JP2002315850A - Wound golf ball having cast polyurethane cover - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a golf ball and a method for forming the golf ball including a center formed of material containing a polybutadiene and having a high resilience, at least one cover layer formed of material containing a polyurethane and at least one wound layer consisting of thread material disposed between the center and the cover. SOLUTION: The polyurethane compound is formed of a reaction product of a prepolymer of at least one polyisocyanate and a polyol and a diamine hardener. The polybutadiene compound includes a butadiene polymer having a resilience index of exceeding about 40 and a weight average molecular weight of greater than about 200,000. Such golf ball has a recovery rate optimized for players slow in a swing speed. The wound layer enables to achieve desired golf ball characteristics when applied to golf balls having liquid or solid centers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present application was filed on July 2, 2000.
Application No. 09 / filed 5th and currently pending
625,544, which is a continuation-in-part application, filed on December 9, 1998, now US Pat. No. 6,132,342, application no.
No. 7,690, which is filed in 199
Filed on May 27, 1995 and now filed in US Pat.
No. 5,863,788, which is U.S. Pat.

[0002] The present invention relates generally to golf balls, and more particularly to a golf ball having at least a center, a cover, and a wound layer having at least one thread disposed between the center and the cover. The present invention relates to a thread wound golf ball. The cover can be formed from a polymer blend that includes a polyurethane compound,
The core can include a polybutadiene blend. In the golf ball of the present invention, the speed is improved, and the resilience is provided, so that the flight distance of a player having a low swing speed can be increased.

[0003]

2. Description of the Related Art Conventional golf balls can be roughly classified into two types. That is, it is a solid ball or a wound ball. The differences in play characteristics provided by these different types of structures are significant. Solid-structured balls are popular with golfers for being extremely durable while maximizing distance. Solid balls are generally
It is formed by surrounding a solid core, usually formed from crosslinked rubber, with a cover material. Such a solid core is typically formed from polybutadiene, which is chemically cross-linked with zinc diacrylate and / or a similar cross-linking agent. In addition to a one-piece solid core, a solid core can include multiple outer layers, such as a dual-core golf ball or the like. The cover is typically an ionomer material such as SURLYN®, which is available from E.M., Wilmington, Del. I. DuPont de Nemours (EI Du)
Pont De Nemours & Co. of W
(Ilmington, DE). The cover is typically a single layer, but can also include one or more layers, such as a double cover with an inner cover layer and an outer cover layer.

[0004] The combination of a solid core and an ionomer cover material provides a ball that is both durable and abrasion resistant. Further, such a combination increases the initial velocity of the ball, thereby increasing the distance. However, these materials are so robust that solid balls have a hard "feel" when hit with a club. Similarly, due to its structure, the spin rate tends to be relatively slow, increasing the distance and increasing the tee-off accuracy.

[0005] Currently, some golfers prefer wound balls in the spin and feel afforded by the structure of wound golf balls. Wound balls have a spherical solid rubber center or liquid center around which an elastomeric thread is wound in a number of yards taut. The wound core is then covered with a durable cover material such as SURLYN® or a similar material or a soft cover material such as balata or polyurethane. Wound balls are generally soft, spin more,
This allows a skilled golfer to further control the flight distance and landing position of the ball. In particular, in the approach shot to the green, the high spin rate of the soft thread-wound ball allows the golfer to stop the ball near the landing position.

[0006] To manufacture wound golf balls, manufacturers can use a winder during the winding process to stretch the elastic yarn to various degrees of elongation without unnecessarily damaging the elastic yarn. . In general, the compression and initial velocity of the ball increase as elongation and winding tension increase. Thus, a more resilient wound ball is created, which is desirable.

[0007] The thread of a thread-wound golf ball is typically formed by a calender and slit method rather than by an extrusion method. Calendered yarns typically have a rectangular cross section, while extruded yarns typically have a circular cross section.

[0008] A number of different windings have been disclosed for use in golf balls. Cloppenberg
U.S. Patent No. 4,473,229 to Nburg et al.
A golf ball having a core formed of graphite fiber and a winding filament formed of graphite filament and resin is disclosed. The yarn, or yarns,
Formed of graphite filament and resin, four or more yarns are combined to form the final yarn for use in the winding thread. U.S. Pat. No. 5,713,801 to Aoyama discloses the use of a layer of high tensile modulus fibers wrapped around a core. The tensile modulus of such fibers is at least 10,000
ksi (10,000,000 psi). Also,
U.S. Pat. No. 5,816,9 to Hamada et al.
No. 39 has a residual ratio of tensile strength of at least 70%,
Hysteresis loss is 50% or less and elongation is 9
A rubber thread or thread (t) of from 00 to 1400%
head).

Prior art wound golf balls and cores use a thread of polyisoprene rubber to provide a
It is typically wrapped around the core with an elongation of ~ 1000%. The amount of thread required for one golf ball is determined by the elasticity of the thread in a stretched state. The elastic modulus of the stretched polyisoprene thread is typically between 10,000 psi and 20,000 psi. In addition, the characteristics of a wound ball or core at a particular resilience depend on how closely the threads are wound during winding. The packing density is controlled by the thread size and the winding pattern. State of the art polyisoprene threads are measured before winding and have a width of at least 0.15875.
cm (1/16 inch), 0.0508 cm thick
(0.02 inches). However, current technology polyisoprene threads typically have thicknesses of 0.03556 cm to 0.06096 c.
m (0.024 inch).

US Pat. No. 6,149,535 discloses a thread for a wound yarn having at least about 10 strands having a maximum diameter of about 0.01 inch. Preferably, it comprises at least 26 strands having a diameter of less than about 0.002 inch (0.00508 cm). The smaller the diameter of the thread, the higher the winding density. Preferably, the elastic modulus of the thread, when wound around the center, is greater than 20 ksi. Preferably, the maximum elongation of the thread is greater than about 8%.

[0011] A variety of golf balls are devised by the manufacturer to provide a wide range of playing characteristics such as compression, speed, "feel" and spin. In addition to ionomers, one of the most commonly used polymers is polybutadiene, and more specifically, polybutadiene having a high cis-ionomer concentration.

[0012] The use of high cis-concentration polybutadiene, especially in combination with a hard cover material, results in a very elastic and robust golf ball. These high-elasticity golf balls have a relatively hard "feel" when hit with a club. However, soft "feel" golf balls composed of high cis-polybutadiene can also be produced and tend to have low resilience. Various other polybutadiene formulations have been adjusted in an effort to provide improved golf balls, and are described below.

US Pat. No. 3,239,228 discloses a solid golf ball having a core and a cover molded from a high sulfur content polybutadiene rubber. The polybutadiene content of such a core is 25 to 100 percent cis-1,4-polybutadiene and trans-1,4-polybutadiene.
It is stereocontrolled to a composition in which the polybutadiene is 0 to 65 percent and the remainder is polybutadiene in the vinyl configuration. A preferred embodiment of the polybutadiene golf ball core is 35
It contains percent cis-polybutadiene, 52 percent trans-polybutadiene and 13 percent vinyl-polybutadiene. It is disclosed that the level of trans- and vinyl content is not critical to the overall playing characteristics of the polymer blend.

British Patent No. 1,168,6069 discloses a molding compound for molding an improved golf ball core and containing cis-polybutadiene as a basic polymer component. Such a core polymer component comprises at least 60 percent of cis-polybutadiene;
Typically, the balance is trans- or vinyl-form polybutadiene. In a preferred embodiment, the core polybutadiene component comprises 90 percent of the cis-configuration and the remaining 10 percent is a trans- or vinyl-configuration polybutadiene.

US Pat. Nos. 3,572,721 and 3,572,722 disclose a solid, one-piece or two-piece golf ball, which comprises:
It has a core and a cover. The cover material can include any of a number of materials or blends thereof, such materials or blends are known to those skilled in the art and include trans-polybutadiene, wherein the polybutadiene has at least 90 percent And the rest is of the cis- and / or vinyl-configuration.

British Patent No. 1,209,032 discloses a two-piece or three-piece golf ball having a core and a cover. The cover or cover material can be any crosslinkable material. In particular, such materials are polymers or copolymers of butadiene or isoprene. Suitably, such a polymer component is a polybutadiene having a cis-content of greater than 50 weight percent.

US Pat. No. 3,992,014 discloses a one-piece solid golf ball. The golf ball material is typically polybutadiene;
The polybutadiene has a configuration selected to be at least 60 percent, with the remaining 40 percent being trans-polybutadiene and / or 1,2-polybutadiene (vinyl) isomer.

US Pat. No. 4,692,497 cures a diene polymer containing polybutadiene and a metal salt of an α, β ethylene (α, β ethylenically) unsaturated acid using at least two free radical initiators. A golf ball and a material thereof are disclosed.

US Pat. No. 4,931,376 discloses a method for making butadiene polymers for use in a variety of applications, including golf ball cover materials. 1 of such invention
In an embodiment, a blended polymeric resin material comprising at least 30 weight percent trans-polybutadiene polymer is disclosed as a two-piece ball golf ball cover. In a preferred embodiment, the golf ball cover material comprises a blend comprising 30 to 90 weight percent of the trans-polybutadiene polymer.

US Pat. No. 4,971,329 discloses a polybutadiene mixture formed from cis-1,4 polybutadiene and 1,2 polybutadiene, a metal salt of an unsaturated carboxylic acid, an inorganic filler and a free radical initiator. An actual golf ball is disclosed. Such mixtures have from about 99.5 to about 95 weight percent cis-1,4 polybutadiene and from about 0.5 to about 5 weight percent 1,2 polybutadiene.

US Pat. No. 5,252,652 discloses a one-piece or multi-layer golf ball core with improved flight characteristics, wherein the core is formed from a rubber compound,
Such a compound is a base rubber, preferably 1,4-polybutadiene having an cis-content of at least 40 mole percent, metal salts of unsaturated carboxylic acids, organic peroxides, and organic sulfur compounds and / or Or it consists of those metal salts. Such organic sulfur compounds and / or metal salts are present in an amount of about 0.0
Typically, it is present in an amount of 5 to 2 parts by weight, and the organic peroxide is typically present in an amount of about 0.5 to 3 parts by weight based on 100 parts of the total polymer component. It is a target.

EP 0 577 058 discloses a golf ball comprising a core and a cover, said cover comprising:
Formed as two separate layers. The inner layer of the cover
Molded on the core and formed from ionomer resin. The outer layer of the cover is molded over the inner layer and formed from a blend of natural or synthetic balata and a crosslinkable elastomer such as polybutadiene. In one embodiment of the outer layer of the cover, the elastomer is 1,4-polybutadiene having at least 40 percent of the cis-structure, with the remaining 60 percent being the trans-isomer. Preferred embodiments include at least 90 percent cis-structure, and more preferably include at least 95 percent cis-structure.

US Pat. No. 5,421,580 has a liquid center contained in a center bag, a rubber thread layer formed on the liquid center, a layer around which the thread is wound, and a cover on the liquid center. The disclosed thread wound golf ball is disclosed. Such a cover material may comprise trans-polybutadiene and / or 1,2-
The cover may be any of a number of materials including polybutadiene (vinyl) or blends thereof, such that the cover has a JIS-C hardness of 70-85 and is preferably a suitable transformer. Percentages are not disclosed.

US Pat. No. 5,697,856 is a solid golf ball having a core and a cover, wherein the core has a cis-polybutadiene structure content of 90 before vulcanization.
Disclosed are solid golf balls produced by vulcanizing a base rubber compound that includes greater than or equal to percent butadiene rubber. The amount of the trans-polybutadiene structure after vulcanization is 10 to 30%, and if it exceeds 30%, it is said that a resilience performance is too low, resulting in a too soft core, which is not preferable, and that the golf ball performance is lowered. ing. Such cores comprise vulcanizing agents, fillers, organic peroxides and organosulphur (organosul).
fur).

GB 2,321,021 discloses a solid golf ball having a core and a cover formed on the core and having a two-layer cover structure of an inner layer and an outer layer. The outer cover layer is made of a rubber composite material,
The rubber composite contains 0.05 to 5 parts by weight of an organic sulfide compound. The core rubber composition comprises a base rubber, a crosslinker, a heterocrosslinker, an organic sulfide and a filler, said base rubber being preferably 1,4-polybutadiene having a cis-content of at least 40% by weight. is there. The crosslinker is an organic peroxide, typically present in an amount of 0.3 to 5 parts by weight, and the heterocrosslinker is a metal salt of an unsaturated fatty acid,
Typically it is present in an amount of 10 to 40 parts by weight.
The organic sulfide compound is typically present at 0.05 to 5 parts by weight.

US Pat. No. 5,816,944 is a solid golf ball having a core and a cover, wherein the core has a JIS-C hardness of 50 to 80 and the cover has a shore of 50 to 60. It has a D hardness. The core material comprises a vulcanized rubber such as cis-polybutadiene with a crosslinking agent, an organic peroxide, an organic sulfur compound and / or an organic sulfur compound containing a metal, and a filler.

In addition, conventional polymers have high percentages of Firestone Corp.
p. Has a trans-polybutadiene conformation, such as DIENE35NF, which is composed of 40 percent cis-isomer and 50 percent trans-polybutadiene isomer, and Shell Corp.
position) CARIFLEX BR1220
And Asahi Chemical (Asahi Chemical)
Co. ) Typically have a mixture of high cis- and high-trans-butadiene isomers, such as FUREN 88, and do not yield high resilience values, and are therefore undesirable.

The most common polymers used by manufacturers and others to modify the properties of golf ball layers and / or covers are E.M. I. SYRLYN commercially available from DuPont / De Nemours
And the like. However, manufacturers have recently investigated the use of alternative polymers such as polyurethane. For example, U.S. Pat. No. 3,147,324 relates to a method for manufacturing a golf ball having a polyurethane cover.

Polyurethane has been recognized as a useful material for golf ball covers since about 1960. Polyurethane formulations are the product of the reaction of a curing agent and a polyurethane prepolymer, the reaction product of the polyurethane prepolymer itself, a polyol and a diisocyanate. The curing agents used previously are typically diamines or glycols. Catalysts are often used to accelerate the reaction between the curing agent and the polyurethane prepolymer.

[0030] Since 1960, various companies have explored the benefits of polyurethane as a golf ball cover material. U.S. Pat. No. 4,123,061 teaches a golf ball formed from a polyurethane prepolymer of polyether and a curing agent such as a trifunctional polyol, a tetrafunctional polyol or a diamine. US Patent 5,3
No. 34,673 discloses the formation of golf ball covers and, in particular, golf balls covered with thermoset polyurethane using two categories of commercially available polyurethanes, thermoset and thermoplastic polyurethanes. The golf ball covered with the thermosetting polyurethane is formed from a blend of a polyurethane prepolymer and a slow reacting amine curing agent, and / or a difunctional glycol. The first commercially available and successful polyurethane-covered golf ball was Titleist® Professio, first launched in 1993.
nal (registered trademark).

Unlike golf balls covered with SURLYN® or other ionomers, polyurethane golf ball covers can be formulated to have the softer “feel” of golf balls covered with balata. However, conventional golf ball covers formed from polyurethane have SURLY for rebound which is a function of resilience or, in part, the initial velocity of the golf ball after being hit with a golf club.
It was not completely comparable to a golf ball covered with N®.

US Pat. No. 3,989,568 discloses a three-component system using one or two polyurethane prepolymers and one or two polyols or a fast-reacting diamine curing agent. The reactants selected for such a system must have different reaction rates in two or more competing reactions.

US Pat. No. 4,123,061 discloses a golf ball formed from a polyurethane prepolymer and a curing agent, wherein the curing agent comprises a trifunctional polyol,
Examples are tetrafunctional polyols or fast-reacting diamine curing agents.

US Pat. No. 5,334,673 is formed from a blend of a polyurethane prepolymer and a slow reacting polyamine curing agent and / or a difunctional glycol. It has been found that the shear and cut resistance of the resulting golf ball is improved compared to a cover formed from Balta or SURLYN®.

US Pat. No. 5,692,974 discloses a method of using a cationic ionomer in a golf ball cover formulation. The patent further relates to a golf ball having a cover and a core enclosing a urethane ionomer. The resilience and initial rate can be improved by adding an alkylating agent such as t-butyl-chloride containing ionic interactions to the polyurethane to form a cationic type ionomer.

International Patent Application No. WO 98/37929 discloses a formulation for a golf ball cover, wherein the formulation comprises a diisocyanate / polyol prepolymer and a curing agent, wherein the curing agent comprises a slow reacting diamine. And a blend of fast reacting diamines. "Feel", playability and durability are improved.

[0037]

Accordingly, it is desirable to produce golf balls having low compression, ie, softness, while having resilience equal to or greater than conventional golf balls. Alternatively, it would be desirable to achieve greater or less resilience while maintaining compression equal to or less than conventional.

[0038]

SUMMARY OF THE INVENTION A golf ball of the present invention includes a center, a cover layer, and a wound layer, wherein the center is formed from a polybutadiene material or a reaction product thereof and has a molecular weight of greater than about 200,000. And one or more layers comprising a material having a resilience index of at least about 40, wherein said cover layer comprises 7.5
A polyurethane compound formed from a prepolymer having less than or equal to percent by weight of unreacted isocyanate groups or a reaction product thereof, and wherein the wound layer has at least one layer disposed between the center and the cover. Yarn or thread material, each thread having at least
It has one strand.

[0039]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thread wound golf ball having a high resilience that increases the distance from the tee while conforming to the USGA Golf Rules, for example, for players with low swing speeds. Methods for measuring golf ball resilience are well known to those skilled in the art. One way to measure the resilience of a ball when struck is to use an air cannon or other means of propelling the ball at a speed comparable to that of a golf club head. The ball is fired at a solid block mass and measures the reciprocating speed. Such a speed can be measured using a light screen and measures the time required for the ball to travel a certain distance. Dividing the fixed distance by the travel time equals the average velocity of the ball traveling the fixed distance. The ratio between the forward speed and the return speed is commonly referred to as the recovery rate ("COR"). COR is a direct measure of the resilience of a golf ball at a particular return speed. Since the behavior of the golf ball is linear and viscoelastic, the return ball speed is functionally equal to the club swing speed. The present invention, in one embodiment, aims to maximize the COR of a player with a slow swing speed. Such a player swings the club at a slow swing speed to hit the ball. Therefore, there is a tendency that the speed of the ball after hitting becomes slow and the distance after teeing off becomes short.

The golf ball of the present invention includes a center, a cover layer, and a wound layer, wherein the center is formed from a polybutadiene material or a reaction product thereof, has a molecular weight of more than about 200,000, and has a resilience index of at least about 200,000. The cover layer comprises a polyurethane formulation formed from a prepolymer having up to 7.5 weight percent unreacted isocyanate groups or a reaction product thereof. And wherein the wound layer includes at least one thread or thread material disposed between the center and the cover, each thread having at least one strand.

The present invention further provides a center, a wound layer surrounding the center, an inner cover layer surrounding the wound layer and having a first hardness, and a first cover layer surrounding the inner cover layer and the first cover layer. An outer cover layer having a second hardness less than the hardness and having a thickness less than about 0.05 inches.

In one embodiment, the cover material has at least one of a dimple coverage of greater than about 60 percent, a hardness of about 10 to 80 Shore D, or a flexural modulus of greater than about 500 psi, and the golf ball has , About 30
Has a compression of ~ 120. In one embodiment, the cover material hardness is about 35 to 70 Shore D. In another embodiment, the resilience index is greater than about 50. The flexural modulus is measured by the method of ASTM D-6272-98.
In yet another embodiment, the golf ball has a compression of about 50-110.

In one embodiment, the cover includes an inner cover layer and an outer cover layer, wherein the inner cover layer is disposed between the wound layer and the outer cover layer. In one embodiment, the inner cover layer is harder than the outer cover layer. In yet another embodiment, the inner cover layer includes at least one thermoplastic material.

In one embodiment, the polyurethane formulation includes at least one isocyanate and at least one curing agent. In yet another embodiment, the polyurethane formulation includes at least one isocyanate, at least one polyol, and at least one curing agent. In a preferred embodiment, the isocyanate is 4,4'-diphenylmethane diisocyanate, polymeric 4,4'-diphenylmethane diisocyanate, carbodiimide-modified liquid 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, p- Phenylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, p-
Methyl xylene diisocyanate, m-methyl xylene diisocyanate, o-methyl xylene diisocyanate, or mixtures thereof. In another preferred embodiment, the at least one polyol comprises a polyether polyol, a hydroxy-terminated polybutadiene, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, or a mixture thereof. In yet another preferred embodiment, the curing agent comprises a polamine curing agent, a polyol curing agent, or a mixture thereof. In a more preferred embodiment, the curing agent comprises a polyamine curing agent. In the most preferred embodiment,
The polyamine curing agent is 3,5-dimethylthio-2,4-
Toluenediamine or an isomer thereof, 3,5-diethyltoluene-2,4-diamine or an isomer thereof, 4,4′-bis- (sec-butylamino) -diphenylmethane, 1,4-bis -(Sec-butylamino) -benzene, 4,4-methylene-bis- (2-chloroaniline), 4,4'-methylene-bis- (3-chloro-2,6-diethylaniline), trimethylene glue Chole-di-p-aminobenzoate, polytetramethylene oxide-di-p-aminobenzoate, N, N'-
Dialkyldiaminodiphenylmethane, p, p'-methylenedianiline, phenylenediamine, 4,4'-methylene-bis- (2-chloroaniline), 4,4'-methylene-bis- (2,6-diethylaniline), 4,4 '
-Diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 2,2 ', 3,3'-tetrachlorodiaminodiphenylmethane, 4,4'-methylene-bis- (3-chloro-2,6 -Diethylaniline), or mixtures thereof.

In different preferred embodiments, the curing agent comprises a polyol curing agent. In a more preferred embodiment, the polyol curing agent is ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol,
Polypropylene glycol, low molecular weight polytetramethylene ether glycol, 1,3-bis (2-hydroxyethoxy) benzene, 1,3-bis- [2- (2-hydroxyethoxy) ethoxy] benzene, 1,3-bis-
{2 [2- (2-hydroxyethoxy) ethoxy] ethoxy} benzene, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, resortinol-di- (β-hydroxyethyl) ether, Hydroquinone-di- (β-hydroxyethyl) ether, trimethylolpropane, or mixtures thereof.

In one embodiment, the prepolymer comprises about 2.5
And up to 7.5 weight percent of unsaturated isocyanate groups. In another embodiment, the thickness of the cover layer is:
Less than about 0.05 inches. In yet another embodiment, the center Mooney
y) The viscosity is from about 40 to about 80. In a preferred embodiment, the Mooney viscosity is from about 45 to about 60.

In another embodiment, the polybutadiene material has a vinyl-isomer content of less than about 2 weight percent. In another embodiment, and in addition to the preceding examples, the cis-isomer content of the polybutadiene is at least about 95 weight percent.

In one embodiment, the outer diameter of the center is at least about 1.3 inches (about 3.32 cm), and preferably about 1.3 inches to about 3.937 cm (about 1.33 cm).
Inches to 1.55 inches). In one preferred embodiment, the outer diameter of the center is between about 3.4036 and 3.556.
cm (approximately 1.34 to 1.4 inches). In another embodiment, the center comprises a material formed from a conversion reaction of polybutadiene having a first amount of the trans-isomer, a source of free radicals, and at least one cis-to-trans catalyst. In a preferred embodiment, the reaction is carried out at a constant temperature and at a constant temperature sufficient to form a polybutadiene reaction product having a second amount of the trans-isomer greater than the first amount of the trans-isomer. Get up over time. In one embodiment, the cis-to-trans catalyst comprises an organosulfur compound, an inorganic sulfur compound, an aromatic organometallic compound, a metal-organosulfur compound, tellurium,
Contains at least one of selenium, elemental sulfur, polymeric sulfur, or an aromatic organic compound. Preferably,
The catalyst comprises an organic sulfur component, and in one preferred embodiment, the catalyst comprises 4,4'-diphenyl disulfide, 4,4'-
At least one of ditolyl disulfide or 2,2'-benzamide diphenyl disulfide or a combination thereof. Typically, the cis-to-trans catalyst is present in an amount of about 0.1 to 10 parts per 100 parts of polybutadiene.

In one embodiment, an additional intermediate layer is further included between the center and the cover layer, the intermediate layer comprising polybutadiene having a first amount of trans-polybutadiene, a source of free radicals and at least A material formed from a conversion reaction of a cis-to-trans catalyst containing one organic sulfur component, wherein the outer diameter of the intermediate layer is at least about 4.0.
The center is 132 cm (about 1.58 inches), and the outer diameter of the center is less than about 3.937 cm (about 1.55 inches).

In another embodiment, the cover includes an inner cover layer and an outer cover layer, wherein the inner cover layer is disposed between the wound layer and the outer cover layer. In a preferred embodiment, the thickness of at least one of the inner and outer layers is about 0.05 inches. In another preferred embodiment, the inner cover layer comprises an ionomer resin, polyurethane, polyetherester, polyetheramide, polyester, dynamically vulcanized elastomer, polyurea, a functionalized styrene butadiene elastomer, a metallocene. polymer,
Including nylon, acrylonitrile butadiene-styrene copolymer, or blends thereof.

In one embodiment, the outer diameter of the inner cover is at least about 1.55 inches.
In another embodiment, the outer diameter of the inner cover is about 4.0132
cm to about 4.1656 cm (about 1.58 inches to about 1.64 inches). In one embodiment, the polyurethane used to form one or both layers is a thermoplastic or thermoset.

1 for a player with a slow swing speed
In an embodiment, the rate of recovery when hitting the golf ball with the golf club head at a speed of 160 feet / second is at least about 0.76, and the magnitude of the rate of recovery to the return speed is at least about 0.16. 001 seconds / feet.

The present invention also provides a center comprising at least a polybutadiene having a molecular weight of greater than about 300,000 and a resilience index of at least about 40, surrounding the center and having an outer diameter of at least about 3.8354 cm.
(About 1.51 inches) and including at least one thread material between the center and the cover, wherein each thread has at least one strand;
An inner cover layer surrounding the outer core layer, and an outer cover layer disposed around the inner cover layer and including a polyurethane formulation formed from a prepolymer having less than 7.5 weight percent unreacted isocyanate groups. And a golf ball having the same.

The present invention also provides a center comprising at least a polybutadiene having a molecular weight of greater than about 300,000 and a resilience index of at least about 40, surrounding the center and having an outer diameter of at least about 3.8354 cm.
(About 1.51 inches) and a hoop stress layer disposed between the center and the cover, wherein the glass, polyamide, aromatic polyamide, carbon, or tensile strength is at least about 250 kpsi; A hoop stress layer comprising metal fibers having a modulus of at least about 10,000 kpsi; and a prepolymer disposed about the wound hoop stress layer and having less than 7.5 weight percent unreacted isocyanate groups. Cover comprising a polyurethane compound.

[0055]Definition  The term "about" is used herein to refer to one or more numbers or numbers.
When used in connection with a range represented by a value, one range
Words about all such numbers, including all numbers in boxes
Should be understood.

As used herein, a substituted and unsubstituted "allyl" group refers to a hydrocarbon ring with a system of conjugated double bonds, typically consisting of 4n + 2π ring electrons. Is an integer. Examples of allyl groups include, but are not limited to, phenyl, naphthyl, anisyl, tolyl, xylenyl, and the like. According to the invention, allyl also includes a heteroallyl group such as, for example, pyrimidine or thiophene. These allyl groups are
It is also possible to substitute with any number of various functional groups. In addition to the functional groups described herein in connection with the carbocyclic group, the functional groups of the allyl group include hydroxy and its metal salts, mercapto and its metal salts, halogen, amino, nitro, cyano and amides, esters, It can include carboxyls, silyls, acrylates and metal salts thereof, including acids and metal salts thereof, sulfonyl or sulfonamides, and phosphates and phosphites, and combinations thereof.

As used herein, “attach compression”
The term is used by Atti Engineering in Union City, NJ
g Corp. of Attach Comp. (Ati Comp., Union City, NJ).
It is defined as the deflection of a given object or material relative to the calibrated spring deflection measured by the response gauge. Atchi compression is typically used to measure the compression of a golf ball. 1.680 inches (4.2672 cm) in diameter using an attach gauge
When measuring a core less than 4.2672c, use metal or other suitable shims to measure the diameter of the object to be measured.
m (1.680 inches). However, when referring to the compression of the core, it is preferred to use a compression load measurement. The term "compressive load" has a diameter of 4.2672 cm (1.68).
Inches) of a spherical object is defined as the nominal load in pounds for a radial deflection of 10.8 percent.

As used herein, the term substituted and unsubstituted "carbocyclic" refers to cyclic carboxyl-containing compounds, including, but not limited to, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and the like. It is not limited. Such a cyclic group may also include
It is possible to include various substituents, in which one or more hydrogen atoms have been replaced by functional groups. Such functional groups include those described above and low acryl groups having from 1 to 28 carbon atoms. The cyclic groups of the present invention can further comprise heteroatoms.

As used herein, “cis-two-
The "trans catalyst" is a catalyst which converts at least a portion of the cis-polybutadiene isomer into a trans-
Means those combinations that convert to polybutadiene.
Such a combination of cis-isomer, trans-isomer and any vinyl-isomer measured at any given time is 10
It should be understood that it consists of zero percent polybutadiene.

As used herein, the term "recovery rate"("COR") of a golf ball is defined as the ratio of the rebound speed to the return speed when the ball is fired at a rigid plate. You. The return speed is 125
Feet / second.

As used herein, “dynamic stiffness”
The term is defined as the load divided by the deflection of a 1.4 mm spherical radius probe for penetration testing oscillating at a frequency of 1 Hz and an amplitude of 100 μm. The probe dynamically penetrates the surface of the sample material. A sample of the spherical core material was cut into 6 mm thick layers along the equator of the core to create a 6 mm thick disk containing the core geometry center on one surface. The probe can be set at any selected radial position on the disk to obtain a measure of dynamic stiffness. Accurate dynamic measurements can be achieved by keeping the material sample at a substantially uniform temperature. Dynamic stiffness was measured by TA Instruments Corp., Newcastle, Delaware.
oration of New Castle, DE)
Obtained using a dynamic mechanical analyzer, model DMA2980, commercially available from R & D Corporation. DMA29
The device settings for 80 are 1 Hz frequency and 100 μm amplitude
m, the static load was 0.3 N, and the automatic stress was 105 percent. The 1.4 mm spherical radius probe is DMA2
It is commercially available from TA Instruments as 980 penetration kit accessories. The DMA 2980 is equipped with a temperature controlled chamber that allows testing at a wide range of ambient temperatures.

The methods and equipment used to measure "dynamic stiffness" can also be used to measure loss tangent. Loss tangent is the ratio between the loss modulus and the storage modulus. The loss tangent is the portion of the elastic modulus out of phase due to the displacement, and the storage elastic modulus is the portion of the elastic modulus out of phase with the displacement. DMA 2980 automatically calculates and reports the loss tangent.

[0063] The term "fluid" as used herein includes liquids, pastes, gels, gases, or any combination thereof.

"Component-mediated groups (Group VI
"A component" or "Group VIA element" means a component that includes a sulfur, selenium, or tellurium component, or a combination thereof.

As used herein, “sulfur component”
The term refers to a component that is elemental sulfur, polymeric sulfur, or a combination thereof. Furthermore, the term "elemental sulfur" means a cyclic structure S _8, "polymeric sulfur" refers to a structure including at least one additional sulfur for elemental sulfur.

As used herein, the term “molecular weight” is defined as the absolute weight average molecular weight. The molecular weight is determined by the following method. That is, about 20 mg
Polymer in 10 mL of tetrahydrofuran ("TH
F "). This can take a few days at room temperature, depending on the molecular weight and distribution of the polymer. Filter and degas 1 liter of THF into a high performance liquid chromatography ("HPLC") container. The HPLC flow rate was set to 1 via a Viscogel separation tube.
Set to mL / min. The non-outflow mixed bed separation tube model GMH _HR- H has an inner diameter of 7.8 mm, a length of 300 mm and is available from Viscotek Corp. of Ho, Houston, Texas.
uston, TX). The THF flow is set at 1 mL / min for at least 1 hour before starting sample analysis or until a stable detector baseline is obtained. During the purging of this separation tube and detector, Viscot
Set ek's TDA model 300 triple detector at 40 ° C. This detector is also commercially available from Viscotek. Thermal equilibrate the three detectors (ie, refractive index, differential pressure, and light scattering) and the separation tube, and scavenge and zero the detectors and calibrate the instrument according to the instructions provided with the instrument Get ready. A 100 μL known aliquot or aliquot of the sample solution is then injected into the instrument and the molecular weight of each sample can be calculated using Viscotek's triple detector software. When measuring the molecular weight of the polybutadiene material, 0.130
Dn / dc is always used. While this device and method provides the molecular weight numbers described and claimed herein, other devices or methods do not necessarily provide equivalent values as used herein.

As used herein, the term “multilayer” means at least two layers and includes a fluid or liquid center ball, a wound ball, a hollow center ball, and at least two intermediate layers and a cover layer. Including balls with.

As used herein, the term known as "parts per hundred" or "phr" is 1
It is defined as the number of parts of a particular component in the mixture relative to 00 parts by weight of total polymer components. Mathematically, this can be expressed as 100 times the weight of one component divided by the total weight of the polymer.

As used herein, the term “resilience index” refers to the difference between the loss tangent (tan σ) measured at 10 cpm and 1000 cpm divided by 990 (frequency span) and divided by 100,000 (normalized And for convenience of unit). Loss tangent is from Alpha Technology, Akron, Ohio.
Measurements are made using RPA2000 manufactured by Technologies, Akron, OH). PRA20
00 is set to sweep from 2.5 to 1000 cpm at a temperature of 100 ° C. using a 0.5 degree arc. An average of the six loss tangent measurements is obtained for each frequency, and the average is used to calculate the resilience index. The calculation of the resilience index is as follows. Resilience index = 100,000 · [(loss tangent at 10 cpm) − (loss tangent at 1000 cpm)] / 9
90

As used herein, the term "substantially free" refers to less than about 5 weight percent, preferably less than about 3 weight percent, more preferably less than about 1 weight percent, Most preferably, it means less than about 0.01 weight percent.

[0071]

DETAILED DESCRIPTION OF THE INVENTION In forming a golf ball core, intermediate and mantle layers and / or covers, the use of a polyurethane compound according to the present invention allows the speed of golf balls made with such a compound to be increased by (1) SURLYN. (Registered trademark)
Up to the speed seen in the golf ball covered with
And (2) speeds can be increased to higher than those shown when using alternative urethane formulations. Also,
It is desirable to combine a polyurethane cover formulation with a polybutadiene core material, especially if the resilience index is greater than about 40 and if there is at least one wound layer between the core and the cover. Cores formed from these polybutadiene materials
It has been found to provide exceptional resilience characteristics without compromising performance characteristics.

Therefore, according to the present invention, an improved golf ball can be manufactured as follows. That is,
(A) The polybutadiene reaction product is contained in the center to reduce the molecular weight of the polybutadiene product to about 200,000.
And a resilience index of at least about 40, and (b) placing a wound layer of taut material around the center and optionally one or more wound layers between the wound layer and the center. Place the layers,
And (c) disposing a cover including at least one layer including a polyurethane material.

Referring to FIGS. 1 and 2, golf balls 10 and 18 according to the present invention are illustrated. The golf ball is a thread-wound golf ball having a high resilience and providing a ball that can extend the distance after teeing off, which is useful for a player having a low swing speed. These slow swing speed players typically swing the club at a slow swing speed to hit the ball, and thus the ball's initial speed after hitting is low and the distance after teeing off is short.

Referring to FIG. 1, a golf ball 10 according to the present invention is illustrated. The golf ball has a center 1
2, including a cover 14 and a layer 16 of windings disposed between the center and the cover. As shown in FIG.
The center of such a golf ball is solid. The center may comprise thermoset solid rubber spheres, thermoplastic solid spheres, wood, cork, metal or any suitable material available or known to those skilled in the art. The center is covered with a wound layer and a cover according to the invention.

Due to the desired properties, balls made in accordance with the present invention can exhibit substantially higher resilience or recovery ("COR") with lower compression or modulus than conventional balls. . In addition, the ball manufactured according to the present invention also has a
Substantially the same or higher resilience or COR can be achieved without increasing compression. Another means of measuring this resilience is “loss tangent” or tan σ, which is obtained by measuring the dynamic stiffness of an object. Terms related to loss tangent and such dynamic properties are: A
It is typically represented according to STM D4092-90. Therefore, a lower loss tangent indicates higher resilience, and thus higher rebound capability. When the loss tangent is low, most of the energy given to the golf ball from the club becomes dynamic energy,
That is, the flight speed is converted to the launch speed, and the flight distance becomes longer.
The stiffness or compression stiffness of a golf ball can be measured, for example, by dynamic stiffness. Higher dynamic stiffness indicates higher compression stiffness. To produce a golf ball having the desired compression stiffness, the dynamic stiffness of the crosslinked polybutadiene reaction product should be about 50,0 at -50 ° C.
It must be less than 00 N / m. Preferably, the dynamic stiffness is between about 10,000 and 40,000 N at -50 ° C.
/ M, more preferably about 20,000 at -50 ° C.
To 30,000 N / m.

The dynamic stiffness is in some sense similar to the dynamic modulus. Dynamic stiffness is determined by the geometry of the probe, as described herein, while dynamic modulus is a unique material property independent of geometry.
Dynamic stiffness is a unique factor that allows quantitative measurement of dynamic modulus and accurate measurement of loss tangent at discrete points within a sample article. In the case of the present invention, such an article is at least part of a golf ball core. Preferably, the polybutadiene reaction product has a loss tangent of about 0.1 at -50 ° C, and more preferably about 0.1 at -50 ° C.
07.

[0077] The center formulation preferably comprises at least one rubber material, such rubber material having a resilience index of at least about 40. Preferably, the resilience index is at least about 50. A comparison of a number of polybutadiene polymers is provided in Table 1 below. Polymers that produce elastic golf balls and are therefore suitable for use in the center or other portion of the golf balls of the present invention include CB23, CB22, BR60 and 120.
Including but not limited to 7G. In order to clarify how to calculate the resilience index,
Measured the resilience index. CB23 is available from Bayer Corporation of Akron, Ohio.
commercially available from Tion of Akron, OH). In CB23, for example, the resilience index is calculated as follows. CB23 resilience index = 100,000
[(0.954)-(0.407)] / 990 CB2
Resilience index of 3 = 55

The molding method and composition of the portion of the golf ball typically results in a gradient in material properties. The methods used in the prior art generally use hardness to quantify these gradients. Hardness is a quantitative measure of the static modulus and does not represent the modulus of the material at the rate of deformation associated with the use of a golf ball, i.e., the impact of a club. As known to those skilled in the art of polymer science,
It is possible to emulate alternative deformation rates using the time-temperature juxtaposition principle. At a portion of a golf ball containing polybutadiene, a 1 Hz vibration at a temperature between 0 ° C. and −50 ° C. is qualitatively considered to be equivalent to the impact speed of the golf ball. Therefore, by measuring the loss tangent and dynamic stiffness at 0 ° C. to −50 ° C., it is possible to accurately predict the performance of a golf ball at a temperature of preferably about −20 ° C. to −50 ° C. Become.

The hardness of the polybutadiene material of the golf ball is typically at least about 15 Shore A, preferably about 30 Shore A to 80 Shore D, and about 50 Shore A to 60 Shore D. Is more preferable. In one preferred embodiment, the center hardness of the golf ball center at the geometric center is about 20 to 85 Shore C, preferably about 40 to 80 Shore C, and about 60 to 70 Shore C.
Is more preferable. The hardness of the surface of the golf ball center is typically higher than the hardness of the geometric center of the golf ball center. For example, a golf ball center having a hardness at the center of 65 Shore C, that is, the hardness of the surface of the sphere is about 80 to 85 Shore C. The specific gravity of the polybutadiene material of the golf ball is 0.1.
It is typically above 7, and preferably above about 1.

The Mooney viscosity of the unvulcanized rubber such as polybutadiene of the golf ball produced by the present invention is about 4
Typically from 0 to about 80, from about 45 to about 6
Preferably it is 0, more preferably from about 45 to about 55. Mooney viscosity is ASTM D-16
Typically measured according to 46-99.

At least one of the center or optional intermediate layer contains a reaction product, the reaction product comprising a cis-trans catalyst, an elastic polymer component comprising polybutadiene, a source of free radicals. And optionally a crosslinking agent, a filler or both. Preferably, the polybutadiene reaction product is used to form at least a portion of the center of a golf ball, and the fabrication of the center is further described below in this example. Preferably, such a reaction product has a first dynamic stiffness measured at -50 ° C and a second dynamic stiffness measured at 0 ° C, wherein the first dynamic stiffness is 2 less than about 130 percent of the dynamic stiffness. More preferably, the first dynamic stiffness is less than about 125 percent of the second dynamic composite. Most preferably, the first dynamic composition is less than about 110 percent of the second dynamic composition.

Accordingly, the present invention also includes a method of converting a cis-isomer of a polybutadiene elastomeric polymer component to a trans-isomer during a molding cycle to form a golf ball. Various combinations of polymers, cis-to-trans catalysts, fillers, crosslinkers, and free radical sources can be used. In order to obtain a high resilience, low compression center or interlayer, during the molding cycle, high molecular weight polybutadiene having a cis-isomer content of preferably greater than about 90 percent is converted to any point on the golf ball. Alternatively, it is preferred to increase the trans-isomer content at the site to increase the percentage of substantially all or part of the golf ball. More preferably, the cis-polybutadiene isomer has a total polybutadiene content of about 95%.
Present in greater than a percent amount. Without being bound to a particular theory, the 1,2-polybutadiene isomer in both the initial polybutadiene and the reaction product ("vinyl-
Preferably, the amount of "polybutadiene") is small. Typically, the content of vinyl polybutadiene isomer is less than about 7 percent. Preferably, the vinyl polybutadiene isomer content is less than about 4 percent. More preferably, the content of vinyl polybutadiene isomer is about 2
Less than percent. Without being bound by a particular theory, the resulting mobilities of the combined cis- and trans-polybutadiene backbones result in lower modulus and higher resilience of the reaction products and golf balls containing the reaction products.

High Resilience and Low Modulus (Low Compression) Desirable and Beneficial for Golf Ball Play Characteristics
Preferably, high molecular weight cis-1,4-polybutadiene is converted to the trans-isomer during the molding cycle to produce a polymer reaction product exhibiting the following characteristics: "High molecular weight" typically means that the molecular weight average of the polybutadiene material is greater than about 200,000. Preferably, the polybutadiene molecular weight is 25
More than 0,000, more preferably 300,000 to 500,000. Without being bound by theory, the cis-to-trans catalyst serves to convert a portion of the polybutadiene polymer component from the cis-to-trans conformation in connection with the source of free radicals. For cis-to-trans conversion, a cis-to-trans catalyst must be present, and organosulfur or metal containing organosulfur compounds, substituted or unsubstituted aromatic or organic compounds containing no sulfur or metal, inorganic sulfide compounds, aromatics Group organometallic compounds, or mixtures thereof. The cis-to-trans catalyst component can include one or more cis-to-trans catalysts described herein. For example, the cis-to-trans catalyst may be a blend of an organic sulfur component and an inorganic sulfide component.

In one embodiment, the at least one organic sulfur component is substantially free of metals. That is, it typically contains less than about 10 weight percent metal,
Preferably, it contains less than about 3 weight percent metal,
More preferably, it contains less than about 1 weight percent metal, and most preferably, only trace metals, such as less than about 0.01 weight percent. In another embodiment, the organosulfur component does not include any metals.

When referring to the present invention, the term “organosulfur compound” or “organosulfur component” as used herein means at least one of the following:
That is, 4,4'-diphenyl disulfide; 4,4'-
2,2'-benzamide diphenyl disulfide; bis (2-aminophenyl) disulfide; bis (4-aminophenyl) disulfide; bis (3-aminophenyl) disulfide; 2,2'-bis (4-amino 2,2'-bis (3-aminonaphthyl) disulfide; 2,2'-bis (4-aminonaphthyl) disulfide; 2,2'-bis (5-aminonaphthyl) disulfide; 2,2 ' -Bis (6-aminonaphthyl) disulfide; 2,2'-bis (7-aminonaphthyl) disulfide; 2,2'-bis (8-aminonaphthyl) disulfide; 1,1'-bis (2-aminonaphthyl) Disulfide; 1,1'-bis (3-aminonaphthyl) disulfide; 1,1'-bis (3-aminonaphthyl) disulfide 1,1′-bis (4-aminonaphthyl) disulfide; 1,1′-bis (5-aminonaphthyl) disulfide; 1,1′-bis (6-aminonaphthyl) disulfide; 1,1′- Bis (7-aminonaphthyl) disulfide; 1,1'-bis (8-aminonaphthyl) disulfide; 1,2'-diamino-1,2'-dithiodinaphthalene;2,3'-diamino-1,2' Bis (4-chlorophenyl) disulfide; bis (2-chlorophenyl) disulfide; bis (3-chlorophenyl) disulfide; bis (4-bromophenyl) disulfide; bis (2-bromophenyl) disulfide; bis (3 -Bromophenyl) disulfide; bis (4-fluorophenyl) disulfide; bis (4-iodophenyl) disulfide; Bis (2,5-dichlorophenyl) disulfide; bis (3,5-dichlorophenyl) disulfide;
Bis (2,4-dichlorophenyl) disulfide; bis (2,6-dichlorophenyl) disulfide; bis (2,5-dibromophenyl) disulfide; bis (3,5-dibromophenyl) disulfide; bis (2
-Chloro-5-bromophenyl) disulfide; bis (2,4,6-trichlorophenyl) disulfide; bis (2,3,4,5,6-pentachlorophenyl) disulfide; bis (4-cyanophenyl) disulfide;
Bis (2-cyanophenyl) disulfide; bis (4-
Bis (2-nitrophenyl) disulfide; 2,2′-dithiobenzoic acid ethyl ester; 2,2′-dithiobenzoic acid methyl ester; 2,2′-dithiobenzoic acid; 4,
4′-disiobenzoic acid ethyl ester; bis (4
-(Acetylphenyl) disulfide; bis (2-aceterphenyl) disulfide; bis (4-formylphenyl) disulfide; bis (4-carbamoylphenyl) disulfide; 1,1′-dinaphthyl disulfide; 2,2′-di 1,2′-bis (1-chlorodinaphthyl) disulfide; 2,2′-bis (1-bromonaphthyl) disulfide; 1,1′-bis (2-naphthyl disulfide; 1,2′-dinaphthyl disulfide; Chloronaphthyl) disulfide; 2,2′-bis (1-cyanonaphthyl) disulfide; 2,2′-bis (1-acetylnaphthyl) disulfide and the like, or a mixture thereof. Suitable organic sulfur components are 4,4'-diphenyl disulfide; 4,4'-ditolyl disulfide, or
2,2'-benzamide diphenyl disulfide, or a mixture thereof. More preferred organic sulfur components are
4,4'-ditolyl disulfide. The organosulfur cis-to-trans catalyst, when present, is present in an amount sufficient to produce the reaction product and is present in at least about 1
Preferably, it contains 2% of trans-polybutadiene isomer and more than about 32% of trans-polybutadiene, based on the total elastic polymer component.
Typically, polybutadiene isomers are present. In another embodiment, a metal-containing organosulfur component can be used in accordance with the present invention. Suitable metal-containing organosulfur components include, but are not limited to, cadmium, copper, lead, and tellurium analogs of diethyldithiocarbamate, diamildithiocarbamate, and dimethyldithiocarbamate, or mixtures thereof. Not something.

Suitable sulfur or metal free substituted or unsubstituted aromatic organic components include 4,4'-diphenylacetylene, azobenzene or mixtures thereof,
It is not limited to them. The range of the size of the aromatic organic group is preferably C _{6 to} C ₂₀ , more preferably C _{6 to} C ₁₀ . Suitable inorganic sulfides are titanium sulfide, manganese sulfide, and
Including, but not limited to, sulfur analogs of iron, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, tin, and bismuth.

Substituted or unsubstituted aromatic organic compounds
Can also be included in the cis-to-trans catalyst.
Noh. Suitable substituted or unsubstituted aromatic organic components are
(R ₁) XR₃-MR₄− (R₂Has the chemical formula of y)
Including, but not limited to,
Medium, R₁And R₂Is hydrogen or substituted or unsubstituted
Exchange C_1-20Linear, branched or cyclic alk
Or an alkoxy or alkylthio group, or a single,
Multiple or fused ring C₆Or C₂₀Is an aromatic group of
x and y are each an integer from 0 to 5. R₃And R
₄Is a single, multiple, or fused ring C₆Or C₂₄
And M is an azo group or gold
Contains genus components. R₃And R₄Are preferably each C₆
Or C₁₀Selected from aromatic groups, more preferably
Phenyl, benzyl, naphthyl, benzamide and benzo
Selected from thiazyl. R₁And R₂Is preferably
Substituted or unsubstituted C, respectively_1-10Straight, branched
Or cyclic alkyl, alkoxy or alkylthio
Group or C₆Or C₁₀Selected from aromatic groups of
You. R₁, R₂, R₃Or R₄Is replaced by
Such substitutions can include one or more of the following substituents
It is. They include hydroxy and its metal salts;
And its metal salts; halogen; amino, nitro, and sia
And amides; esters, acids and their metal salts
Ruboxyl; silyl; acrylates and metal salts thereof;
Rufonyl or sulfonamide; and phosphate and
Phosphite. When M is a metal component,
Is any suitable elemental metal available to those skilled in the art.
Is also good. The metal may be tellurium or selenium.
Although preferred, they are typically transition metals. One fruit
In embodiments, the aromatic organic compound is substantially metallic
Not included. On the other hand, in another embodiment, the aromatic organic
The und contains no metal.

[0088] The cis-to-trans catalyst may also include component mediated groups. Elemental sulfur and polymeric sulfur are available, for example, from Elastochem Inc. of C, Chardon, Ohio.
Hardon, OH). Representative sulfur catalyst compounds include PB (RM-S) -80 elemental sulfur and PB (CRST) -65 polymer sulfur, each of which is commercially available from Elastchem. Representative tellurium catalysts and representative selenium catalysts are, respectively,
RT Van under the brand names TELLOY and VANDEX
It is commercially available from derbilt.

[0089] The cis-to-trans catalyst is present in the total elastic polymer component in an amount of about 0.1 to 10 parts. Preferably, the cis-to-trans catalyst is typically present in the total elastic polymer component in an amount of about 0.1 to 8 parts. More preferably, the cis-to-trans catalyst is typically present in the total elastic polymer component in an amount of about 0.1 to 5 parts. The cis-to-trans catalyst is present in an amount sufficient to produce the reaction product, increasing the content of trans-polybutadiene isomer, from about 5 percent to about 5 percent, based on the total elastic polymer component. Typically, it will contain 70 percent trans-polybutadiene.

The determination of the trans-isomer content of polybutadiene as referred to herein is achieved as follows. Calibration standards are made using at least two polybutadiene rubber samples (known trans-content, eg, high and low percent trans-polybutadiene).
These samples can be used alone and together to create a ladder or ladder of trans-polybutadiene of at least about 1.5% to 50%, or leave unknown quantities in a blanket; The resulting calibration curve includes at least 13 evenly spaced points.

Using a commercial Fourier Transform Infrared ("FTIR") spectrometer equipped with a photoacoustic ("PAS") cell, the PAS spectra for each reference were obtained using the following instrument parameters. 2.5KHz (0.16c
(light speed of m / s), using an electronic filter of 1.2 KHz, setting the undersampling ratio (number of laser signal zero crossings before collecting the sample) to 2, and setting the sensitivity setting to 1. was extra added minimum 128 scans the range of 375 to 4000 cm ^-1 with a resolution of ^{4 cm -1.}

The cis-, trans- and vinyl-polybutadiene peaks are between 600 and 1 in the PAS spectrum.
Typically between 100 cm ⁻¹ . The area under each of the trans-polybutadiene peaks can be integrated. It is possible to determine the fraction of the individual peak areas relative to the total area of the three isomer peaks and construct a calibration curve of the trans-polybutadiene region fraction versus the actual trans-polybutadiene content. The correlation coefficient (R ² ) of the resulting calibration curve must be at least 0.95.

Using the parameters described above, the PAS is filled with a sample containing a freshly cut, uncontaminated surface that does not contain foreign matter such as a mold release, and is filled with important points (for example, the core surface). Or center)
Obtain the PAS spectrum of the unknown core material at. The unknown trans-polybutadiene region fraction is analyzed to determine the actual trans-isomer content from the calibration curve.

Under one known situation involving barium sulfate, the accuracy of the above-described method for testing trans content may be reduced. Thus, an additional or alternative test for the trans-content of polybutadiene is as follows. Calibration standards are made using polybutadiene with at least two known trans-contents (eg, high and low percentages of trans-polybutadiene). These samples can be used alone or blended together to create a ladder with a trans-polybutadiene content of at least about 1.5% to 50%,
Alternatively, an extra unknown quantity is added so that the resulting calibration curve includes at least 13 evenly spaced points.

Using a Fourier Transform Raman ("FT-Raman") spectrometer equipped with a near infrared laser, a Stokes Raman spectrum is obtained from each reference using the following instrument parameters. That is, excessive heat or fluorescence (typically 400
８００800 mW is appropriate), with sufficient laser power to obtain a good signal-to-noise ratio (“S / N”); at a resolution of 2 cm ⁻¹ ;
Over the range of the Raman shift spectrum of 00 cm ^-1 ; and at least an additional 300 scans.

Chemometric methods and Galactic Industries, Inc., Salem, NH
actic Industries Corp. of
PLS Plus / available from Salem, NH)
A calibration curve is constructed from the data generated above using software such as IQ. Acceptable calibration is SNV
(Detrend) path length correction, average center data creation, about 1600 to 1700 cm
^The software obtained using a PLS-1 curve generated using a 5-point SG second function over a spectral range of ^-1 . The correlation coefficient (R
² ) must be a minimum of 0.95.

A Raman spectrum of the core material is obtained using such an instrument at a critical point on the sample (eg, at the surface or center of a golf ball core). The sample must not contain foreign matter such as a release agent. The spectrum of the sample is analyzed using the PLS calibration curve to determine the trans-polybutadiene isomer content of the sample.

The source of free radicals, often referred to alternatively as free radical initiators, is required in the above formulations and methods. The source of free radicals is typically a peroxide, and is preferably an organic peroxide. A suitable source of free radicals is
Di-t-amyl peroxide, di (2-t-butyl-peroxyisopropyl) benzene peroxide, 3,
3,5-trimethylcyclohexane, a-abis (t-
Butylperoxy) diisopropylbenzene, 1,1-
Bis (t-butylperoxy) -3,3,5-trimedylcyclohexane, chicumyl peroxide, di-t-butyl peroxide, 2,5-di- (t-butylperoxy) -2,5-dimethylhexane, n -Butyl-4,4
-Bis (t-butylperoxy) valerate, lauryl peroxide, benzoyl peroxide, t-butyl hydroperoxide, and the like, and mixtures thereof. The peroxide is typically present in an amount greater than about 0.1 parts by weight of the elastomeric polymer component, and is preferably present in an amount of about 0.1 to 15 parts by weight of the elastomeric polymer component. And about 0.2 to 5 with respect to the elastic polymer component.
More preferably, it is present in parts amounts. It will be appreciated by those skilled in the art that the presence of certain cis-to-trans catalysts according to the present invention will require large amounts of free radical sources, such as those described herein, as compared to conventional crosslinking reactions. It is understandable. Preferably, 100% active initiator is added in an amount ranging from about 0.05 to 5 parts per 100 parts of polybutadiene. More preferably, the amount of initiator added ranges from about 0.15 parts to 4 parts;
Most preferably, it ranges from about 0.25 parts to 3 parts. One or more of electron beam, ultraviolet or gamma rays, x-rays, or any other high energy radiation source capable of producing free radicals may be used in place of or in addition to free radical sources. It is possible. It should be further understood that heat often facilitates the onset of free radical generation.

The inclusion of a crosslinking agent increases the hardness of the product. Suitable crosslinkers include one or more metal salts of unsaturated fatty acids or monocarboxylic acids, such as zinc, aluminum, sodium, lithium, nickel, calcium or magnesium acrylates, and the like, and mixtures thereof. Preferably, the acrylate is zinc, zinc acrylate, zinc diacrylate, zinc methacrylate and zinc dimethacrylate,
And mixtures thereof. The crosslinker must be present in an amount sufficient to crosslink some of the polymer chains in the elastomeric polymer component. For example, it is possible to obtain a desired compression by adjusting the amount of the crosslinking agent. For example, it is possible to achieve the desired compression by changing the type and amount of the crosslinking agent, a method known to those skilled in the art. The crosslinker is typically present in the elastomeric polymer component in an amount greater than about 0.1 percent, and is preferably present in an amount of about 10 to 40 percent relative to the elastomeric polymer component. More preferably, it is present in an amount of about 10 to 30 percent relative to the polymer component. If organic sulfur is selected as the cis-to-trans catalyst, zinc diacrylate can be selected as the cross-linking agent and is preferably present in an amount less than about 25 parts. Suitable, commercially available zinc diacrylates include those from Sartomer Corporation.

The formulations of the present invention may also include fillers, added to the polybutadiene material to adjust the density and / or specific gravity of the core, or added to the cover. As used herein, the term "filler" includes compounds or compounds that can be used to adjust the density and / or other properties of the golf ball core in question. The fillers useful in the golf ball cores of the present invention include, for example, zinc oxide, barium sulfate, flakes, fibers, and regrind or regrind (e.g., to about 30 mesh particle size) which is a ground and recycled core material. Pulverized). The amount and type of filler used is the maximum golf ball weight,
It is determined by the amount and weight of the other ingredients in the formulation, as it is established by the United States Golf Association (USGA) at 45.93 g (1.62 ounces). Commonly used and suitable fillers have a specific gravity of about 2 to 20. In one preferred embodiment, the specific gravity can be about 2 to 6. In one embodiment, the center material has a specific gravity of about 1 to 5, preferably about 1.1 to 2.

[0102] The filler is typically a polymer or mineral particle. Representative fillers are precipitated hydrated silica; clay; talc; asbestos; glass fiber;
Aramid fiber; mica; calcium silicate; barium sulfate; zinc sulfide; lithopone;
Diatomaceous earth; polyvinyl chloride; carbonates such as calcium carbonate and magnesium carbonate; metals such as titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, lead, copper, boron, cobalt, beryllium, zinc and tin; Alloys such as brass, bronze, boron carbide whiskers and tungsten carbide whiskers; metal oxides such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide and zirconium oxide; graphite, carbon black, cotton flock, natural asphalt, cellulose flock And micro-balloons such as glass and ceramic; fly ash; and combinations thereof.

[0102] The center polybutadiene material produced according to the present invention can optionally include an antioxidant. Antioxidants are compounds that inhibit or prevent oxidative degradation of polybutadiene. Antioxidants useful in the present invention are dihydroquinophosphorylation inhibitors,
It includes, but is not limited to, amine type antioxidants and phenol type antioxidants.

Other optional components such as, for example, tetramethylthiuram, peptizers, processing aids, processing oils, plasticizers, dyes and pigments, and accelerators, which are other additives known to those skilled in the art, Sufficient amounts can be used in the present invention to achieve the purpose for which the components are typically used.

In accordance with the present invention, the polymers, free radical initiators, fillers and any other materials used to form the golf ball center or any portion of the center may be combined with any of the materials known to those skilled in the art. It is possible to form a mixture by mixing of the following types: Suitable types of mixing include single pass and multi-pass mixing and the like. The crosslinker and other optional additives used to modify the properties of the golf ball center or additional layers can be similarly combined in any type of mix. Single pass mixing in which the components are added sequentially is preferred. This is because this type of mixing tends to increase efficiency and reduce processing costs. A preferred mixing cycle is single step,
The polymer, cis-trans catalyst, filler, zinc diacrylate, and peroxide are added sequentially. Suitable mixing equipment is known to those skilled in the art, and such equipment can include a Banbury mixer, a two-roll mill, or a twin screw extruder. It is typical to use conventional mixing speeds to bind the polymer, but the speed must be fast enough to allow the components to be substantially uniformly dispersed. On the other hand, if the speed is too high, high mixing speeds tend to break down the polymer during mixing, which can reduce the molecular weight of the elastic polymer component, which is undesirable. The mixing speed is therefore
It should be slow enough to avoid high shear, at which point the desired high molecular weight portion of the polymer component can be lost. On the other hand, if the mixing speed is too high, heat is generated so much that the preform starts to crosslink before it is shaped and assembled around the core, which is not desirable. The mixing temperature is determined by the type of polymer component, and more importantly, by the type of free radical initiator. For example, if di (2-t-butyl-peroxyisopropyl) benzene is used as the free radical initiator, it may be about 80 ° C to 125 ° C, preferably about 88 ° C to 110 ° C, more preferably about 90 ° C. A mixing temperature of between 100C and 100C is suitable for safely mixing the components. It is also important to keep the mixing temperature below the peroxide decomposition temperature. For example, if dicumyl peroxide was selected as the peroxide, the mixing temperature would be about 9
Do not exceed 200 ° F (3.3 ° C). Suitable mixing speeds and temperatures are known to those skilled in the art and can be readily determined without undue experimentation.

The mixture is, for example, compressed or injection-molded to give hemispherical shells which form solid spheres or intermediate layers for the center. The polymer mixture is subjected to a molding cycle and heat and pressure are applied while the mixture is trapped in a mold. The shape of the cavity is determined by the part that forms the golf ball. Partial compression and heat liberates free radicals by decomposing one or more peroxides, thereby simultaneously initiating cis-to-trans conversion and crosslinking. The temperature and duration of the molding cycle can be readily selected based on the type of peroxide and cis-trans catalyst selected.
A molding cycle is a single step cycle in which the mixture is molded at a single temperature for a fixed period of time. In an example of a single step molding cycle of a mixture containing dicumyl peroxide, the polymer mixture is about 168.3.
Hold at about 2,500 psi at 335 ° F. for 11 minutes. Such a molding cycle can also include a two-step process, in which the polymer mixture is held in the mold at an initial temperature for an initial time, and then a second step is performed. At a typically higher temperature for a second time. In an example of a two-step molding cycle, the mold is heated to about 143.3 ° C. (2
90 ° F.), and then the mold is
C. (340.degree. F.) and hold for 20 minutes. In the preferred embodiment of the present invention, a single-step cure cycle is used. Single-step processes are effective and efficient, reducing the time and cost of a two-step process. The elastomeric polymer component, polybutadiene, cis-to-trans conversion catalyst, added polymer, free radical initiator, filler, and any other components used to form any portion of the center or core of a golf ball according to the present invention. The materials can be combined to form a golf ball by an injection molding process, and such processes are known to those skilled in the art. Curing times are determined by the various materials selected, but particularly suitable times are from about 5 minutes to 18 minutes, preferably from about 8 minutes to 15 minutes, and more preferably from about 10 minutes. Minutes to 12 minutes. One skilled in the art can easily vary the cure time based on the particular materials used and the description herein.

The cured elastomeric polymer component contains more trans-polybutadiene than the uncured elastomeric polymer component and has a surface having a first hardness and a second hardness at certain points inside. And the second hardness is increased by 10% of the first hardness. Preferably, such an article is a sphere,
Further, the point is an intermediate point of the article. In another embodiment, the second hardness is 20% higher than the first hardness. The cured article also has, at an interior site, a first amount of trans-polybutadiene and at a surface site, a second amount of trans-polybutadiene, wherein the first amount of trans-polybutadiene is the first amount. Is at least about 6 percent less than the second amount, preferably at least 10 percent less than the second amount, and more preferably at least about 20 percent less than the second amount. The interior portion is preferably a midpoint, and the article is preferably a sphere. Typically, the compression of a center or a portion of a center of a golf ball made in accordance with the present invention is about 15 to 100. In one embodiment, the compression is less than about 50;
More preferably, it is less than about 25. In a preferred embodiment,
The compression is about 60-90, more preferably about 70
To 85. Equivalent methods of measuring compression vary. For example, 70-atch compression (formerly referred to as "PGA compression") has a deflection of 3.000 at a load of 100 kg.
Equivalent to a hardness of 2 mm and equal to a "spring constant" of 36 kg / mm. In one embodiment, the deflection of the center of the golf ball is about 3.0 in a 130 kg-10 kg test.
3 mm to 7 mm. In one preferred embodiment, the natural frequency of the core is about 1,500-3,500 Hz.

Referring to FIG. 2, there is illustrated a golf ball 18 having a center 20, a cover 22, and a layer of wound yarn 24 disposed between the center and the cover. The center of FIG. 2 is a sphere or shell 26, such as a rubber sack, thermoplastic or metal shell design, filled with fluid.
It is. In the present embodiment, the polybutadiene reaction product of the present invention can be arranged in a shell.
It is preferably located around a shell (not shown) or in the layer used to form the taut threads of the wound layer 24. From the above description, it is possible for a solid center to be formed according to the present invention from a polybutadiene reaction product. The compression or viscosity of the fluid 28 used in the embodiment illustrated in FIG. 2 can be any suitable. It is also possible to construct such centers with empty (hollow) or "gas" centers. The center is covered with an optional intermediate layer (not shown), a wound layer and a cover according to the invention. 1
In embodiments, the cover includes at least two layers, at least one of the two cover layers including the polyurethane cover material of the present invention.

The envelope or shell 26 can be filled with a wide variety of fluid materials, including air, gas, aqueous solution,
Gels, foams, hot melts, other fluid materials and combinations thereof, as disclosed in US Pat. No. 5,683,31.
No. 2 including the materials described therein. Such U.S. patents are incorporated herein by reference. The fluid or liquid in the center can be varied to modify ball performance parameters such as moment of inertia, weight, initial spin, and spin decay.

Suitable gases contained in the fluid-filled center include air, nitrogen and argon. Preferably, such a gas is inert. Examples of suitable liquids include solutions or oils such as saline, corn syrup, saline and corn syrup, glycols and water. The liquid may further include water in which the organic compound is dissolved or dispersed, a paste, clay, barite, a colloidal suspension in carbon or water, or a mixture of salt and water / glycol. Can be done. Examples of suitable gels are aqueous gelatin gels, hydrogels, water /
Gels comprising a copolymer rubber based material such as methylcellulose gel and styrene-butadiene-styrene rubber, and paraffin and / or naphthion oil. Examples of suitable melts include waxes and hot melts. Hot melts are solid at or near normal room temperature, but become liquid at elevated temperatures.

The fluid can also be a reactive liquid system that combines to form a solid or creates an internal pressure within the envelope. Suitable reactive liquids that form solids are silicate gels, agar gels, peroxide-cured polyester resins, two-part epoxy resin systems, and peroxide-cured liquid polybutadiene rubber formulations. Of particular interest are liquids that react to form a foamed foam. One skilled in the art should understand that other reactive liquid systems can be used as well, depending on the properties of the envelope and the final golf ball.

Preferably, the outer diameter D ₁ of the centers 12 and 18 of FIGS. 1 and 2 is at least about 2.54 cm (about 1
Inches), and more preferably about 1.32 to 1.55 inches. In one embodiment, the outer diameter of the center is about 3.4036.
cm to 3.556 cm (approximately 1.34 inches to 1.4 cm)
Inches). Preferably, the outer diameter _{D 2} of the wound layer, 16 and 24, respectively, from about 3.81 to 4.1148c
m (about 1.5 to 1.62 inches), and more preferably about 3.9116 to 4.064 cm (about 1.54 to 1.6 inches). The wound layer of the golf ball is formed by at least one thread 30.
Thus, the amount of threads used tends to be small compared to the size of the core. The wound layer reduces compression and produces a ball with a softer feel. 1
In embodiments, the thickness of the wound layer is less than about 0.3 inches. In one preferred embodiment, the thickness of the wound layer is about 0.1 inches. In this preferred embodiment, the thread material comprises polyether urea or very hard high tensile modulus threads. "Hard and high tensile modulus" as used herein means a tensile modulus of at least about 10,000 ksi.

[0112] Thread materials including polyisoprene, polyether urea, polyester, polyethylene, polypropylene, or combinations thereof, can be used in the present invention. The relatively high and low modulus threads are simultaneously wrapped around the center. Further, in another embodiment, threads that "soften" during compression and / or injection molding cycles of polyether urea or the like to create a "mantle" layer or melt cover can be used.
Threads that do not show softening during molding, such as polyisoprene, can also be used in the present invention. In one embodiment, a thread containing polyether urea is preferably used for the wound layer.

The threads used in the present invention can be formed using various methods, including conventional calendering and slitting. Further, it is possible to provide the threads using melt spinning, wet spinning, dry spinning or polymer spinning. Melt spinning is a very economical and costly process. The polymer is extruded through a spinneret by a heated spin pump. The resulting fiber is pulled at a speed of up to 1200 m / min. The fiber is pulled and solidified and cooled in air. Because high temperatures are required,
Only melt and heat stable polymers can be melt spun.
These polymers include poly (olefins), aliphatic polyamides, and aromatic polyesters, all of which are suitable thread materials.

For a polymer that decomposes when melted, a wet spinning method is used. Approximately 5 to 20% of the solution is passed through the spinneret by a spin pump. A precipitation bath is used to solidify the filament, and a tension or elongation bath is used to pull the filament. The filament production rate in this process is typically less than the melt spinning production rate, about 50 to 100 m / min. The process is uneconomic due to the cost of solvent recovery.

In dry spinning, air becomes a precipitation bath. This method can be used for polymers that decompose when melted, but only if only readily volatile solvents can be used for such polymers. A solution of about 20-55% is used. After passing through the mouthpiece, the resulting filaments enter a chamber approximately 5 to 8 m in length. In this chamber, warm air is injected toward the filament. Thereby, the solvent evaporates and the filament solidifies. This method has a higher spinning speed than the wet spinning method. Typical filament production speeds are about 300-500 m / min. The initial capital investment of the equipment is higher, but the operating costs are lower than wet spinning. Furthermore, this method can only be used for spinning polymers where only readily volatile solvents can be used.

In another spinning method, polymerization spinning, the monomers are polymerized together with initiators, fillers, pigments and flame retardants or other selected additives. The polymer is spun directly at a speed of about 400 m / min. The polymer is not sequestered. Only monomers that polymerize rapidly are suitable for the process. For example, LYCRA® is manufactured by polymerization spinning.

[0117] Many different types of threads can be used with the present invention. For example, referring to FIG. 3, a conventional single layer golf ball thread 300 is illustrated. In general, a single-layer golf ball thread 300 mixes synthetic cis-polyisoprene rubber, natural rubber, and a cured system together, and rolls such a mixture to form a sheet;
The sheet is cured and the sheet is finely cut, or slit, into threads. The thread is generally rectangular and has dimensions of 0.15875 × 0.0508c
m (0.0625 x 0.02 inches) is preferred. Typical cross-sectional areas of such thread 300 is _{a 1,}
It is approximately about 0.0013 square inches. This material can be used in a very thin layer on the center.

Referring to FIG. 4, there is illustrated a conventional two-layer golf ball thread 400 that can also be used with the present invention. For this two-layer golf ball thread, the mixing and calendering steps are the same as for the single-layer thread. However, after the sheet is formed, the sheet is rolled and cured together to join the layers or sheets together and slit into threads. The thickness of each layer of threads 400, respectively, are _{t 1} and _{t 2.} Generally, these thicknesses are substantially the same, and each layer also has the same physical properties.

As shown in FIG. 5, another two-layer thread that can be used with the present invention is to mix conventional thread material and roll the thread material into a two-layer sheet. Alternatively, it is formed by rolling the layers together, bonding the layers together, and slitting the sheet into two layers of threads 500. The step of joining the layers together is accomplished by vulcanizing the material while applying pressure to hold the two layers together, such that the layers are joined together. Vulcanization systems are systems with sulfur, activated by heat and also known to those skilled in the art. Preferably, the first layer 51
0 is more elastic and the second layer 520 is more manageable, as evidenced by the physical properties of each layer.

Another type of thread that can be used with the present invention is illustrated in FIG. The thread 600 is composed of a number of individual filaments or strands 610. Preferably, 1
Zero or more strands 610 make up thread 600, more preferably 50 or more strands 610 form thread 600, and most preferably 10 threads.
Contains more than 0 strands. The strand 610 is
Small diameter, typically about 0.00508
cm (about 0.002 inch), and more preferably about 0.0001 inch (about 0.000025 inch).
Is less than. Preferably, the cross-sectional area a of the strand of the present invention a
₂ is less than about 0.0001 square inches, and most preferably is 0.00001 square inches. Preferably, the thread diameter _{a 3} of the present embodiment is about 0.001 square inches and most preferably a about 0.0005 square inches. Threads formed from multiple strands can be made in accordance with the present invention with reference to US Pat. No. 6,149,535. The disclosure of such a U.S. patent is hereby incorporated herein by reference for clarity.

Preferably, the elongation at break of the thread is greater than about 8%. More preferably, the elongation at break of the thread is greater than about 25%. At a minimum elongation before break of about 8%, the golf ball deforms during impact. About 8% during typical driver impact
A golf ball that deforms significantly below will have a hard feel when hit and undesirable spin and feel properties. In one embodiment, the elongation at break of the thread is about 2
00% to 1000%. Preferably, the elastic modulus of the thread when wound is greater than about 10,000 psi. In a preferred embodiment, the modulus is about 20,0.
More than 00 psi. In another preferred embodiment, the modulus is greater than about 25,000 psi.

The strand 610 of the thread 600 shown in FIG.
Can be held together with a binder as shown, or can be spun together. Threads can be produced using melt spinning, wet spinning, dry spinning, and polymer spinning. Each method is described in detail herein.

The thread 600 of FIG. 6 preferably comprises a polymer material. Suitable polymers are LYCRA®; polyester urea; polyester block copolymers such as HYTREL®; isotactic-poly (propylene); polyethylene; polyamide; poly (oxymethylene); polyketone;
Poly (ethylene terephthalate) such as N (R);
Poly (p-phenylene terephthalamide) such as KEVLAR®; poly (acrylonitrile) such as ORLON®; trans, trans-diaminodicyclohexylmethane and dodecanedicarboxylic acid such as QUIINA®. LYCRA®, HYTREL®, DACRON®, KEVLAR®, ORLON®, and QUIINA® are trademarks of Delaware,
Wilmington's E. I. DuPont de Nemours & EI Dupont de Nemours &
Co. of Wilmington, DE). For example, S-GLAS from Corning
Glass fibers, S®, can also be used. Globe Manufacturing, Fall River, Mass.
Manufacturing of Fall Riv
er, MA) can be used. In fact, mixtures of any of the thread materials described herein can be included in the thread layers of the present invention.

The thread 600 can also be made up of strands 610 having different physical properties to achieve the desired elongation or elongation characteristics. For example, the thread may comprise a combination of strands of a weak but elastic first elongation type material and a strong but less elastic second elongation type material. In another example,
The thread can include at least one strand of a polyisoprene rubber having a diameter of less than about 0.02 inches. The strands can be surrounded by ten to fifty strands of polyether urea each having a diameter of less than about 0.002 inches.

In another embodiment, the golf ball may include a wound hoop stress layer, such layer being provided instead of or in addition to the wound layer as described above. The wound layer is formed from high tensile fibers wound around the inner core, preferably in contact with the inner core. Various high tensile modulus fibers can provide the necessary hoop stress for layers of minimal thickness, preferably glass, Dacron (Dac).
ron), polyamides, aromatic polyamides (such as Kevlar aramid fiber bars from DuPont), carbon or metal fibers. Metals such as steel (especially stainless steel), Monel metal, or titanium are preferred. The hoop layer is formed from metal fibers and has a high moment of inertia, and thus can rotate at a low speed when struck by a golf club, thereby maintaining its rotational speed for an extended period of time during flight.

The strength of these fibers having a high tensile modulus is very suitable for absorbing the very high stresses applied to the windings of golf balls when hit with a golf club. However, modifications can be made to impart good feel and durability to the golf ball. A tensile strength of at least about 250 kpsi is preferred, but a tensile strength of at least about 500 kpsi is more preferred. The tensile modulus of a fiber with a high tensile modulus can be changed to provide a softer or more durable ball with higher stiffness as desired by changing either the gauge or the thickness. Become. A modulus of at least 10,000 kpsi is preferred. A modulus of at least 20,000 kpsi is most preferred. Preferably, the hoop layer is wrapped to a thickness of about 0.01 to 0.10 inches (0.0254 to 0.254 cm). In one hoop layer embodiment, at least 10
Preferably, 0% of the initial stress is applied to the taut material.

In an embodiment of such a hoop layer, a wound layer is formed using fibers having a high tensile modulus, and the initial tension applied to such fibers during the winding process is less than about 4%. Preferably, it is the initial stress. About 1
Initial stresses of less than 0% are more preferred. An initial stress of less than about 25% is most preferred. The fiber itself is preferably continuous because it is easy to wind around the core.

The golf ball 10 of FIGS. 1 and 2 can be formed by a conventional method used in the technical field of golf balls. For example, the golf ball of FIG. 1 can be manufactured by injection or compression molding of the solid center 12. The thread 30 is then wrapped around the solid core 12 and, as already described,
The wound layer 16 is formed. The cover layer or layers are then injected or compression molded around the wound layer 16 by methods known in the art, or
It is cast. Most preferably, the golf ball of the present invention has a solid center and is formed from at least 100 strands of polyether urea LYCRA.
Surrounded by a ® thread, each strand has a diameter of about 0.0001 inches and is wrapped with a wrap extension of about 200 to about 500%.

Returning to FIG. 2, the golf ball 18 of the present invention
Can be formed by first forming a shell 26 by compression molding a hemispherical cup, such a cup being:
Joined together to form a shell to create a cavity and fill the cavity with a fluid or liquid 28 to form a fluid-filled center 20. As described herein, FIG. 2 illustrates one embodiment of the present invention, in which a golf ball is fluid-filled.
In an alternative embodiment, the center layer (s) is solid. The thread 30 is then wrapped directly around the shell to form a wrapping layer, as described above, if no additional layer is desired between the center and the wrapping layer, and if additional layers are desired. If present, an intermediate layer is formed around the shell before placing the taut material around the center layer. A cover is then placed around the wound layer, according to the invention, by injection or compression molding, or by casting.

Referring to FIG. 7, a golf ball 32 having a solid center 34, a cover 36 and a wound layer 38 disposed between the center and the cover is illustrated.
The center 34 can also be a liquid-filled center formed as described above. Additional layer or layers 40 can be formed on the center. For example, as shown in FIG. 7, a mantle layer 40 is formed on the center. According to the present invention, as described above, a wound layer formed from at least one thread material is formed on the mantle layer. The cover is formed on the wound layer. Further, FIG. 7 can be modified in various ways, including a variant in which the wound layer of the present invention is formed directly adjacent to the center and an optional intermediate layer (mantle layer) is formed on the wound layer. . Furthermore, instead of a solid mantle layer, it is also conceivable to form a second wound layer or wound layers between the center and the wound layer according to the invention, or between the wound layer and the cover according to the invention. . As already described herein, a number of materials can be used to form the additional layers described above.

Referring to FIGS. 1, 2 and 7, the covers 14, 22 and 36 provide an interface between the ball and the club. Covers 14, 22 and 34 provide the interface between the ball and the club. Desirable properties for the cover are, among others, good mobility, high abrasion resistance, high tear strength, high resilience and good release properties. The cover typically has a thickness that provides sufficient strength, enhanced performance characteristics, and durability. The thickness of the cover is preferably less than about 0.1 inch (about 0.254 cm) and about 0.05 inch (about 0.127 cm).
More preferably, it is less than about 0.0508 to about 0.116 cm (about 0.02 to about 0.04 inch).
Is most preferred. The present invention, more particularly,
The present invention relates to a multi-layer golf ball including a core having at least one wound layer, an inner cover layer, and an outer cover layer. In this embodiment, preferably, the thickness of at least one of the inner cover layer and the outer cover layer is less than about 0.05 inches, more preferably, less than about 0.05 inches.
08 to about 0.1016 cm (about 0.02 to about 0.016 cm)
4 inches). Most preferably, each cover layer has a thickness of about 0.03 inches.

In the above embodiment having an inner cover layer and an outer cover layer, the inner cover layer can be made as follows. Injection molding, compression molding or casting can be used, but in the preferred embodiment, the inner cover layer is formed on the winding center using compression molding. The appropriate rate of increasing the pressure to close the mold around the winding center can be readily determined, but if the pressure on the mold and the center within the mold is increased too rapidly, for example, as little as a second. It must be borne in mind that the center may break and / or break without inadvertence. Therefore, a time of about 1 second to more than 30 seconds, preferably a time of 2 seconds to more than 20 seconds is appropriate,
This also depends on other processing conditions and materials used. In one preferred embodiment, a time of 15 seconds is most appropriate for closing the mold. This time is measured from when each mold half of the mold contacts the material in between, and relates to the time until the pressure applied to the mold and the center therein is increased and the mold is completely closed. The method effectively contributes to avoiding or eliminating weld lines that occur when using injection molding methods.

In one suitable injection molding embodiment, a high speed injection mold is used, where a screw speed of about 14 inches per second is used. Such devices are available from K in Munich, Germany.
commercially available from rass Maffei Machines. A cycle time of about 20 to 30 seconds can be used. This high speed injection molding method is suitable for effectively strengthening the welding line and also for forming the inner and outer cover layers.

If the cover layer optionally and preferably includes an inner layer, the inner layer can be formed from the same types of materials described herein as the outer cover layer. 1
In embodiments, the inner cover layer comprises a thermoplastic, such as an ionomer, a polyamide, a polyetherester, a polyurea, or a metallocene catalyzed polymer, or a combination thereof. In a preferred embodiment, the inner cover layer comprises:
50 weight percent SURLYN 8940 (Na neutralized) and 50 weight percent SURLYN 794
0 (Li neutralized). In another embodiment, the inner cover layer can include one or more polyureas, which can be made by reacting an organic isocyanate with an organic amine, each having two or more functional groups. Having a group. Particularly useful isocyanates include aliphatic, allylaliphatic and aromatic isocyanates, and in one embodiment, the isocyanate content is at least about 29%. In a preferred embodiment, the isocyanate can be present in an amount of about 29-34 weight percent. Typical amine curing agents used in polyureas include one or more organic diamines and triamines. Aromatic diamines are preferred. Particularly suitable polyureas include those described in US Pat. No. 5,484,870, the disclosure of which is incorporated herein by reference.

The outer diameter of the inner cover layer is about 3,937 cm.
It is typically about 1.55 inches to 1.65 inches. In one embodiment, the outer diameter is between about 4.064 cm and 4.1656 cm (about 1.6 cm).
Inches to 1.64 inches). The outer diameter of a typical inner layer is 1.614 inches (4.1148 cm).
The thickness of the inner layer is between about 0.0635 cm and 0.2032
Typically about 0.025 inches to 0.08 inches, and preferably about 0.03 inches to 0.05 inches. In one preferred embodiment, the thickness of the inner cover layer is between about 0.032 inches and 0.038 inches. In one preferred embodiment, the hardness of the inner cover layer is about 20 to 80 Shore D, preferably about 50 to 75 Shore D, and more preferably about 50 to 75 Shore D, as measured on the wound layer. 65 to 72 Shore D. The hardness of the slab made of the material is slightly lower, and if the inner layer has a hardness of 68 Shore D, when the material is measured directly,
It becomes about 64 Shore D. The compression of the inner cover layer is about 20
It is typically between about 100 and 100, preferably between about 50 and 95. In one preferred embodiment, the compression of the inner cover layer is about 75-90. In one embodiment, the specific gravity of the inner cover layer is about 0.8 to 1.3, and preferably about 0.9 to 1.1. In one embodiment, the weight of the partially formed golf ball including the inner cover layer is between about 40 g and 46 g, and preferably between about 40 and 42 g. In one embodiment, the loss tangent of the inner cover layer is about 0.03 at about -30 to 20 ° C.
To 0.08. The complex modulus of the inner cover layer is approximately
About 5,000 to 1 at temperatures over -30 to 20 ° C
It can be 2,000 kgf / cm ² .

The cover layer, or the inner and outer cover layers, can each comprise any material known to those skilled in the art, including thermoplastic and thermoset materials, while the inner cover layer comprises ethylene and Any material may be included, such as an ionic copolymer of an unsaturated monocarboxylic acid, said ionic copolymer being a product of E.M. of Wilmint, Del.
I. Dupont de Nemours under the trade name SURLYN, and Exxon under the name IOTE
It is commercially available under the trade name K or ESCOR. These are copolymers or terpolymers of methacrylic acid or acrylic acid partially neutralized with salts of ethylene and zinc, sodium, lithium, magnesium, potassium, calcium, manganese, nickel, etc.
Olefins having 2 to 8 carbon atoms and 3 to 8
Is a reaction product of an unsaturated monocarboxylic acid having three carbon atoms. The carboxylic acid groups of the copolymer are wholly or partially neutralized and can include methacrylic acid, crotonic acid, maleic acid, fumaric acid, or itaconic acid.

The golf ball can also include one or more homopolymer or copolymer materials, including (1) polymerizing vinyl chloride, or vinyl chloride and vinyl acetate, acrylic acid Vinyl resin formed by copolymerization with ester or vinylidene chloride; (2) polyolefin such as polyethylene, polypropylene, polybutylene and ethylene methacrylate, ethylene ethacrylate, ethylene vinyl acetate, ethylene methacrylic acid, ethylene acrylic acid or propylene acrylic acid And copolymers and homopolymers purified using single-site or metallocene catalysts; (3) polyurethanes made from polyols and diisocyanates or polyisocyanates; (4) Polyureas as disclosed in US Pat. No. 5,484,870; (5) Poly (hexamethylene adipamide) and made from diamines and dibasic acids Polyamide, and polyamide made from amino acids such as poly (caprolactam), and polyamide and SURLYN, polyethylene, ethylene copolymer, ethyl-propylene-
A blend with a non-coagulated diene terpolymer or the like; (6) an acrylic resin and the resin and polyvinyl chloride;
(7) thermoplastic plastics such as urethane; olefin thermoplastic rubber which is a blend of polyolefin and ethylene-propylene-non-coagulated diene terpolymer; block copolymer of styrene and butadiene, isoprene or ethylene-butylene rubber Polymer; or Atofi, Philadelphia, PA
PEBA commercially available from Na of Philadelphia, PA) (formerly Elf Atochem).
Copoly (ether-amide) such as X; (8) Polyphenylene oxide resin or polyphenylene oxide with General Electric, Pittsfield, Mass.
ric Company of Pittsfield
(9) polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / modified glycol and E.M., Wilmington, Del. I. Under the trade name HYTREL from Dupont de Nemours,
And thermoplastic polyesters such as elastomers commercially available from General Electric Company of Pittsfield, Mass. Under the trade name LOMOD; Blends and alloys of anhydrides, polyethylene, elastomers, etc., and polyvinyl chloride with acrylonitrile butadiene styrene or vinyl acetate ethylene or other elastomers; and (11) thermoplastic rubber, polyethylene, propylene, polyacetal, nylon, polyester, cellulose It is a blend with an ester or the like.

In one embodiment, the cover layer comprises butene-1 or hexane-containing functional monomers such as ethylene, propylene, acrylic acid and methacrylic acid and fully or partially neutralized ionomer resins and blends thereof.
1-based homopolymer or copolymer, methyl acrylate, methyl methacrylate homopolymer and copolymer, imidized amino groups containing polymer, polycarbonate, reinforced polyamide, polyphenylene oxide,
High impact polystyrene, polyether ketone, porsulfone, poly (phenylene sulfide), acrylonitrile-butadiene, acryl-styrene-acrylonitrile, poly (ethylene terephthalate), poly (butylene terephthalate), poly (ethylene vinyl alcohol), poly (ethylene vinyl alcohol) (Fluoroethylene) and their copolymers, including functional comonomers, and blends thereof. Suitable cover formulations also include low modulus ionomers, such as polyether or polyester thermoplastic urethanes, thermoset polyurethanes, acid-containing ethylene copolymer ionomers including E / X / Y terpolymers, and the like. E / X / Y
In the terpolymer, E is ethylene, X is a softener component based on acrylate or methacrylate,
Present in an amount of about 0 to 50 weight percent, Y is acrylic acid or methacrylic acid, present in an amount of about 5 to 35 weight percent. More preferably, in low spin rate embodiments designed to maximize distance, acrylic or methacrylic acid is present at about 15 to 35 weight percent, making the ionomer a high modulus ionomer. In high spin rate embodiments, the cover comprises an ionomer, wherein the acid contains about 10 to 15 acids.
It is present in weight percent and contains a softening comonomer. In a preferred embodiment of the present invention, one or more polyurea components can be included in the inner cover layer, the outer cover layer, or both.

The cover preferably comprises a polyurethane compound, the compound comprising the reaction product of at least one polyisocyanate and at least one hardener. The curing agent can include, for example, one or more diamines, one or more polyols, or a combination thereof. The at least one polyisocyanate is
One or more polyols can be combined to form a prepolymer, which is then combined with the at least one curing agent. Thus, as described herein, polyols are suitable for use in one or both components of the polyurethane material, as part of a prepolymer, and in a curing agent. Polyurethane formulations can be used to form the inner cover layer, the outer cover layer, or both. In a preferred embodiment, the outer cover comprises a polyurethane compound.

Any polyisocyanate available to those skilled in the art is suitable for use in the present invention. Representative polyisocyanates are described below, but are not limited thereto. That is, 4,4 '
-Diphenylene methane diisocyanate ("MD
I "), polymer MDI, carbodiimide-modified liquid M
DI, 4,4′-dicyclohexylmethane diisocyanate (“H ₁₂ MDI”), p-penylene diisocyanate (“PPDI”), toluene diisocyanate (“TDI”), 3,3′-dimethyl-4,4′-biphenylene Diisocyanate ("TODI"), isophorone diisocyanate ("IPDI"), hexamethylene diisocyanate ("HDI"), naphthalene diisocyanate ("NDI"), xylene diisocyanate ("XDI"), para-tetramethyl xylene diisocyanate ("p- TMXDI "), meta-tetramethylxylene diisocyanate (" m-TMXDI "), ethylene diisocyanate, propylene-1,2-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexyldiiso Aneto, 1,6-hexamethylene - diisocyanate ( "HDI"), 1,12-diisocyanate, cyclobutane-1,3
-Diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5
-Isocyanatomethylcyclohexane, methylcyclohexylenediisocyanate, HDI triisocyanate, 2,4,4-trimethyl-1,6-hexanediisocyanate triisocyanate ("TMDI"), tetracene diisocyanate, naphthalene diisocyanate, anthracene diisocyanate, and the like Is a mixture of Polyisocyanates are known to those skilled in the art as having two or more isocyanate groups, for example, di-, tri- and tetra-isocyanates. Preferably, the polyisocyanate comprises MDI, PPDI, TDI or a mixture thereof, more preferably MDI. As used herein, the term "MDI" refers to 4,4'-
Diphenylmethane diisocyanate, polymer MDI,
The diisocyanates used, including carbodiimide-modified liquid MDI and mixtures thereof, and furthermore, those skilled in the art will recognize that they have lower levels of "free" monomeric isocyanate groups than conventional diisocyanates. It can be understood to be "free monomers", ie, the formulations of the present invention typically have less than about 0.1% free monomer groups. . Examples of "low free monomer" diisocyanates are
Including but not limited to low free monomer MDI, low free monomer TDI and low free monomer PPDI.

[0141] The at least one polyisocyanate must have less than about 14% unreacted NCO groups. Preferably, the at least one polycyanate has an NCO of about 7.5% or less, more preferably, about 2.5% to about 7.5% NCO, and most preferably. , About 4% to about 6.5% NCO.

Any polyol known to those skilled in the art is suitable for use in the present invention. Examples of polyols are as follows, but are not limited thereto. That is, polyether polyols, hydroxy-terminated polybutadienes (partially / fully hydrogenated derivatives), polyester polyols, polycaprolactone polyols, and polycarbonate polyols. In one preferred embodiment, the polyol comprises a polyether polyol, more preferably a polyol having the general structure: Wherein R ₁ and R ₂ are linear or branched hydrocarbon chains, each containing from 1 to about 20 carbon atoms, and n
Is a complete integer in the range of 1 to about 45. An example is polytetramethylene ether glycol ("PTME
G "), polyethylene propylene glycol, polyoxypropylene glycol and mixtures thereof,
It is not limited to them. The hydrocarbon chain can have saturated or unsaturated bonds and substituted or unsubstituted aromatic and cyclic groups. Suitably, the polyol of the present invention comprises PTMEG.

In another embodiment, a polyester polyol is included in the polyurethane material of the present invention. Suitable polyester polyols have the following general structure: Wherein R ₁ and R ₂ are linear or branched hydrocarbon chains, each containing from 1 to about 20 carbon atoms, and n
Is a complete integer in the range of 1 to about 25. Suitable polyester polyols include polyethylene aditoglycol, polybutylene aditoglycol, polyethylenepropylene aditoglycol, ortho-phthalate-
Including, but not limited to, 1,6-hexanediol, and mixtures thereof. The hydrocarbon chain is
It can have saturated or unsaturated bonds and substituted or unsubstituted aromatic and cyclic groups.

In another embodiment, a polycaprolactone polyol is included in the materials of the present invention. Preferably, all polycaprolactone polyols have the following general structure: Where R ₁ is a straight or branched hydrocarbon chain, containing 1 to about 20 carbon atoms, and n is the length of the chain, a complete integer in the range 1 to about 20. . Suitable polycaprolactone polyols include 1,6-hexanediol-initiated polycaprolactone, diethylene glycol initiated polycaprolactone,
Trimethylolpropane-initiated polycaprolactone, neopentylglycol-initiated polycaprolactone, 1,4-butanediol-initiated polycaprolactone, and mixtures thereof, but are not limited thereto. The hydrocarbon chain is
It can have saturated or unsaturated bonds and substituted or unsubstituted aromatic and cyclic groups.

In yet another embodiment, polycarbonate polycarbonate
Riol is included in the polyurethane material of the present invention.
Preferably, any of the polycarbonate polyols is
Having the general structure ofWhere R₁Is mainly bishenol A unit- (p-C
₆H₄) -C (CH₃) ₂− (P−C₆H₄)-Or
A derivative thereof, where n is the length of the chain, 1-2
It is a complete integer in the range of 0. Suitable polycarbonate
Includes but is not limited to polyphthalate carbonate
It is not something to be done. Hydrocarbon chains are saturated or unsaturated
It must have a bond and substituted or unsubstituted aromatic and cyclic groups.
Can be. In one embodiment, the molecular weight of the polyol is about
200 to about 4000.

Polyamine curing agents have also been found to be suitable for use as curing agents in the polyurethane formulations of the present invention and can improve the cut, shear and impact resistance of the resulting balls. ing. Suitable polyamine curing agents include 3,5-dimethylthio-2,4-toluenediamine and its isomers such as 3,5-diethyltoluene- such as 3,5-dimethyltoluene-2,6-diamine.
2,4-diamine and its isomer, 4,4′-bis-
(Sec-butylamino) -diphenylmethane, 1,4-
Bis- (sec-butylamino) -benzene, 4,4-methylene-bis- (2-chloroaniline), 4,4′-methylene-bis- (3-chloro-2,6-diethylaniline), polytetra Methylene oxide-di-p-aminobenzoate, N, N'-dialkyldiaminodiphenylmethane, p, p'-methylenedianiline ("MD
A "), m-phenylenediamine (" MPDA "),
4,4'-methylene-bis- (2-chloroaniline)
("MOCA"), 4,4'-methylene-bis- (2,
6-diethylaniline), 4,4′-diamino-3,
3′-diethyl-5,5′-dimethyldiphenylmethane, 2,2 ′, 3,3′-tetrachlorodiaminodiphenylmethane, 4,4′-methylene-bis- (3-chloro-2,6-diethylaniline), Including, but not limited to, trimethylene glycol di-p-aminobenzoate, and mixtures thereof. Preferably,
The curing agent of the present invention comprises 3,5 such as ETHACURE300.
-Includes dimethylthio-2,4-toluenediamine and its isomers. Suitable polyamine curing agents include both primary and secondary amines and have a weight average molecular weight in the range of about 64 to about 2000.

Other suitable polyamine curing agents include those having the following general structure: Wherein n and m each independently have a value of 0, 1, 2 or 3, and Y is 1,2-cyclohexyl, 1,3
-Cyclohexyl, 1,4-cyclohexyl, oroto-
It is phenylene, meta-phenylene, or para-phenylene, or a combination thereof. Preferably, n and m
Have each independently a value of 0, 1 or 2;
It has a value of 1 or 2.

It is possible to add diol, triol, tetraol, or hydroxy-terminated curing agents to the polyurethane formulations described above. Suitable diol, triol, and tetraol groups include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, low molecular weight polytetramethylene ether glycol,
1,3-bis (2-hydroxyethoxy) benzene,
1,3-bis- [2- (2-hydroxyethoxy) ethoxy] benzene, 1,3-bis- {2 [2- (2-hydroxyethoxy) ethoxy] ethoxy} benzene, 1,4
-Butanediol, 1,5-pentanediol, 1,6
-Hexanediol, resorutinol-di- (β-hydroxyethyl) ether, hydroquinone-di- (β-hydroxyethyl) ether, and mixtures thereof. Preferably, the hydroxy-terminated curing agent comprises ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane and mixtures thereof.

Preferably, the hydroxy-terminated curing agent has a molecular weight in the range of about 48 to 2000. As used herein, molecular weight is the absolute weight average molecular weight, as understood by those skilled in the art. Other suitable hydroxy-terminated curing agents include
It has the following general chemical structure: Wherein n and m each independently have a value of 0, 1, 2 or 3, and X is oro-phenylene, meta-phenylene, para-phenylene, 1,2-cyclohexyl,
1,3-cyclohexyl, 1,4-cyclohexyl, or a mixture thereof. Preferably, n and m
Have each independently a value of 0, 1 or 2;
It has a value of 1 or 2.

Both the hydroxy-terminated curing agents and the amine curing agents can contain one or more saturated, unsaturated, aromatic and cyclic groups. Also, the hydroxy-terminated and amine curing agents can include one or more halogen groups. Polyurethane formulations can be formed with blends or mixtures of curing agents. However, if desired, the polyurethane formulation can be formed from a single curing agent.

Any method known to those skilled in the art can be used to bind the polyisocyanate, polyol, and curing agent of the present invention. A commonly used method, known in the art as the one-shot method, is to simultaneously mix a polyisocyanate, a polyol and a curing agent. In this way, the mixing becomes heterogeneous (more random) and the manufacturer has less control over the molecular structure of the resulting formulation. A suitable mixing method is known as a prepolymer method. In this method, the polyisocyanate and the polyol are separately mixed, after which the curing agent is added. In this way, the mixing becomes more homogeneous and thus a more uniform polymer blend is obtained.

Optionally, a filler component is selected to increase the density of the blend of components described above. The choice of filler component depends on the desired properties of the golf ball. Examples of fillers used in the polyurethane filler component include the fillers for the polybutadiene reactive component described herein. Similar or identical additives, such as nanoparticles, fibers, glass spheres, and / or various metals such as titanium and tungsten are needed to modify one or more golf ball properties in the polyurethane formulations of the present invention. Any amount can be added. Additional components that can be added to the polyurethane formulation include UV stabilizers and other dyes, as well as optical brighteners and fluorescent pigments and dyes. Such additional components are added in amounts that achieve their respective desired purposes.

It has been found by the present invention that the castable reactive material applied in the form of a fluid due to its very thin nature can provide a very thin outer cover layer on a golf ball. I have. In particular, it has been found that castable reaction liquids that react to form a urethane elastomeric material provide the desired very thin outer cover layer.

The castable reaction liquid may be used to form a urethane elastomer material and may be sprayed, dipped, spin-coated, or known in the art.
The urethane elastomer material can be applied on the inner core using various application techniques, such as a flow coating method. An example of a suitable coating technique is the technique disclosed in U.S. Pat. No. 5,733,428, filed May 2, 1995, entitled "Method and Apparatus for Forming a Polyurethane Cover on a Golf Ball." And the disclosure of such a patent is hereby incorporated by reference in its entirety as an express reference.

If a cover or both an inner cover layer and an outer cover layer are present, the outer cover is preferably formed around the core by mixing the material and introducing it into the mold half. Viscosity is measured throughout, filling each mold half, introducing the core into one mold half, and centering and melting the core cover half melt so that the subsequent steps to close the mold occur at the appropriate time. To achieve uniformity. A suitable viscosity range of the urethane mix for curing to introduce the core into the mold half is about 2,000 cP
To about 30,000 cP, with a preferred range from about 8,000 cP to about 15,000 cP.

When the formation of the cover is started, metered amounts of hardener and prepolymer are fed through the line to achieve mixing of the prepolymer and hardener in an automatic mixer that includes a mixing head. Fill the top pre-heated mold halves and place them in the fixed unit using pins that go into the holes in each mold.
After the reaction material has been left in the top mold half for about 50 to about 80 seconds, the core is controlledly lowered into the gelled reaction mixture. Thereafter, the bottom mold half or series of bottom mold halves introduces a similar amount of the mixture into the cavity.

When the pressure in the hose is reduced (partial vacuum), the ball cup holds the ball core. After about 50-80 seconds of gelling, the coated core is placed in the mold half while the vacuum is released to release the core. A core and a solidified cover half are placed on the mold half. The core and the solidified cover half are removed from the centering fixing unit, turned upside down, and fitted with the other mold halves. The other mold half has already introduced the selected amount of the reactive polyurethane prepolymer and the curing agent and has begun to gel.

Similarly, both US Pat. No. 5,006,297 to Brown et al. And US Pat. No. 5,334,673 to Wu disclose suitable molding techniques. Such techniques can be used to apply the castable reaction liquid used in the present invention. The disclosure of each patent is expressly incorporated herein by express reference by reference to such patent. However, the method of the present invention is not limited to using these techniques.

In one embodiment, the temperature of the cover is between -30 ° C and 20 ° C.
The loss tangent at 0 C is typically between 0.16 and 0.075. In one embodiment, the complex modulus of the cover layer on the ball ranges from about 1000 to 28 at -30C to 20C.
00 kgf / cm ² . In one preferred embodiment, the specific gravity of the cover material is about 1-2, preferably about 1.1.
To 1.4. In one embodiment, the specific gravity of the cover material is between about 1.15 and 1.25.

When making golf balls in accordance with the present invention, the dimple area of the golf ball is typically greater than about 60 percent, preferably greater than about 65 percent, and more preferably greater than about 75 percent. It is. The flexural modulus of the cover on the golf ball typically exceeds about 500 psi, and is about 500 ps.
Preferably, i to 150,000 psi. As described herein, the outer cover layer is preferably formed from a relatively soft polyurethane material.
In particular, the hardness of the material of the outer cover layer is ASTM-224.
When measured at 0, it should be about 30 to 70 Shore D, preferably about 45 to about 60 Shore D. In one embodiment, the hardness of the outer cover layer is about 52 Shore D. When measuring the hardness of the outer cover material by measuring the hardness of the golf ball, such hardness is:
It tends to be higher than the hardness of the material itself. For example, if the hardness of the cover material is 45 Shore D, the hardness of the material measured on the ball will be 55 Shore D. When there is an inner cover layer, the material hardness of the inner cover layer is preferably about 50 to about 75 Shore D,
More preferably, it is 60 to 65 Shore D. The hardness of the material is determined by a number of factors, including the thickness and hardness of the other cover layers.

The recovery of golf balls made as a result of the present invention is typically greater than about 0.7, preferably greater than about 0.75, and greater than about 0.78. Is more preferable. The golf ball of the present invention has an attraction compression (previously referred to as PGA compression) of at least 40, preferably from about 50 to 120, and more preferably from about 60 to 100. is there. The flexural modulus of the polybutadiene material for golf balls of the present invention is typically between about 500 psi and 300,000 psi, and between about 2,000 and 200,000 ps.
i is preferred. The flexural modulus of the polybutadiene material for golf balls of the present invention typically ranges from about 500 psi to 300,000 psi, and
Preferably, it is between 000 and 200,000 psi.

[0162]An example  For the above and other aspects of the present invention, see the examples below.
Can be more fully understood, and such an example
The preferred embodiment of the structure of the Ming golf ball is merely illustrated.
Things. These examples are intended to limit the invention.
Not to be understood.

Various cores were made in accordance with the present invention, and some cores were made using conventional materials.
All cores in Table 2 have a diameter of about 4.0132 cm (1.5
8 inches). Table 2 shows the composition of each core and the measured values of compression and COR.

Table 3 shows various metal sulfide cis-to-trans catalysts that successfully converted some of the cis-polybutadiene isomers to the trans-isomers. CARIFFL
EXBR1220 polybutadiene (100 parts) was reacted with zinc oxide (5 parts), dicumyl peroxide (3 parts, free radical initiator) and zinc diacrylate (25 parts) to form a reaction product of the present invention.

The percent conversion of the trans-isomer ranges from less than 8 percent to more than 17 percent, corresponding to the various catalysts described above, and the amount of catalyst present is less than 1.7 parts. It spreads over a range of 3.7 parts or more. The effect of a number of different cis-to-trans catalysts in increasing the content of trans-polybutadiene at various concentrations is clearly shown in the table.

Example 1:Organic sulfur cis-to-trans catalyst
The core formed according to the present invention using  Organic-sulfur compound for cis-to-trans conversion catalyst
Used to create a core according to the invention. That
The properties of the resulting core are constructed using conventional techniques.
Golf made in accordance with the present invention, as compared to the example of
The advantages of the ball core are clearly illustrated. Those ingredients
And the physical properties are shown in Table 4.

The compressive load of the core manufactured according to the present invention is:
U.S. Pat. No. 5,697,856, U.S. Pat. No. 5,25
2,652, and approximately half the compressive load of a core constructed in accordance with U.S. Pat. No. 4,692,497, while the COR (resilience) is substantially the same while achieving the aforementioned compressive load. , In some cases, is higher. The compressive load of the core made according to the invention is low (soft) but elastic (fast). The compressive load of the core of the present invention is as disclosed in U.S. Pat.
Although greater than the compressive load of a core constructed according to No. 9,228, the COR is much higher. U.S. Pat. No. 3,239,2
No. 28 core is very soft and very slow (CO
R is very low).

The change in percent dynamic stiffness from 0 ° C to -50 ° C was also measured at the edge and center of the core. The change in dynamic stiffness at both the edge and center of the present invention was negligible, less than 20 percent over the pre-temperature range investigated. The change in core made according to U.S. Pat. No. 3,239,228 is greater than 230 percent, while the dynamic stiffness for cores made according to other conventional techniques is 130, over the same temperature range. It has changed by more than a percent, typically by as much as 150 percent.

The percent conversion of the trans-isomer at both the center and the edges of cores made in accordance with the present invention is also determined, as well as cores made as disclosed in the same four patents. Then, the trans-gradient was calculated. The trans-gradient of the core according to the invention was about 32 percent from edge to center. For cores made in accordance with the present invention, pre-cured trans-percent and post-cured trans-percent were also measured to determine the effectiveness of the method. Transformer
The percent of polybutadiene converted to isomers ranged from about 40 percent at the center to over 55 percent at the edges. Among cores made according to the prior art, U.S. Pat.
The trans-gradient of the two cores made according to 9,228 and U.S. Pat. No. 4,692,497 was zero. The trans-gradient of the third core made according to U.S. Pat. No. 5,697,856 was only slight and less than 18 percent from edge to center. The trans-gradient of the fourth core made according to U.S. Pat. No. 5,252,652 was very large, approximately 65 percent from edge to center.

Example 2:Inorganic sulfide-two-tolan
Core prepared according to the present invention using a catalyst  The core according to the invention is used as a cis-to-trans catalyst.
It was made using an inorganic sulfide compound. its
The resulting core properties are examples of cores constructed with conventional technology.
The advantage of the golf ball produced according to the present invention is
Points are clearly shown. Table 4 shows their components and physical properties.
Represent.

[0171] The compressive load is determined in US Pat. No. 5,697,85.
No. 6, almost half of the compressive load of three cores constructed according to U.S. Pat. No. 5,252,652 and U.S. Pat. No. 4,692,497, while COR (resilience) is less than the half compressive load. And at the same time achieved, and in some cases, higher. Cores made in accordance with the present invention are soft but elastic (fast). The compressive load is greater than a core constructed according to US Pat. No. 3,239,228, but the COR is significantly higher. The core of US Pat. No. 3,239,228 is very soft and very slow (low COR).

The change in percent dynamic stiffness from 0 ° C to -50 ° C was also measured at the edge and center of the core. The change in dynamic stiffness at both the edge and center of the invention was negligible, less than 125 percent over the pre-temperature range investigated. The change in core made according to U.S. Pat. No. 3,239,228 is greater than 230 percent, while the dynamic stiffness for cores made according to other conventional techniques is 130, over the same temperature range. It has changed by more than a percent, typically by as much as 150 percent.

The percentage of trans-conversion at both the center and the edge of a core made in accordance with the present invention was also determined, as was a core made as disclosed in the same four patents above. Transformer
The slope was calculated. The trans-gradient of the core according to the invention was about 45 percent from edge to center. Among cores made according to the prior art, U.S. Pat. No. 3,239,228 and U.S. Pat.
The trans-gradient of the two cores made according to No. 7 was zero. The trans-gradient of the third core made according to U.S. Pat. No. 5,697,856 was only slight and less than 18 percent from edge to center. The trans-gradient of the fourth core made according to U.S. Pat. No. 5,252,652 was very large, approximately 65 percent from edge to center.

Example 3:Organic sulfur sulfide and inorganic sulf
Using a cis-to-trans catalyst consisting of a blend of
Core prepared according to the present invention  The core according to the invention comprises a cis-to-trans conversion catalyst and
Of organic sulfur and inorganic sulfide compounds
It was made using a metal. The resulting core properties are
Compared to the example of a core constructed with the prior art, the present invention
The advantages of the golf ball made in this manner are clearly shown. So
Table 4 shows their components and physical properties.

[0175] The compressive load is the same as in US Patent No. 5,697,85.
No. 6, almost half of the compressive load of three cores constructed according to U.S. Pat. No. 5,252,652 and U.S. Pat. No. 4,692,497, while COR (resilience) is less than the half compressive load. And at the same time achieved, and in some cases, higher. Cores made in accordance with the present invention are soft but elastic (fast). The compressive load of the present invention is disclosed in U.S. Pat. No. 3,239,2.
28 larger than the fourth core constructed according to
R is significantly higher. The core constructed according to U.S. Pat. No. 3,239,228 is very soft and very slow (low COR).

The change in percent dynamic stiffness from 0 ° C to -50 ° C was also measured at the edge and center of the core. The change in dynamic stiffness at both the edge and center of the core of the present invention was negligible, less than 121 percent over the pre-temperature range investigated. The change in core made according to U.S. Pat. No. 3,239,228 is greater than 230 percent, while the dynamic stiffness for cores made according to other conventional techniques is 1% over the same temperature range.
Has changed by more than 30 percent, typically 15
0 percent has changed.

The percent conversion of the trans-isomer at both the center and the edges of cores made in accordance with the present invention is also determined, as well as cores made as disclosed in the same four patents. Then, the trans-gradient was calculated. The trans-gradient of the core according to the invention was about 44 percent from edge to center. For cores made in accordance with the present invention, pre-cured trans-percent and post-cured trans-percent were also measured to determine the effectiveness of the method. Transformer
The percent of polybutadiene converted to isomers ranged from about 26 percent at the center to more than 45 percent at the edges. Among cores made according to the prior art, U.S. Pat.
The trans-gradient of the two cores made according to 9,228 and U.S. Pat. No. 4,692,497 was zero. The trans-gradient of the third core made according to U.S. Pat. No. 5,697,856 was only slight and less than 18 percent from edge to center. The trans-gradient of the fourth core made according to U.S. Pat. No. 5,252,652 was very large, approximately 65 percent from edge to center.

Example 4:Wound ball produced according to the present invention  A dual core golf ball according to the present invention, comprising:
And a taut around the solid center
An intermediate layer of material and concentrically arranged around the intermediate layer
A golf ball having the multi-layer cover thus prepared. So
The components and physical properties of are shown in Table 5.

A solid center for a golf ball of the present invention was manufactured. The center will use CARIFFL as the starting material
Made from EX BR1220 polybutadiene. The only difference is that VAROX 802-40KE-HP peroxide (prior art) has been replaced by the DTDS cis-to-trans catalyst and dicumyl peroxide of the present invention. This substitution allows a portion of the polybutadiene material to be converted to the trans configuration during the molding process. The resulting outer diameter of the solid center is approximately 2.92.
1 cm (about 1.15 inches). The trans-isomer content of the resulting polybutadiene reaction product was 40 percent as compared to the conventional ball trans-isomer content of 1.5 percent. An intermediate layer having an outer diameter of about 1.56 inches was wound around the solid center with the thread material stretched to form a wound core. The taut material includes conventional cis-polyisoprene threads.

[0180]Example 5: Representative Bodies Made According to the Invention
Rule  CB23 polybutadiene rubber having a Mooney viscosity of about 50,
DTDS cis-to-trans catalyst, 33 parts of diacrylate
Uses zinc luate and a filler to control the density of the center
To create a representative ball. Center
Diameter should be about 3.5 inches (about 1.4 inches)
Can be. Center compression should be about 50
The deflection in the 130kg-10kg test is about
4.26 mm. Then, the diameter is about 0.06096c
m (approximately 0.024 inch) thread 800% elongation
And wound around the center to have a diameter of about 3.9624c.
m (about 1.56 inches).

The 8945 SURLYN sodium ionomer provides a 50% inner cover and the 7940 SURLYN lithium ionomer provides a 50% inner cover. The hardness of such a blend is 64 Shore D, and the inner cover is preferably formed to be about 0.035 inches thick. The outer cover is formed from a hardened RC11b cast urethane material having a hardness of about 45 Shore D to a thickness of about 0.03 inches. RC11b urethane is 6.0% of one equivalent
/ PTMEG polyol 200 with low NCO
0 prepolymer and 0.95 equivalent of Ethacure 3
It can be made from 00 and 3.5% HCC-19584 (white dispersion). RC11b is a material having a hardness of about 45 Shore D. ETHACURE300
Albermar Corporation of Baton Rouge, Los Angeles
f Baton Rouge, LA). Conventional paint or other colored stable packages can be applied on the golf ball cover. A suitable dimple pattern is 392 dual dimple 20
It is a face pattern, and the volume of the dimple is about 590mm
³ .

[0182]Example 6-22: Wound, with solid center
Comparison between the ball of the present invention and the prior art  Some Golf Balls Made According to the Invention (Example 11)
To 17) for some commercially available golf balls (eg,
6 to 10). Ball of the invention, ie Example 1
1 to 17 are formed of a polyisoprene material.
6096 cm (0.024 inch)
The diameter is about 4.0005 cm (1.575 inch)
H) The tension has been changed.
It is shown in the table. Mantle consisting of the same SURLYN of Example 10
Molded and applied on the cores of Examples 11 to 22 according to the present invention
did. The mantle then buffs for extra material.
Remove it to a diameter of 4.162 cm (1.62 inches)
To give a polyurethane material with a hardness of 45 Shore D
Thus, an outer cover layer was formed on the ball of the present invention.Golf balls of Examples 11 to 17 manufactured according to the present invention
Has the same initial velocity as the commercially available golf balls of Examples 6 to 10.
Degree, lower while retaining cover material compression and CoR
Exhibits ball compression. Golf made according to the present invention
The ball has a center with an increased diameter.
By using an equal amount of zinc diacrylate for
Effective compression of the ball without affecting the CoR value of the ball
It can be seen that it can be reduced to

[0183]Examples 18 to 25: filled with a fluid according to the invention
Comparison between golf ball and conventional technology  Making or Obtaining Conventional Golf Balls of Examples 18 to 23
In comparison with the golf balls of the present invention of Examples 24 to 25,
Was. Example 24 was made as noted below and had about 4.11
With a 48 cm (1.62 inch) inner cover layer
Together, the thread and tension are from Example 22. Example 2
5 was made as noted below and was approximately 4.1148 cm
(1.62 inches) inner cover layer and
Red and tension are from Example 23. Then, Example 2
4 to 25 balls were each made of the urethane compound of Example 20.
Coated.A fluid-filled ball made according to the invention is described in Example 18
Overall lower compression than 23 commercially available golf balls
No.

[0184]Examples 26 to 34: Wound golf balls of the present invention
Tool and conventional technology  Making or Obtaining Conventional Golf Balls of Examples 26-30
In comparison with the golf balls of the present invention of Examples 24 to 25,
Was. The invention of Examples 31 to 34 is based on CB23 rubber and
About 3.5306 cm (1.39) with gustene filler
Inch) core and is commercially available
Material and same as TitleistDT spin golf ball
Covered with a wound layer using the winding specification
3.937 cm (1.55 inches). Then the example
Consists of cover material using the same cover material as 28
The two layers have an outer diameter of approximately 4.1148 cm (1.62 cm).
Inch) urethane material inner cover layer and outer diameter
Is about 1.68 inches (4.272 cm).
An outer cover layer consisting of an onomer blend is applied to each wound layer.
Granted.

Example 31 according to the present invention, having a cover material hardness of 38 Shore D, was made as noted below. Example 32 was made according to the invention in which the hardness of the cover material was 38 Shore D and the core contained a material that converted some of the cis-isomer to the trans-isomer in the CB23 polymer during the core forming step. . The hardness of the cover material of Example 33 is 45
Shore D. The hardness of the cover material of Example 34 is 45
Shore D, containing the same materials as in Example 32,
A portion of the cis-isomer in 3 was converted to the trans-isomer. The compression of golf balls having a soft cover material made in accordance with the present invention is generally lower than the commercially available golf balls of Examples 26-30.

[0186]Examples 35 to 41: Polyurea thread-wound golf balls
Tool and conventional technology  The commercially available conventional golf balls of Examples 35 to 37 are
The golf balls of the present invention of Examples 38 to 41 were compared. Book
The cores of examples 38 to 39 according to the invention provide a winding thread
The previous compression is 75 and the diameter is about 3.556 cm (1.
400 inches). Examples 40 to 41 according to the invention
The core has a compression of 79 before applying the winding yarn, and has a diameter of
Is approximately 1.470 inches (3.7338 cm).
Was. Then, Examples 38 to 41 according to the present invention further describe
A wound layer made of a polyether urea material having an outer diameter of about 3.9
Adjust to 37cm (1.550 inch)
Consists of cover material using the same cover material as 37
The two layers have an outer diameter of approximately 4.1148 cm (1.62 cm).
Inch) urethane material inner cover layer and outer diameter
Is about 1.68 inches (4.272 cm).
An outer cover layer composed of an onomer blend is applied to the wound layer.
Granted.The golf balls produced according to the present invention are described in Examples 35 to 3
7 and the same compression and cover material hardness as the conventional golf ball of No. 7.
While maintaining the degree, overall CoR is higher than the conventional one
Is getting higher.

While it is clear that the above-exemplified embodiments of the invention disclosed herein fulfill the above-mentioned objectives, those skilled in the art will devise various modifications and other embodiments. It is understandable that things are possible. For example, the present invention may use two or more threads, each of which is chemically, physically or mechanically different. Therefore, it is not difficult to understand that the appended claims are intended to cover all such modifications and embodiments that fall within the spirit and scope of the invention.

[0188]

The use of the polyurethane composition according to the present invention in forming the golf ball core, the intermediate and mantle layers and / or the cover allows the speed of golf balls made with such a composition to be increased by (1) It can be increased to near the speed found with SURLYN® covered golf balls, and (2) to a speed higher than that shown when using alternative urethane formulations.

It is also desirable to combine a polyurethane cover formulation with a polybutadiene core material, where the resilience index is greater than about 40 and at least one wound layer is provided between the core and the cover. Especially so. Cores formed from these polybutadiene materials can provide exceptional resilience properties without compromising performance properties.

[Brief description of the drawings]

The features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the drawings described below.

FIG. 1 is a sectional view of a first embodiment of a golf ball according to the present invention.

FIG. 2 is a sectional view of a second embodiment of the golf ball according to the present invention.

FIG. 3 is an enlarged partial perspective view of a conventional single-ply thread used for the golf ball of the present invention.

FIG. 4 is an enlarged partial perspective view of a conventional two-ply sled used for the golf ball of the present invention, but is not necessarily on a correct scale as compared with other figures.

FIG. 5 is an enlarged partial perspective view of another two-ply sled used in the golf ball of the present invention, but not necessarily to the correct scale as compared to the other figures.

FIG. 6 is an enlarged partial perspective view of a thread used in the golf ball of the present invention, but is not necessarily on a correct scale as compared with other figures.

FIG. 7 is a cross-sectional view of a golf ball according to the present invention having an additional layer.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) C08L 101/00 C08L 101/00 (72) Inventor Herbert Seaboom Massachusetts, 02061 Norwell Judges Hill Road 34 (72) Inventor Edmund A. Hubert, Massachusetts, United States 02719 Fairhaven Ivy Lane 7 (72) Inventor William E. Morgan, Rhode Island, United States 02806 Barrington Meadow Circle 8, (72) Inventor Christopher Caballero, United States Massachusetts, United States 02347 Lakeville, Bachhand Road 17 (72) Inventor Roman Dee Halco United States Massachusetts Tsu Tsu State 02048 Mansfield East scan Treat 1143 F-term (reference) 4J002 AC07X AC08X BB22X CF00X CF09X CK01X CK02W CK02X CL00X CL07X GC01

Claims (44)

[Claims] 1. A center comprising one or more layers comprising polybutadiene having a molecular weight greater than about 200,000 and having a resilience index of at least about 40, and having not more than 7.5 weight percent of unreacted isocyanate groups. A cover having at least one layer with a polyurethane compound formed from the pre-polymer, and at least one thread material disposed between the center and the cover, wherein each thread comprises at least one thread. A golf ball comprising: a wound layer having the following strands. 2. The golf goal according to claim 1, wherein said cover includes an inner cover layer and an outer cover layer, and wherein said inner cover layer is disposed between said wound layer and said outer cover layer. Golf ball. 3. The golf ball according to claim 2, wherein said inner cover layer is harder than said outer cover layer. 4. The golf ball according to claim 2, wherein said inner cover layer comprises at least one thermoplastic material. 5. The golf ball according to claim 2, wherein said inner cover layer comprises an ionomer resin, polyurethane, polyetherester, polyetheramide, polyester,
Dynamically vulcanized elastomers, polyureas, functionalized styrene butadiene elastomers, metallocene polymers,
A golf ball comprising nylon, acrylonitrile butadiene-styrene copolymer, or a blend thereof. 6. The golf ball of claim 2, wherein the outer diameter of the inner layer is at least about 1.5 inches.
5 inch) golf ball. 7. The golf ball of claim 2, wherein the outer diameter of the inner cover is from about 4.0132 cm to about 4.16.
A golf ball that is 56 cm (about 1.58 inches to about 1.64 inches). 8. The golf ball of claim 1, wherein said polyurethane compound comprises at least one isocyanate, at least one polyol, and at least one curing agent. 9. The golf ball of claim 8, wherein the isocyanate is 4,4'-diphenylmethane diisocyanate, polymer 4,4'-diphenylmethane diisocyanate, carbodiimide-modified liquid 4,
4'-diphenylmethane diisocyanate, 4,4'-
Dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, p-methyl xylene diisocyanate, m-methyl xylene diisocyanate, o
A golf ball comprising methyl xylene diisocyanate or mixtures thereof. 10. The golf ball of claim 8, wherein said at least one polyol comprises a polyether polyol, a hydroxy-terminated polybutadiene, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, or a mixture thereof. Golf ball. 11. The golf ball according to claim 8, wherein said curing agent comprises a polamine curing agent, a polyol curing agent, or a mixture thereof. 12. The golf ball according to claim 11, wherein said curing agent comprises a polyamine curing agent. 13. The golf ball according to claim 11, wherein said curing agent comprises a polyol curing agent. 14. The golf ball of claim 1, wherein said prepolymer has from about 2.5 to up to 7.5 weight percent of unsaturated isocyanate groups. 15. The golf ball of claim 1, wherein the thickness of the cover layer is less than about 0.05 inches. 16. The golf ball according to claim 1, wherein said inner cover layer has a thickness of about 0.127 cm (about 0.05 cm).
Inch) golf ball. 17. The golf ball of claim 1, wherein said inner cover layer and said outer cover layer have a combined thickness of:
A golf ball that is less than about 0.07 inches. 18. The golf ball according to claim 1, wherein the polybutadiene material of the cover layer is made of a Mooney.
ney) A golf ball having a viscosity of about 40 to about 80. 19. The golf ball of claim 8, wherein said Mooney viscosity is from about 45 to about 60. 20. The golf ball of claim 1, wherein the polybutadiene has a vinyl-isomer content of less than about 2 weight percent. 21. The golf ball of claim 1, wherein said polybutadiene has a cis-isomer content of at least about 9%.
A golf ball that is 5 weight percent. 22. The golf ball of claim 1, wherein the center has an outer diameter of at least about 1.3 inches. 23. The golf ball of claim 1, wherein the center is formed from a conversion reaction of a polybutadiene having a first amount of a trans-isomer, a source of free radicals and at least one cis- A golf ball comprising a two-trans catalyst. 24. The golf ball of claim 23, wherein the reaction is a second amount greater than the first amount of the trans-isomer.
A golf ball that occurs at a constant temperature and for a period of time sufficient to form a polybutadiene reaction product having an amount of trans-isomer. 25. The golf ball according to claim 23, wherein said cis-to-trans catalyst comprises an organic sulfur compound, an inorganic sulfur compound, an aromatic organometallic compound, a metal-organic sulfur compound, tellurium,
A golf ball comprising at least one of selenium, elemental sulfur, polymeric sulfur, or an aromatic organic compound. 26. The golf ball of claim 1, wherein said polyurethane is a thermoplastic or thermoset. 27. The golf ball according to claim 1, wherein
The golf ball has a recovery rate of at least about 0.76 when hit with a golf club head at a speed of 0 feet / second, and the magnitude of the recovery rate gradient to the return speed is at least about 0.001 seconds / foot. Golf ball. 28. A center comprising polybutadiene having a molecular weight of greater than about 300,000 and a resilience index of at least about 40, and surrounding the center and having an outer diameter of at least about 3.8354.
cm (about 1.51 inches) and comprising at least one thread material between the center and the cover, each thread surrounding a wound layer having at least one strand, and an outer core layer. An inner cover layer, and an outer cover layer surrounding the inner cover layer and comprising a polyurethane formulation formed from a prepolymer having less than 7.5 weight percent unreacted isocyanate groups. Golf ball to play. 29. A center comprising polybutadiene having a molecular weight of greater than about 300,000 and a resilience index of at least about 40, and a center surrounding the center and having an outer diameter of at least about 3.8354.
a hoop stress layer disposed between the center and the cover, wherein the hoop stress layer is glass, polyamide, aromatic polyamide, carbon, or at least about 250 kpsi. A hoop stress layer comprising metal fibers having a modulus of at least about 10,000 kpsi; and at least one layer disposed about the wound hoop stress layer, wherein less than 7.5 weight percent of unreacted isocyanate And a cover comprising a polyurethane compound formed from a prepolymer having a base. 30. A center, a wound layer surrounding the center, an inner cover layer surrounding the wound layer and having a first hardness, and surrounding the inner cover layer and having a hardness less than the first hardness. And a thickness of about 0.127 cm (about 0.127 cm).
And an outer cover layer that is less than 0.05 inches). 31. The golf ball of claim 30, wherein the inner cover is less than about 0.05 inches. 32. The golf ball of claim 30, wherein said inner cover comprises at least one ionomer. 33. The golf ball of claim 30, wherein said outer cover comprises at least one castable material. 34. The golf ball of claim 30, wherein said at least one castable material is a thermoset or thermoplastic polyurethane compound. 35. The golf ball of claim 34, wherein said polyurethane compound comprises at least one isocyanate and at least one curing agent. 36. The golf ball of claim 35, wherein said isocyanate is 4,4'-diphenylmethane diisocyanate, polymer 4,4'-diphenylmethane diisocyanate, carbodiimide-modified liquid 4,4'-diphenylmethane diisocyanate,
4'-dicyclohexylmethane diisocyanate, p-
A golf ball comprising phenylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, p-methyl xylene diisocyanate, m-methyl xylene diisocyanate, o-methyl xylene diisocyanate, or a mixture thereof. 37. The golf ball of claim 35, wherein the curing agent comprises a polamine curing agent, a polyol curing agent, or a mixture thereof. 38. The golf ball of claim 37, wherein said curing agent comprises a polyamine. 39. The golf ball of claim 37, wherein said curing agent comprises at least one polyol. 40. The golf ball of claim 39, wherein said at least one polyol is a polyether polyol, a hydroxy-terminated polybutadiene, a polyester polyol, a polycaprolactone polyol,
A golf ball comprising a polycarbonate polyol or a mixture thereof. 41. The golf ball of claim 30, wherein the combined thickness of the inner cover layer and the outer cover layer is less than about 0.07 inches. 42. The golf ball of claim 30, wherein said center is a material formed from a conversion reaction of a polybutadiene having a first amount of a trans-isomer, a source of free radicals and at least one cis- A golf ball comprising a two-trans catalyst. 43. The golf ball of claim 42, wherein said reaction is a second amount greater than the first amount of the trans-isomer.
A golf ball that occurs at a constant temperature and for a period of time sufficient to form a polybutadiene reaction product having an amount of trans-isomer. 44. The golf ball of claim 42, wherein said cis-to-trans catalyst comprises an organic sulfur compound, an inorganic sulfur compound, an aromatic organometallic compound, a metal-organic sulfur compound, tellurium,
A golf ball comprising at least one of selenium, elemental sulfur, polymeric sulfur, or an aromatic organic compound.