today, the mainstream technique used to emphasize whiteness is to produce white-tone covers with titanium dioxide, such as corona treatment, plasma treatment, UV treatment, flame treatment, or electron beam treatment. The treatment is performed on the cover and a transparent paint that can contain a fluorescent whitening agent is applied to one or more layers.

Golf Ball Properties Golf ball properties of the present invention, such as hardness, elastic modulus, core diameter, intermediate layer thickness and cover layer thickness, are determined by the play characteristics of the golf ball of the present invention, such as rotation, initial speed and feel. Has been found to affect For example, the flexural modulus and / or tensile modulus of the intermediate layer is considered to affect the “feel” of the golf ball of the present invention.

Component Size The size, ie, thickness and diameter, of the components of the golf ball can be varied depending on the desired properties. For the purposes of the present invention, any thickness of the layer can be used. Examples of the various aspects outlined above are provided with respect to layer dimensions, but are not limited thereto.
The present invention relates to golf balls of all sizes. The USGA regulations limit the size of a competition golf ball to exceed 1.68 inches in diameter, but any size golf ball can be used for play golf play. . The preferred diameter of the golf ball is from about 1.68 inches to about 1.8 inches. A more preferred diameter is from about 1.68 inches to about 1.76 inches. A diameter of from about 1.68 inches to about 1.74 inches is most preferred, but in any case from about 1.7 inches to about 1.95 inches. ) Range of diameters can be used. Preferably, the total diameter of the core and all intermediate layers combined is about 80% to about 98% of the total diameter of the finished ball.

The core may have a diameter ranging from about 0.09 inches to about 1.65 inches. In one embodiment, the diameter of the core of the present invention is from about 1.2 inches to about 1.630 inches. In other embodiments, the core has a diameter of about 1.3 inches to about 1.6 inches, preferably about 1.39 inches to about 4.064 cm (1). .6 inches), more preferably from about 1.5 inches to about 1.6 inches. In yet another aspect, the core has a diameter of about 1.55 inches to about 1.65 inches.
The core of the golf ball may be extremely large relative to the rest of the ball. For example, in certain embodiments, the core comprises from about 90% to about 98% of the ball, preferably from about 94% to about 96% of the ball. In this embodiment, the core diameter is preferably about 1.54 inches or greater, preferably about 1.55 inches or greater. In some embodiments, the core diameter is about 1.59 inches or greater. In other embodiments, the core diameter is about 1.64 inches or less.

Where the core includes an inner core layer and an outer core layer, the inner core layer is preferably about 0.9 inches or larger and the outer core layer is preferably about 0.1 inches. Or a greater thickness. In some embodiments, the inner core layer has a diameter of about 0.09 inches to about 1.2 inches and the outer core layer has a diameter of about 0.1 inches. It has a thickness of about 2.032 cm (0.8 inches). In yet another aspect, the inner core layer has a diameter of about 0.095 inches to about 1.1 inches and the outer core layer is about 0.20 inches. It has a thickness of about 0.03 inches.
The cover typically has a thickness that provides sufficient strength, good operating characteristics and durability. In some embodiments, the cover has a thickness of from about 0.02 inches to about 0.35 inches. The cover preferably has a thickness of about 0.02 inches to about 0.12 inches, preferably about 0.1 inches or less. When a golf ball outer cover is manufactured using the composition of the present invention, the cover is about 0.154 cm or less, preferably about 0.07 inch or less. Has a smaller thickness. In some embodiments, the outer cover has a thickness of about 0.02 inches to about 0.07 inches. In other embodiments, the cover has a thickness of about 0.127 cm (0.05 inch) or less, preferably about 0.02 inch to about 0.05 inch. . In yet another aspect, the outer cover layer of the golf ball is from about 0.02 inches to about 0.045 inches. In yet another aspect, the outer cover layer is from about 0.025 inches to about 0.04 inches thick. In some embodiments, the outer cover layer is about 0.03 inches thick.

  The golf ball intermediate layer has a wide range of thicknesses, which has great potential when using the intermediate layer, i.e., as an outer cover layer, an inner cover layer, a wound layer, and a humidity / vapor barrier layer. Because there is. For use with 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 certain embodiments, the thickness of the intermediate layer is from about 0.002 inches to about 0.1 inches, preferably about 0.01 inches or greater. In some embodiments, the intermediate layer thickness is about 0.09 inches or less, preferably about 0.06 inches or less. In other embodiments, the intermediate layer has a thickness of about 0.127 cm (0.05 inches) or less, more preferably from about 0.0254 cm (0.01 inches) to about 0.1143 cm (0.045 inches). It is. In some embodiments, the thickness of the intermediate layer is from about 0.02 inches to about 0.04 inches. In other embodiments, the thickness of the intermediate layer is from about 0.025 inches to about 0.035 inches. In yet another aspect, the thickness of the intermediate layer is about 0.035 inches. In yet another aspect, the thickness of the inner cover layer is from about 0.03 inches to about 0.035 inches. Combinations with varying thickness ranges of the intermediate layer and the outer cover layer can be used in combination with other embodiments described herein.

The ratio of the thickness of the intermediate layer to the outer cover layer is preferably about 10 or less, preferably about 3 or less. In other embodiments, the ratio of the thickness of the intermediate layer to the outer cover layer is about 1 or less.
The core and one or more intermediate layers together form an inner ball, preferably about 1.48 inches in diameter for a 1.68 inch ball. Greater than. In one embodiment, the inner ball of a 1.68 inch ball has a diameter of about 1.52 inch or greater. In another aspect, the inner ball of a 1.68 inch ball has a diameter of about 1.66 inch or less. In yet another aspect, a 1.772 inch (or larger) ball has an internal ball with a diameter of about 1.50 inches or larger. In yet another aspect, the inner ball diameter of a 1.772 inch ball is about 1.70 inches or less.

Hardness Many golf balls are composed of a plurality of layers having different hardnesses, eg, gradients in hardness, to achieve the desired operating characteristics. The present invention contemplates a golf ball having a layer having the same hardness as the golf ball having a hardness gradient between the layers.
One skilled in the art should particularly understand that there is a fundamental difference between “material hardness” and “hardness measured directly on a golf ball”. The hardness of a material is defined by the procedure described in ASTM-D2240 and generally includes measuring the hardness of a “slab” or “button” made from the material whose hardness is to be measured. When measured directly on a golf ball (or other spherical surface), the hardness is a completely different measurement and therefore exhibits different hardness values. This difference arises from a number of factors including the composition of the ball (ie, core type, number of core and / or cover layers, etc.), ball (or sphere) diameter, and material composition of adjacent layers. However, it is not limited to these. The two measurement techniques are not linearly correlated and therefore one hardness value cannot be easily related to the other value.

The core of the present invention can have a hardness that varies depending on the configuration of the particular golf ball. In some embodiments, the hardness of the core is at least about 15 Shore A, preferably about 30 Shore A, as measured on the manufactured sphere. In other embodiments, the core has a hardness of about 50 Shore A to about 90 Shore D. In yet another aspect, 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 hardness of one or more intermediate layers of the present invention can vary depending on the particular configuration of the ball. In some embodiments, the intermediate layer has a hardness of about 30 Shore D or greater. In other embodiments, the intermediate layer has a hardness of about 90 Shore D or less, preferably about 80 Shore D or less, and more preferably about 70 Shore D or less. In yet another aspect, the intermediate layer has a hardness of about 50 Shore D or greater, preferably about 55 Shore D or greater. In some embodiments, the intermediate layer has a hardness of about 55 Shore D to about 65 Shore D. The intermediate layer may be about 65 Shore D or greater.

If the intermediate layer is intended to be harder than the core layer, the ratio of hardness of the intermediate layer to the core is preferably about 2 or less. In some embodiments, this ratio is about 1.8 or less. In other embodiments, the ratio is about 1.3 or less.
As with the core and intermediate layer, the hardness of the cover can vary depending on the configuration and desired characteristics of the golf ball. The ratio of the hardness of the cover to the inner ball is uniquely variable and is used to control the aerodynamics of the ball, particularly the rotation of the ball. In general, the harder the internal 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 part in the ball, for example from about 50 Shore D to about 75 Shore D, the cover material is measured on the slab to be about 20 Shore D. Or greater, preferably about 25 Shore D or greater, more preferably about 30 Shore D or greater. In other embodiments, the cover itself has a hardness of about 30 Shore D or greater. In particular, the cover can be about 30 Shore D to about 60 Shore D. In some embodiments, the cover has a hardness of about 40 Shore D to about 65 Shore D. In other embodiments, 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 some embodiments, the cover has a hardness of about 30 Shore D to about 40 Shore D.

In embodiments where 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 layer material to the intermediate layer material is about 0.8 or less, preferably about 0.75 or less, More preferably about 0.7 or less. In other embodiments, the ratio is about 0.5 or less, preferably about 0.45 or less.
In yet another aspect, the ratio is about 0.1 or less if the cover and interlayer material have substantially the same hardness. The cover can have a hardness of about 55 Shore D to about 65 Shore D if the hardness difference between the cover layer and the intermediate layer is intended to be insignificant. In this embodiment, the ratio of the Shore D hardness to the outer cover intermediate layer is about 1.0 or less, preferably about 0.9 or less.

The hardness of the cover can be defined in terms of Shore C. For example, the cover can have a hardness of about 70 Shore C or greater, preferably about 80 Shore C or greater. In other embodiments, the cover can have a hardness of about 95 Shore C or less, preferably about 90 Shore C or less.
In other embodiments, 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.
If a two-piece ball is configured, the core may be softer than the outer cover. For example, the hardness of the core can be in the range of about 30 Shore D to about 50 Shore D, and the hardness of the cover can be about 50 Shore D to about 80 Shore D. In such mold configurations, the ratio between the hardness of the cover and the hardness of the core is preferably about 1.75 or less. In other embodiments, 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 ratio of the hardness of the cover to the core is preferably about 1.25. Or smaller.

The compression value depends on the diameter of the component to be measured. The Atti compression of a golf ball core or core portion 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” is defined as the measurement of the deviation of an object or material relative to the calibrated spring deviation with an Atti Compression Gauge. Available through the market from Atti Engineering Corp. of Union City, New Jersey. In other embodiments, the core compression is from about 40 to about 80, preferably from about 50 to about 70. In yet another aspect, the core compression is preferably less than about 50, more preferably less than about 25.
In another small compression aspect, 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, cores made in accordance with the present invention may be smaller than atti compression gauge measurements.
In one aspect, the golf balls of the present invention preferably have an Atti compression of 55 or greater, preferably from about 60 to about 120. In another aspect, the golf ball of the present invention has an Atti compression of at least about 40, preferably from about 50 to about 120, more preferably from about 60 to 100. In yet another aspect, the golf ball of the present invention has a compression of about 75 or greater 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 limit on golf ball COR, the initial velocity of a golf ball cannot exceed 76.2 ± 1.5 m / s (250 ± 5 feet / second (ft / s)). Thus, in some embodiments, the initial speed is about 74.676 m / s (245 ft / s) or greater, and about 77.724 m / s (255 ft / s) or greater. In other embodiments, the initial speed is about 76.2 m / s (250 ft / s) or greater. In some embodiments, the initial speed is from about 77.1144 m / s (253 ft / s) to about 77.4192 m / s (254 ft / s). In yet another aspect, the initial speed is about 77.724 m / s (255 ft / s). While current rules require golf ball manufacturers to stay within this limit for initial speed, those skilled in the art will understand that the golf ball of the present invention will immediately convert to a golf ball with an initial speed outside this range. Will do.
As a result of the initial speed limitation by the USGA, the goal is to maximize the COR without exceeding the 77.724 m / s (255 ft / s) limit. The present invention contemplates golf balls having a COR of about 0.7 to about 0.85. In some embodiments, the COR is about 0.75 or greater, preferably about 0.78 or greater. In other embodiments, the ball has a COR of about 0.8 or greater. Further, the inner ball preferably has a COR of about 0.780 or greater. In some embodiments, the COR is about 0.790 or greater.

Flexural Modulus Accordingly, the golf ball of the present invention preferably has an intermediate layer having a flexural modulus of from about 3.447 MPa (500 psi) to about 3447.4 MPa (500,000 psi). More preferably, the flexural elasticity of the intermediate layer is from about 6.895 MPa (1,000 psi) to about 1723.7 MPa (250,000 psi). Most preferably, the flexural modulus of the intermediate layer is from about 13.790 MPa (2,000 psi) to about 1379.0 MPa (200,000 psi).
The flexural modulus of the cover layer is preferably about 13.790 MPa (2,000 psi) or greater, more preferably about 34.474 MPa (5,000 psi) or greater. In some embodiments, the flexural modulus of the cover is from about 68.948 MPa (10,000 psi) to about 1034.2 MPa (150,000 psi). More preferably, the cover layer has a flexural modulus of about 103.42 MPa (15,000 psi) to about 827.4 MPa (120,000 psi). Most preferably, the cover layer has a flexural modulus of about 124.11 MPa (18,000 psi) to about 758.42 MPa (110,000 psi). In other embodiments, the flexural modulus of the cover layer is about 689.5 MPa (100,000 psi) or less, preferably about 551.6 MPa (80,000 psi) or less, more preferably about 482.6 MPa ( 70,000 psi) or less. In certain embodiments, when the cover layer has a hardness of about 50 Shore D to about 60 Shore D, the cover layer preferably has a flexural modulus of about 379.2 MPa (55,000 psi) to about 448.2 MPa (65,000 psi). Have
In some embodiments, the ratio of the flexural modulus to the cover layer of the intermediate layer is from about 0.003 to about 50. In another aspect, the flexural modulus ratio of the intermediate layer to the cover layer is about 0.006 to about 4.5. In yet another aspect, the ratio of flexural modulus to the cover layer of the intermediate layer is about 0.11 to about 4.5.

Adhesive Strength The adhesive strength or peel strength of the composition of the present invention is preferably about 5 or greater. In some embodiments, the adhesive strength is about 446.4 kg / m (25 lb / in) or less. For example, the adhesive strength is preferably about 178.6 kg / m (10 lb / in) or greater and about 357.2 kg / m (20 lb / in) or less.
Shear Resistance / Cut Resistance The cut resistance of a golf ball cover can be determined using a shear test with 1-9 steps to assess breakage and appearance. In some embodiments, the stage of failure is preferably about 3 or less, more preferably about 2 or less. In other embodiments, the stage of failure is about 1 or less. The stage of appearance of the golf ball of the present invention is preferably about 3 or less. In some embodiments, the stage of appearance is about 2 or less, preferably 1 or less.
The light stability of the photostable cover can be quantified by the difference in yellowness (ΔYI), ie the yellowness measured after a given exposure time minus the yellowness before the exposure field. In some embodiments, ΔYI is about 10 or less after 5 days of exposure (120 hours), preferably about 6 or less after 5 days of exposure, more preferably about 4 or less after 5 days of exposure. In some embodiments, ΔYI is about 2 or less after 5 days of exposure, more preferably about 1 or less after 5 days of exposure. The difference in the b color dimension ( ^* b ^* , yellow to blue) is also a way to quantify the light stability of the cover. In some embodiments, ^* b ^* after 5 days (120 hours) exposure is about 4 or less, preferably about 3 or less after 5 days of exposure, more preferably about 2 or less after 5 days of exposure. . In some embodiments, ^* b ^* after 5 days exposure is about 1 or less.

^*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ナートとポリテトラメチレンエーテルグリコールの反応生成物である。
^**HCC-19584はホーウィック ケミカル（Harwick Chemical）社が製造する白−青着色剤分散物である。
米国特許第５，７３３，４２８号の教示に従って上記の組成物から製造したカバーを有するゴルフボールを製造した。得られたボールの物理特性及び作動特性を表４に示す。

EXAMPLES The following examples merely illustrate preferred embodiments of the present invention and are not to be construed as limiting the invention, the scope of the invention being defined by the appended claims. Unless otherwise indicated, parts represent parts by mass.
Example 1: Saturated Polyurethane Golf Ball Cover Table 3 shows the ingredients used to make a saturated polyurethane golf ball cover composition.

^* Prepolymer is the reaction product of 4,4'-dicyclohexylmethane diisocyanate and polytetramethylene ether glycol.
^** HCC-19584 is a white-blue colorant dispersion manufactured by Harwick Chemical Company.
A golf ball having a cover made from the above composition was made according to the teachings of US Pat. No. 5,733,428. Table 4 shows the physical characteristics and operating characteristics of the balls obtained.

The following QUV tests were further performed on balls molded from the compositions listed in Table 4.
Method :
ASTM G 53-88 “Standard procedure for light and water-exposure equipment (fluorescent UV-concentrated) for exposure to non-metallic materials” was followed with minor modifications as follows.
Q-Panel model OUV / SER accelerated weathering manufactured by Q-Panel Lab Products, Cleveland, Ohio, with 6 types of balls to be evaluated in special golf ball holders Inserted into the sample shelf of the sex tester. The sample holder was positioned so that, at the closest point, each ball was approximately 1.75 inches from the UVA-340 ball. Then, the weather resistance test was conducted by repeating every 4 hours between the following two sets of conditions (specific total time is 24, 48, and 120 hours).
Condition 1: The temperature of the warm bath is set to about 50 ° C., the UV lamp is turned on, and the irradiation power is set to 1.00 W / m ² / mm and controlled.
Condition 2: The temperature of the warm bath is about 40 ° C., and the UV lamp is turned off.

Color was measured using a BYK-Gardner model TCS II spherical spectrophotometer fitted with a 25 mm port before the weathering test and after each time cycle. AD65 / 10 ° irradiation was used in a mode that included specular reflectance.
Molded test results after irradiation 24 h UV balls shown in Table 5, where, [Delta] L ^* is equal to the difference in the L dimension (light to dark), the difference in .DELTA.a ^* is a color dimension (red to green) Δb ^* is equal to the difference in the b color dimension (yellow to blue), ΔC ^* is equal to the combined chromaticity difference (a ^* and b ^* scale), hue and saturation, and ΔH ^* is saturation and emission. Is equal to the difference in total hues, with the effect of ΔE ^* equal to the overall color difference, ΔWI equals the difference in whiteness, and ΔYI equals the difference in yellowness.

成形したボールを１２０時間ＵＶ照射した後の試験結果を表７に示す。

Table 6 shows the test results after the molded balls were irradiated with UV for 48 hours.

Table 7 shows the test results after the molded balls were irradiated with UV for 120 hours.

^* シェア試験の段階評価：１〜９の段階に基づく、１は最良、９は最悪。 Example 2: Diol-cured H ₁₂ MDI polyether urea Prepared from a composition containing a prepolymer made from H ₁₂ MDI and polyoxyalkylene and having a molecular weight of about 2000, cured with 1,4-butanediol. A golf ball having a cover was produced. The physical properties and ball operating characteristics of the obtained are listed in Table 8. As in Example 1, a light stable aliphatic polyurethane golf ball was used for comparison.

^* Share test stage evaluation: 1 is the best, 9 is the worst, based on stages 1-9.

^* シェア試験の段階評価：１〜９の段階に基づく、１は最良、９は最悪。
先に引用した特許及び特許出願の全てを、それに言及することによってその全てを本明細書に取り込む。
明細書に記載し特許請求の範囲に記載した発明は、本明細書に開示した特定の態様にその範囲が限定されることはなく、それはこれらの態様が本発明のいくつかの特定の態様を説明することを意図しているからである。均等な態様の全ては本発明の範囲に含まれることを意図している。実際、本明細書に示しかつ記載した変形に加えて種々の変形が、本明細書の先の記載から当業者にとって明らかとなろう。これらの変形も添付の特許請求の範囲の範囲にはいることを意図している。 Example 3: include H ₁₂ MDI polyether urea H ₁₂ MDI and prepolymers made from polyoxyalkylene cured with a diamine, the composition having a molecular weight of about 2000, 4,4'-bis - (sec-butylamino A golf ball having a cover made by curing with) -dicyclohexylmethane (Clearlink 1000) was produced. The physical properties and ball operating characteristics of the resulting material are listed in Table 9. As in Example 1, a light stable aliphatic polyurethane golf ball was used for comparison.

^* Share test stage evaluation: 1 is the best, 9 is the worst, based on stages 1-9.
All of the previously cited patents and patent applications are hereby incorporated by reference herein.
The invention described in the specification and set forth in the claims is not limited in scope to the specific embodiments disclosed herein, as these embodiments define some specific embodiments of the present invention. This is because it is intended to explain. All equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description of this specification. These modifications are also intended to fall within the scope of the appended claims.

FIG. 1 is a cross-sectional view of a two-piece golf ball, where the cover is made from a composition comprising at least one polyurea. FIG. 2 is a cross-sectional view of a multi-component golf ball, wherein at least the cover is made from a composition comprising at least one polyurea. FIG. 3 is a cross-sectional view of a multi-component golf ball wherein the cover is made from a composition containing at least one polyurea and the intermediate layer is made from a composition containing at least one ionomer resin. FIG. 4 is a cross-sectional view of a multi-component golf ball including a core and a cover, where the core is made of a tensioned elastic material and the cover is made from a composition that includes at least one polyurea. Yes. FIG. 5 is a cross-sectional view of a golf ball having a liquid center, wherein the liquid core is taken up by a tensioned elastic material, and the cover is manufactured from a case containing at least one polyurea. . FIG. 6 is a cross-sectional view of a multi-component golf ball including a core, a thin inner cover layer, and a thin outer cover layer disposed thereon, the cover being made from a composition comprising at least one polyurea. . FIG. 7 is a cross-sectional view of a multi-component golf ball including a core, an outer core layer, a thin inner cover layer, and a thin outer cover layer disposed thereon, wherein the cover is from a composition comprising at least one polyurea. It is manufactured. FIG. 8 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 made from a composition that includes at least one polyurea.

Claims (15)

A golf ball comprising at least one cover layer produced from a composition comprising a polyurea prepolymer comprising a polyetheramine and at least one polyurea produced from an amine-terminated curing agent. The golf ball of claim 1, wherein the polyurea prepolymer further comprises at least one diisocyanate.   The golf ball of claim 2, wherein the diisocyanate is saturated and the saturated diisocyanate is selected from the group consisting of: ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene Diisocyanate; tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate; 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-diisocyana Cyclohexane-1,4-diisocyanate; methyl-cyclohexylene 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; isocyanate Ethylcyclohexane isocyanate; bis (isocyanatomethyl) -cyclohexanediisocyanate; 4,4′-bis (isocyanatomethyl) dicyclohexane; 2,4′-bis (isocyanatomethyl) dicyclohexane Isophorone diisocyanate; triisocyanate of HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexane diisocyanate; 4,4′-dicyclohexylmethane diisocyanate; 2,4-hexahydrotoluene Diisocyanates; 2,6-hexahydrotoluene diisocyanates; and mixtures thereof.   4. The golf ball of claim 3, wherein the saturated diisocyanate is selected from the group consisting of: isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, or A combination of these.   The golf ball of claim 2, wherein the diisocyanate is selected from the group consisting of: araliphatic isocyanate; meta-tetramethylxylene diisocyanate; para-tetramethylxylene diisocyanate; polyisocyanate Quantified isocyanurate; dimerized ureasione of polyisocyanate; modified polyisocyanate; and mixtures thereof. The golf ball of claim 1 , wherein the polyether amine is selected from the group consisting of: polytetramethylene ether diamine, polyoxypropylene diamine, poly (oxypropylene terminated ethylene oxide) ether diamine, triethylene glycol diamine, Propylene oxide based triamines, trimethylolpropane based triamines, glycerin based triamines, and mixtures thereof. The golf ball of claim 6, wherein the polyetheramine has a molecular weight of 1000 to 3000 . The golf ball of claim 1 or 2 , wherein the amine-terminated curing agent is selected from the group consisting of: ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; tetrahydroxypropyleneethylenediamine; , 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); diethyleneglycol 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamine; Bis-propylamine; monoethanolamine, diethanolamine; triethanolamine; monoisopropanolamine, diisopropanolamine; isophoronediamine; and mixtures thereof.   The golf ball of claim 1, wherein the composition further comprises a catalyst selected from the group consisting of: bismuth catalyst, zinc octoate, di-butyltin dilaurate, di-butyltin diacetate, tin (II) chloride, tin (IV ) Chloride, di-butyltin dimethoxide, dimethyl-bis [1-oxonedecyl) oxy] tin, di-n-octyltin bis-isooctyl mercaptoacetate, triethylenediamine, triethylamine, tributylamine, oleic acid, acetic acid; delayed catalyst, And mixtures thereof. The golf ball of claim 9 , wherein the catalyst is present from 0.005% to 1% of the composition. The golf ball of claim 1, wherein the cover layer has a difference in yellowness of 12 or less after exposure to ultraviolet light for 5 days in accordance with ASTM G 53-88 . The golf ball of claim 1, wherein the cover layer has a difference in b color dimension of 6 or less after 5 days of exposure to ultraviolet light according to ASTM G 53-88 . The golf ball of claim 1, wherein the cover layer has a thickness of 0.02 inches to 0.035 inches . Polyurea prepolymer
Ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene diisocyanate; tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate; octamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate; cyclobutane-1 , 3-diisocyanate; cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methyl-cyclohexylene diisocyanate; 2,4-methyl Cyclohexanedi 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 (isocyanatomethyl) -cyclohexanediisocyanate; 4,4′-bis (isocyanatomethyl) 2,4′-bis (isocyanatomethyl) dicyclohexane; isophorone diisocyanate; triisocyanate of HDI; tri of 2,2,4-trimethyl-1,6-hexanediisocyanate A diisocyanate selected from the group consisting of and mixtures thereof; Soshianato; 4,4'-dicyclohexylmethane diisocyanate; 2,4-hexa hydro-toluene diisocyanate; 2,6-hexahydrotoluene diisocyanate
Polytetramethylene ether diamine, polyoxypropylene diamine, poly (oxypropylene terminated ethylene oxide) ether diamine, triethylene glycol diamine, propylene oxide based triamine, trimethylolpropane based triamine, glycerin based triamine, and these The golf ball of claim 1, wherein the golf ball is a reaction product with a polyetheramine selected from the group consisting of a mixture. The golf ball according to claim 1, wherein the at least one cover layer is manufactured by casting, injection molding, or reaction injection molding.

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