JP2002263220A - Thermoplastic polyurethane golf ball with improved resilience - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve durability and a carry. SOLUTION: In this gold ball, at least one of a cover and at least one of intermediate layers is formed of a thermoplastic polyurethane composition. The thermoplastic polyurethane composition consists of a reaction product between at least one polyol, at least one diisocyanate, and a curing agent. The curing agent substantially consists of at least one diol, and the formula of the diol is expressed by HOH2 CH2 C(OH2 CH2 C)n O-X-O(CH2 CH2 O)m CH2 CH2 OH; wherein, n and m independently represent a value of 0, 1, 2, or 3; and X represents o-phenylene, m-phenylene, p-phenylene, 1,2-cyclohexyl, 1,3-cyclohexyl, or 1,4-cyclohexyl and a mixture of them.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention is filed on May 14, 1999.
It is a continuation-in-part of the application number 09 / 311,591 filed on the date of which is incorporated herein by reference in its entirety.

The present invention relates generally to golf balls, and more particularly to golf balls having elements such as a core, an intermediate layer, and a cover formed from a polymer blend of a thermoplastic polyurethane composition. The thermoplastic polyurethane composition comprises at least one diisocyanate and a polyol and at least one diol or second diamine curing agent. The golf balls of the present invention have been found to provide desired playing characteristics such as durability and improved resilience.

[0003]

2. Description of the Related Art Conventional golf balls can be divided into two groups as a whole. That is, a solid ball and a wound ball. The differences in play characteristics resulting from these different structures are quite significant.
Balls having a solid structure are most popular among golfers playing golf as an average leisure as a whole, because they provide maximum distance and provide a durable ball. One-piece solid golf balls are well known in the art. Other types of solid balls are well known in the art and are usually formed from a solid core formed from crosslinked rubber, which is surrounded by a cover material. Typically, the solid core is formed from polybutadiene chemically cross-linked with zinc diacrylate and / or a similar cross-linking agent. Solid core is tough, cut-proof
f), which cover is generally made by E.M. of Wilmington, Delaware. I. EI DuPont de N
emours and Co. of Wilmington
on, DE) is an ionomer resin manufactured by SURL
It is formed from YN (registered trademark).

As a cover material, ionomer resins have largely replaced balata. Chemically, ionomer resins are copolymers of olefins and a, β-ethylenicaly-unsaturated carboxylic acids, wherein the carboxylic acids have carboxylic acid groups neutralized with 10 to 90% metal ions. Chemically available ionomer resins include, for example, copolymers of methacrylic acid or acrylic acid neutralized with ethylene and a metal salt, such copolymers being commercially available from SURLYN® and Exxon Corporation. IOTEK (registered trademark). These ionomer resins are classified according to metal ion, amount of acid and degree of neutralization.

[0005] When the core is surrounded by an ionomer cover material, the ball is substantially not broken by the golfer. Further, in such a combination, the initial velocity of the ball is increased, and as a result, the distance is improved.
Because the material forming the ball is very robust,
Solid balls generally have a hard feel or feel when hit with a club. Similarly, due to the hardness of the material, the spin rate of the ball is relatively low, which is another factor that increases distance.

The typical single-layer core and single-layer cover structure is modified to provide a double-layer cover, a multi-layer ball with a double-layer core, and / or a ball with a mantle layer between the cover and the core. Modifying the properties of a conventional solid ball in this manner is well known in the art. Like the solid core, the various cover layers, mantle layers and interlayers are typically formed of polybutadiene chemically cross-linked with zinc diacrylate and / or similar cross-linking agents. The play characteristics, such as "feel" and compression, of a multi-layer ball can be customized by altering the characteristics of one or more of the intermediate layers described above.

Wound balls are preferred by higher players due to their spin rate and feel characteristics. Wound balls typically have a solid rubber or liquid central core with a tight, elastic thread or yarn wound around it. Then, the wound core is SURLYN
It is covered with a durable cover material such as (registered trademark) or a soft cover material such as Balta or polyurethane. Balta is a natural or synthetic trans-polyisoprene rubber and is the preferred cover material for golfers with a high degree of technology because of its softness. Wound balls are generally softer and have a higher spin rate than non-wound balls, and this property allows a skilled golfer to precisely control the direction, flight profile and distance of a golf ball. . Proof of the high control and stopping ability of the wound ball covered with Balta can be seen by approach shot to the green. That is, the high spin rate of these wound balls allows the golfer to stop the ball very close to its landing position. However, balata covered balls are susceptible to damage and therefore lack the durability required for a golfer at leisure.

The properties of the layers used in forming conventional solid balls, multi-layer balls having double cover layers, double core layers and / or balls and wound balls having a mantle layer disposed between the cover and core. A number of related patents have been issued. For example, polyurethane is 1960
It has been considered a useful material for golf ball covers since circa. U.S. Pat. No. 3,147,324,
The present invention relates to a method for manufacturing a golf ball having a polyurethane cover.

[0009] Thermoplastic polyurethanes are the reaction products of at least one diisocyanate and at least one polyol with a curing agent. The curing agent used in the thermoplastic polyurethane composition is typically a secondary diamine or diol. Often a catalyst is used to facilitate the reaction between the diisocyanate, polyol and secondary diamine or diol. Typical catalysts are metal catalysts such as bismuth, organic acids such as acetic acid and oleic acid, POLYCAT SA-1 and POLYCAT.
Includes thermal activity retarding catalysts such as SA-102 and other catalysts such as triethylenediamine and di-butyltin dilaurate.

[0010] Polyurethanes typically fall into two categories. That is, there are two classifications of thermosetting and thermoplastic. Thermoplastic polyurethanes include at least diisocyanates such as 4,4'-diphenylmethane diisocyanate or 3,3'-dimethyl-4,4'-biphenylene diisocyanate and diols such as 1,4-butanediol or Unilink 4200 or Clear.
It is formed by the reaction of a polyol cured with a secondary diamine such as ink 1000. Thermosetting polyurethanes include diisocyanates such as 2,4-toluene diisocyanate or methylene-bis-4-cyclohexyl isocyanate and polyamines (excluding secondary diamines);
Triols such as trimethylolpropane or N, N,
N ', N'-tetra-bis-2-hydroxyprofile is formed by the reaction of a polyol cured with a tetrafunctional glycol such as ethylenediamine.

[0011] Since 1960, various companies have explored the benefits of polyurethanes as golf ball covers. U.S. Pat. No. 4,123,061 discloses a polyurethane prepolymer of polyester and a trifunctional polyol,
A golf ball formed from a curing agent such as a tetrafunctional polyol or diamine is taught. US Patent No. 5,33
No. 4,673, covered with thermosetting polyurethane,
Formation of golf ball covers using two classes of commercially available polyurethanes, namely thermoset and thermoplastic polyurethanes, particularly polyurethane prepolymers and slow reacting amine curing agents and / or bifunctional glycols. A golf ball comprising the composition is disclosed. The first commercially successful polyurethane-covered golf ball was the Titleist, first launched in 1993.
(Registered trademark) professional ball.

Unlike golf balls covered with SURLYN®, polyurethane golf ball covers can be formulated to have the soft “feel” of golf balls covered with balata. However, to date, golf ball covers made from polyurethane have, to date, been SURLYN in terms of golf ball cover rebound as a function of resilience or initial velocity of the golf ball after being hit with a golf club.
(Registered trademark) golf ball.

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

US Pat. No. 4,123,061 discloses a golf ball formed from a polyurethane prepolymer of polyether and a curing agent such as a trifunctional polyol, a tetrafunctional polyol or a fast-reacting diamine curing agent.

US Pat. No. 5,334,673 discloses a golf ball cover formed from a composition of a thermosetting polyurethane prepolymer and a slow-reacting polyamine curing agent and / or a bifunctional glycol. The resulting golf ball is judged to have improved shear and cut resistance 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. Further, such patents relate to golf balls having a cover and a core incorporating a urethane ionomer. Addition of an alkylating agent, such as t-butyl-chloride, which produces cation-type ionomers through ionic interactions in the polyurethane improves resilience and initial rate.

International Patent Application WO 98/37929 states that
A composition for a golf ball cover comprising a blend of a diisocyanate / polyol prepolymer and a curing agent comprising a blend of a slow reacting diamine and a fast reacting diamine is disclosed. Improvements in properties such as "feel", playability and durability are shown.

[0018]

Conventional polyurethane elastomers are known for their lower resilience than SURLYN® and other ionomer resins. Golf ball core comprising the polyurethane composition of the present invention,
When used to form intermediate and mantle layers and / or covers, the speed of golf balls made with such compositions can be increased by
It can be increased to the speed obtained with a golf ball covered with URLLYN®. Further, the curatives used in the compositions of the present invention include:
Air Products and Chemical
VER, an oligomeric diamine manufactured by s
It is less expensive than many hardeners typically used by those skilled in the art, such as SALINK® P-250. Also, the compositions of the present invention are more environmentally friendly than other cost-effective options such as ETHACURE® 300 and ETHACURE® 100.

[0019]

SUMMARY OF THE INVENTION The present invention provides a center,
Bar and optionally between the center and cover
Golf ball with at least one intermediate layer disposed
, The cover and the at least one intermediate layer
At least one is formed of a thermoplastic polyurethane composition.
Wherein the thermoplastic polyurethane composition is at least
Also one polyol and at least one diisocyanate
And a reaction product of a curing agent and the curing agent.
But consists essentially of at least one diol
The diol is mixed with HOH₂CH₂C (OH₂
CH₂C)_nO-X-O (CH₂CH ₂O)_mCH₂C
H₂OH, wherein n and m are each independently 0,
Has a value of 1, 2, or 3, wherein X is 0-phenylene,
m-phenylene, p-phenylene, 1,2-cyclohexyl
Sil, 1,3-cyclohexyl or 1,4-cyclohexyl
It is characterized by being xyl and a mixture thereof.

[0020]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a center, a cover and
Optionally placed between the center and cover
Golf ball with at least one intermediate layer
The cover and the at least one intermediate layer
At least one is formed of a thermoplastic polyurethane composition.
Wherein the thermoplastic polyurethane composition comprises at least one
One polyol and at least one diisocyanate
And a reaction product of a curing agent, wherein the curing agent is
Qualitatively composed of at least one diol,
The mixture of diol is HOH₂CH₂C (OH₂CH
₂C)_nO-X-O (CH₂CH ₂O)_mCH₂CH₂
OH, wherein n and m are each independently 0, 1,
Has a value of 2 or 3, wherein X is 0-phenylene, m-
Phenylene, p-phenylene, 1,2-cyclohexyl
1,3-cyclohexyl or 1,4-cyclohexyl
It is characterized by sill and a mixture thereof. Suitable
In a preferred embodiment, n and m are each independently a value of 1 or 2.
Having.

In another embodiment, the polyurethane composition further comprises ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol,
1,4-dibutanediol, 1,5-pentanediol,
It comprises at least one diol hardener selected from the group consisting of 1,4-sidehexane-dimethanol, 1,6-hexanediol, and polytetramethylene ether glycol having a molecular weight of less than 2000. In another embodiment, the thermoplastic polyurethane composition includes at least two curing agents. Further, the molecular weight of the diol curing agent is at least about 50.

The diisocyanate is preferably 4,4 '
-Diphenylmethane diisocyanate, polymer 4,
4'-diphenylmethane diisocyanate, liquid 4,
4'-diphenylmethane diisocyanate, toluene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, p-tetramethyl xylene diisocyanate, m-tetramethyl xylene diisocyanate, nephthalene diisocyanate , 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, m-phenylene diisocyanate, low free isocyanate monomers and mixtures thereof.

The polyol is polytetramethylene ether glycol, polyoxypropylene glycol,
Polyethylene adipate glycol, polyethylene propylene adipate glycol and polybutylene adipate glycol, ortho-phthalate-1,6-hexanediol polyester polymer, diethylene glycol-initiated polycaprolactone, trimethyllorpropane-initiated polycaprolactone, neopentyl glycol-initiated polycaprolactone, 1, 4-butanediol-initiated polycaprolactone, 1,6-hexanediol-initiated polycaprolactone, saturated and unsaturated hydrocarbon polyols, hydroxy-terminated liquid isoprene rubber, hydroxy-terminated polybutadiene, copolymers of the above polyols and mixtures thereof It is possible.

In a preferred embodiment, the polyol is selected from the group consisting of polytetramethylene ether glycol, polyethylene adipate glycol, polybutylene adipate glycol, diethylene glycol initiated polycaprolactone, and mixtures thereof. In another embodiment, the polyol has a molecular weight of about 2
00 to 4000.

The polyol is present in an amount of about 70 to 98 weight percent of the diisocyanate and the polyol, and the diisocyanate is present in an amount of about 2 to 30 weight percent of the diisocyanate and the polyol. Present, and wherein the diol curing agent has an amount of the diisocyanate and the polyol of 1
It is present in amounts from 0 to 110 weight percent. In yet another embodiment, the diisocyanate is present in an amount of about 2.5 to 12 weight percent of the diisocyanate and the polyol. In a preferred embodiment,
The thermoplastic polyurethane composition further includes at least one secondary diamine curing agent.

In another embodiment, the secondary diamine curing agent is 4,4'-bis-sec-butylamino-diphenylmethane, 1,4-bis-sec-butylamino-benzene, 1,2-bis -Sec-butylamino-benzene,
Derivatives of 4,4'-bis-sec-butylamino-diphenylmethane, 1,4-bis-sec-butylamino-cyclohexane, 1,2-bis-sec-butylamino-cyclohexane, 4,4'-bis-secane -Butylamino-diclohexylmethane (diclohexylmetha)
ne), a derivative of 4,4'-bis-sec-butylamino-dicyclohexylmethane, and mixtures thereof. In a preferred embodiment, the thermoplastic polyurethane composition comprises a reaction product of 4,4'-diphenylmethane diisocyanate, polytetramethylene ether glycol, and 1,3-bis- (2-hydroxyethoxy) benzene and 1,3- [Bis- (2-hydroxyethoxy)]-diethoxybenzene. The cover can also include a thermoplastic polyurethane composition.

In one embodiment, the ball includes at least one intermediate layer, the intermediate layer including a thermoplastic polyurethane composition. The center can be a fluid-filled center, a solid center, a gel center, or a hollow center. The thermoplastic polyurethane composition can also include a density modifying filler.

The present invention also relates to a golf ball comprising a center, a cover and optionally at least one intermediate layer disposed between said center and said cover, wherein at least one of said cover and said at least one intermediate layer is provided. One relates to a golf ball formed of a thermoplastic polyurethane composition comprising a curing agent comprising a reaction product of at least one polyol and at least one diisocyanate and a secondary diamine.

Preferably, the diisocyanate is 4,4 '
-Diphenylmethane diisocyanate, polymer 4,
4'-diphenylmethane diisocyanate, liquid 4,
4'-diphenylmethane diisocyanate, toluene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, p-tetramethyl xylene diisocyanate, m-tetramethyl xylene diisocyanate, naphthalene diisocyanate, It is selected from the group consisting of 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, m-phenylene diisocyanate, low-free isocyanate monomers and mixtures thereof.

In another embodiment, the polyol is polytetramethylene ether glycol, polyoxypropylene glycol, polyethylene adipate glycol,
Polyethylene propylene adipate glycol and polybutylene adipate glycol, ortho-phthalate
1,6-hexanediol polyester polymer, diethylene glycol-initiated polycaprolactone, trimethylolpropane-initiated polycaprolactone, neopentyl glycol-initiated polycaprolactone, 1,4-plandiol-initiated polycaprolactone, 1,6-hexanediol- Starting polycaprolactone, saturated and unsaturated hydrocarbon polyols, hydroxy-terminated liquid isoprene rubber,
It is selected from the group consisting of hydroxy-terminated polybutadiene polyols, copolymers of the above polyols, and mixtures thereof.

Preferably, said polyol is selected from the group consisting of polytetramethylene ether glycol, polyethylene adipate glycol, polybutylene adipate glycol, diethylene glycol initiated polycaprolactone and mixtures thereof. The polyol has a molecular weight of about 200 to 4000.

In another embodiment, the polyol comprises about 70 to 9 of the diisocyanate and the polyol.
8% by weight, the diisocyanate is present in an amount of about 2 to 30% by weight of the isocyanate and the polyol, and the secondary diamine curing agent is the diisocyanate and the polyol. Is present in amounts from 10 to 110 weight percent. In a preferred embodiment, the diisocyanate is present in an amount of about 2.5 to 12 weight percent of the isocyanate and the polyol.

The secondary diamine curing agent is 4,4′-
Bis-sec-butylamino-diphenylmethane, 1,4
-Bis-sec-butylamino-benzene, 1,2-bis-sec-butylamino-benzene, derivatives of 4,4′-bis-sec-butylamino-diphenylmethane, 1,4
-Bis-sec-butylamino-cyclohexane, 1,2
-Bis-sec-butylamino-cyclohexane, 4,
It may be 4′-bis-sec-butylamino-dicyclohexylmethane, a derivative of 4,4′-bis-sec-butylamino-dicyclohexylmethane, or a mixture thereof.

In yet another embodiment, the thermoplastic polyurethane composition comprises a reaction product of 4,4'-dicyclohexylmethane diisocyanate, a copolymer of polytetramethylene ether glycol and polycaprolactone, and 4,4'-bis- ( (Sec-butylamino) -dicyclohexylmethane. In a preferred embodiment, the cover comprises a thermoplastic polyurethane composition. In another preferred embodiment, the ball comprises at least one intermediate layer comprising a thermoplastic polyurethane composition. The center can be a fluid-filled center, a solid center, a gel center, or a hollow center. Further, the thermoplastic polyurethane composition can include a density modifying filler.

[0035]

DETAILED DESCRIPTION OF THE INVENTION The present invention is particularly directed to a golf ball having a core, a cover and, optionally, an intermediate layer, wherein at least one of the cover and the optional intermediate layer comprises at least one diisocyanate and at least one polyol, and at least one polyol. The resulting golf ball is formed from a thermoplastic polyurethane composition comprising a curing agent comprising one diol or a secondary diamine, preferably a blend of a diol and a secondary diamine, resulting in resilience, initial speed and durability. The present invention relates to a golf ball characterized in that the golf ball has improved performance. The present invention
It also relates to the use of the thermoplastic polyurethane composition in the manufacture of golf club inserts and golf-related equipment such as the golf balls described herein.

The golf ball formed according to the present invention comprises:
It is possible to have a one-piece structure formed entirely from a uniform mass of the thermoplastic polyurethane composition of the present invention. Such balls can further include a blend of conventional golf ball covers and / or interlayer materials as described herein, if desired. One-piece balls formed from the materials disclosed herein are fairly durable, but do not extend significantly over distance due to relatively high and low spin rates. More preferred embodiments of the present invention include two-piece balls, multi-element balls and wound balls, wherein the balls comprise a core, a liquid center, an intermediate layer and / or a thermoplastic polyurethane blend of the type disclosed herein. With a cover.

As used herein, "golf ball core" can refer to any portion of a golf ball that is encased in a cover. For golf balls having three or more layers, the term "golf ball core" includes at least one inner layer, and typically refers to the center and at least one intermediate layer. Such balls are known as "double core" golf balls. The center may be solid, gel-like, hollow, or filled with a fluid. The term "inner core" may be used interchangeably with "center" or "golf ball center," while the term "outer core" refers to "intermediate layer" or "at least one intermediate layer." May be used interchangeably. For example, one optional type of intermediate layer is a taut elastic material wrapped around a center. When the taut elastic material is included as an intermediate layer, the composition of the present invention is preferably incorporated into the elastic material, the center or both. The intermediate layer is, for example,
Can be included in a ball with a single-layer or multilayer cover, a ball with a single-layer or multilayer core, a ball with both a single-layer cover and a core, or a ball with both a multilayer cover and a multilayer core It is. Interlayers of the type described above are sometimes referred to in the art,
Also referred to herein as the inner cover layer, outer core layer or mantle layer.

The thermoplastic polyurethane composition of the present invention comprises:
Preferably, at least one diisocyanate, less
At least one polyol and at least one
The curing agent is composed of HOH₂CH₂C (OH₂CH₂C)_nO-X-O (C
H₂CH₂O)_mCH ₂CH₂OH, where n and m are each independently 0, 1, 2, or
Or 3 wherein X is 0-phenylene, m-phenylene.
Len, p-phenylene, 1,2-cyclohexyl, 1,
3-cyclohexyl or 1,4-cyclohexyl
You. Preferably, the values of n and m are 1 or 2. Mr
Various finylene structures are illustrated in FIGS. 1-3 below.

The thermoplastic polyurethane composition of the present invention comprises:
It contains at least one polyol. Suitable polyether polyols include, but are not limited to, polytetramethylene ether glycol, polyoxypropylene glycol, and mixtures thereof. Suitable polyester polyols are o-phthalate-1,6-
Includes, but is not limited to, hexanediol, polyethylene adipate glycol, polyethylene propylene adipate glycol, porbutylene adipate glycol, and mixtures thereof. Suitable polycaprolactone polyols include diethylene glycol-initiated polycaprolactone, trimethylolpropane-initiated polycaprolactone, neopentyl glycol-initiated polycaprolactone, 1,4-butanediol-initiated polycaprolactone, 1,6-hexanediol-initiated polycaprolactone, and the like. Including but not limited to copolymers and mixtures thereof.

Suitable moisture resistant polyols include saturated and unsaturated hydrocarbon polyols, hydroxy-terminated liquid isoprene rubber, hydroxy-terminated polybutadiene polyols, copolymers, and mixtures thereof. Suitable polyols for use with the present invention include polytetramethylene ether glycol, polyethylene adipate glycol, polybutylene adipate glycol and diethylene glycol initiated polycaprolactone, copolymers and mixtures thereof. In another embodiment, the molecular weight of the polyol is between 200 and 4000.

The thermoplastic polyurethane composition of the present invention comprises:
Contains diisocyanate. Suitable diisocyanates for use in the present invention include 4,4'-diphenylmethane diisocyanate ("MDI"), polymeric MDI, liquid M
DI, toluene diisocyanate ("TDI"), 3,
3'-dimethyl-4,4'-biphenylene diisocyanate ("TODI"), para-phenylene diisocyanate ("PPDI"), isophorone diisocyanate ("IPDI"), 4,4'-dicyclohexylmethane diisocyanate ("HMDI") , Hexamethylene diisocyanate (“HDI”), p-tetramethylxylene diisocyanate (“p-TMXDI”), m-tetramethylxylene diisocyanate (“m-TMXD
I "), naphthalene diisocyanate (" NDI "),
m-phenylene diisocyanate ("MPDI"), low free isocyanate monomers, and mixtures thereof. Raw free monomers are low levels of "free" monomeric isocyanate groups, typically about 0.1%
With less than free monomer groups. Examples include, but are not limited to, raw free monomer MDI, raw free monomer TDI, and raw free monomer PPDI.

The diisocyanate is preferably used when the amount of the diisocyanate and the polyol is from about 2.5 to 14
Weight percent, more preferably, the amount of the diisocyanate and the polyol is about 2.5 to 12 weight percent, and most preferably, the amount of the diisocyanate and the polyol. It is present in about 5 to 12 weight percent.

The thermoplastic polyurethane composition of the present invention comprises:
Consists of at least one diol curing agent. Suitable diol curing agents for use in the present invention are at least 1,4
-Consisting of butanediol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, low molecular weight polytetramethylene ether glycol and mixtures thereof. The average molecular weight of the low molecular weight polytetramethylene ether glycol,
250 to 1,000. Preferably, the polyurethane composition comprises a blend or mixture of diol curing agents. In one embodiment, the polyurethane composition comprises a single diol hardener. 1,3- [bis- (2-
Hydroxyethoxy)] diethoxybenzene is 2,2 '
It is well known in the art that it can be referred to as-[1,3-phenylenebisoxy-2,1-ethanediyloxy] bis-ethanol. Suitably, the molecular weight of the at least one diol curing agent is at least about 50.

In a preferred embodiment, the thermoplastic polyurethane composition comprises the reaction product of 4,4'-diphenylmethane diisocyanate, polytetramethylene ether glycol, and 1,3-bis- (2-hydroxyethoxy) benzene and 1 , 3- [bis- (2-hydroxyethoxy)]-diethoxybenzene.

Optionally, it is possible to add a secondary diamine curing agent to the thermoplastic polyurethane composition of the present invention. Suitable secondary diamine curing agents are 4,4'-
Bis-sec-butylamino-diphenylmethane, 1,4
-Bis-sec-butylamino-benzene, 1,2-bis-sec-butylamino-benzene, derivatives of 4,4′-bis-sec-butylamino-diphenylmethane, 1,4
-Bis-sec-butylamino-cyclohexane, 1,2
-Bis-sec-butylamino-cyclohexane, 4,
It includes, but is not limited to, 4'-bis-sec-butylamino-dicyclohexylmethane, derivatives of 4,4'-bis-sec-butylamino-dicyclohexylmethane, and mixtures thereof.

In a preferred embodiment, the thermoplastic polyurethane composition comprises a reaction product of 4,4'-dicyclohexylmethane diisocyanate, a copolymer of polytetramethylene ether glycol and polycaprolactone, and 4,4'-bis- (sec. -Butylamino) -dicyclohexylmethane.

Preferably, the polyol is present in an amount of about 70 to 98 weight percent of the diisocyanate and the polyol, and the diisocyanate is present in an amount of about 2 to 30 weight percent of the isocyanate and the polyol. And the secondary diamine curing agent is present in an amount of 10 to 110 weight percent of the diisocyanate and the polyol.

It is possible to select any filler component to add further density to the above components. The choice of such filler is determined by the type of golf ball desired, ie, one-piece, two-piece multi-element, or wound. Examples of useful fillers include zinc oxide, barium sulfate, potassium oxide, calcium carbonate and silicon dioxide, and their corresponding other known salts and oxides. Additional fillers such as foaming agents, glass spheres and metals can be added to the polyurethane compositions of the present invention in the required amounts to achieve the known objectives. Additional components that can be added to the thermoplastic polyurethane composition include UV stabilizers and other dyes, as well as optical brighteners and fluorescent pigments and dyes. Such additional components can each be added in amounts that achieve the desired purpose.

The core of a golf ball formed according to the present invention can typically be formed from various elastomeric materials. A typical elastomeric base composition for forming a portion of a golf ball core made in accordance with the present invention comprises a base rubber, a crosslinker, and a filler. The base rubber typically includes natural rubber and synthetic rubber. A preferred base rubber is 1,4-polybutadiene having at least 40% cis-structure. Natural rubber, polyisoprene rubber and / or styrene-butadiene rubber can optionally be added to 1,4-polybutadiene. Crosslinking agents include metal salts of unsaturated fatty acids, such as zinc or magnesium salts of acrylic or methacrylic acid. The filler is typically zinc oxide,
Includes materials such as barium sulfate, silicon dioxide, calcium carbonate, metals, glass spheres and the like. The core of a golf ball formed according to the present invention can be a solid or hollow core, a fluid-filled or semi-solid filled core, a one-piece or multi-element core, or, if desired, a wound core. Is also possible.

In the above embodiment where the cover or cover inner layer of the golf ball is formed of the thermoplastic polyurethane composition of the present invention, the cover is made of US Pat. No. 5,733,4.
Molded around the core according to the teachings of No. 28 and 5,888,437. Said U.S. Patent is incorporated herein by reference for immediate reference.

The term "about" when used herein in connection with one or more numerical or numerical ranges, includes all such numbers, including all numbers within the range. It refers to a numerical value.

The term “Atti compression”
When used in the examples below, New Jersey,
Atchi Engineering Company of Union City
Engineering Corp. of Union
(City, NJ) is defined as the deflection of an object or material relative to the calibrated spring deflection measured with an Attach Compression Gauge commercially available from US Pat. Atchi compression is typically used to measure the compression of a golf ball. However, when referring to core compression, it is preferred to use compression load measurements.

The following examples are given for illustrative purposes and do not limit the scope of the invention in any case.

[0054]Example 1: Conventional golf ball and diol hard
Comparison with the golf ball of the present invention produced by using the agent  Two identical construction golf balls were made. Each golf
The ball is removed from the liquid filling center, wound layer and cover
Become. First Golf Ball Control Formulation (control
formation) covers traditional polyurethane
Formed from controlled blending using tan composition technology
It is. In the second golf ball experimental formulation, the cover layer
Is formed of the thermoplastic polyurethane composition of the present invention,
Such a composition comprises 4,4'-diphenylmethanediisocy
Anate, polytetraethylene ether glycol and
1,3-bis- (2-hydroxyethoxy) benzene and
And 1,3- [bis- (2-hydroxyethoxy)]-die
Consists of the reaction product of a mixture of toxicbenzenes. Color dispersion
The agent was added to both formulations. Golf ball products usa
Patent Nos. 5,733,428 and 5,888,437
It was processed according to the method described in the item. Golf for both
Table 1 shows the composition of the balls. ¹ About 9% of MDI and about 91% of PTMEG² Manufactured by Indspec Chemical
1,3-bis- (2-hydroxyethoxy) benze
And 1,3- [bis- (2-hydroxyethoxy)]-
Diethoxybenzene mixture³ Air Products and Chemical
Oligomeric diamines manufactured by al

As can be clearly seen from Table 2 below,
Golf balls made with the experimental formulations of the present invention have an improved initial velocity of 3.5 feet / second when compared to control golf balls. An improvement in the initial velocity of the golf ball of 3.5 feet / second is a significant improvement, as known to those skilled in the art. USGA
If the initial speed is to be as close as possible to the maximum limit of 255 ft / sec set by the above, the increase in the initial speed shown above can be very beneficial. Further, the golf balls of the present invention exhibited significantly lower compression. In other words, it provides a better "feel" while maintaining the same hardness as a golf ball formed by controlled blending. As those skilled in the art will notice, low compression of the golf ball will result in a low spin rate at the driver and will more closely match the launch conditions for maximum distance.

[0056]Example 2: Conventional golf ball and secondary dia
Golf ball manufactured by the present invention manufactured with a min curing agent
Comparison with  Two identical construction golf balls were made. Each golf
The ball is removed from the liquid filling center, wound layer and cover
Become. First Golf Ball Control Formulation (control
formation) covers traditional polyurethane
Formed from controlled blending using tan composition technology
It is. In the second golf ball experimental formulation, the cover layer
Is formed of the thermoplastic polyurethane composition of the present invention,
Such a composition comprises 4,4'-dicyclohexylmethanediamine.
Isocyanate, polytetraethylene ether glycol
And 4,4'-bis- (sec-butylamino) -disi
Consists of chlorhexylmethane. Color dispersant in both formulations
Was added. Golf ball products are disclosed in US Pat.
No. 3,428 and 5,888,437
Treated according to the method. Combining both golf balls
It is described in Table 3. ¹ About 8% of MDI and about 92% of PTMEG² H₁₂About 8% of MDI and PTMEG / Polycap
About 92% of Lactone³ Aliphatic secondary dia manufactured by UOPLLC
Min⁴ Air Products and Chemical
Oligomeric diamines manufactured by al

Table 4 below shows the golf ball characteristics of both the conventional golf ball and the golf ball manufactured according to the present invention.

The thermoplastic polyurethane composition of the present invention comprises:
It can be used for other golf equipment such as golf club inserts. For example, such inserts can be inserted into the face of a golf club as disclosed in U.S. Pat. No. 5,316,298 and the back of a golf club as disclosed in U.S. Pat. No. 5,575,472. Can be used in the cavity. The two U.S. patents are incorporated herein by reference in their entirety.

When making golf balls in accordance with the present invention, the area covered by the dimples is typically greater than about 60 percent, preferably greater than about 65 percent, and greater than about 75 percent. Is more preferred. Typically, the flexural modulus of the golf ball cover, as measured by ASTM method D6272-98, is greater than about 500 psi, and is preferably between about 500 psi and 150,000 psi. As mentioned herein, the outer cover layer is preferably formed from a relatively soft polyurethane material. In particular, the material hardness of the material of the outer cover layer is about 30 to about 60 Shore D as measured by ASTM-2240, and preferably about 35 to about 55 Shore D. The inner cover layer, in some cases, preferably has a material hardness of about 50 to about 75 Shore D, more preferably about 60 to about 65 Shore D.

The present invention as described and claimed herein, specific embodiments described herein are merely illustrative of some aspects of the present invention. The scope is not limited by the examples. All equivalent embodiments are within the scope of the present invention. Indeed, various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications also fall within the scope of the appended claims.

[0061]

When the polyurethane composition of the present invention is used to form golf ball cores, intermediate and mantle layers and / or covers, the speed of golf balls made with such compositions was covered by SURLYN®. It can be increased to the speed obtained with golf balls.

Further, the curatives used in the composition of the present invention may be AirProducts
VERSALLINK® P, an oligomeric diamine manufactured by And Chemicals, Inc.
It is less expensive than many hardeners typically used by those skilled in the art, such as -250.

The composition of the present invention comprises ETHACUR
E (registered trademark) 300 and ETHACURE (registered trademark)
Environmentally friendly than other cost effective options such as 100.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI Theme Court ゛ (Reference) C08G 18/32 C08G 18/32 Z (72) Inventor Murali Rajagopalan Massachusetts, USA 02748 South Dartmouth Flagship Drive 11 F-term (reference) 4J034 CA04 CA15 CB02 CB03 CB05 CC12 CC15 CC45 CC52 CC62 CD04 HA01 HA02 HA07 HC12 HC46 HC52 HC61 HC64 RA03 SA02 SB04 SB05 SC04 SD02 SD03

Claims (32)

[Claims] 1. A center, a cover, and optionally said center
At least one located between the center and the cover
A golf ball having two intermediate layers, wherein the cover
And at least one of the at least one intermediate layer,
The thermoplastic polyurethane formed of thermoplastic polyurethane;
The ethane comprises at least one polyol and at least
It consists of a reaction product of one diisocyanate and a curing agent.
Wherein the curing agent is essentially at least one diol
And the compounding of the diol is HOH₂CH₂C (OH₂CH₂C)_nO-X-O (C
H₂CH₂O)_mCH ₂CH₂OH, where n and m are each independently 0, 1, 2, or
Or 3 wherein X is 0-phenylene, m-phenylene.
Len, p-phenylene, 1,2-cyclohexyl, 1,
3-cyclohexyl or 1,4-cyclohexyl and
A golf ball characterized by being a mixture thereof. 2. The golf ball according to claim 1, wherein said n
And m each independently have a value of 1 or 2. 3. The golf ball according to claim 1, wherein the polyurethane composition further comprises ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,4-dibutanediol, 1,5-pentanediol, 4-sidehexane-dimethanol,
A golf ball comprising 1,6-hexanediol and at least one diol curing agent selected from the group consisting of polytetramethylene ether glycol having a molecular weight of less than 2000. 4. The golf ball of claim 1, wherein said thermoplastic polyurethane composition comprises at least two curing agents. 5. The golf ball of claim 1, wherein said diol curing agent has a molecular weight of at least about 50. 6. The golf ball of claim 1, wherein the diisocyanate is 4,4'-diphenylmethane diisocyanate, polymer 4,4'-diphenylmethane diisocyanate, liquid 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 3'-
Dimethyl 4,4'-biphenylenediisocyanate, p
-Phenylene diisocyanate, hexamethylene diisocyanate, p-tetramethyl xylene diisocyanate, m-tetramethyl xylene diisocyanate, nephthalene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, m-phenylene diisocyanate, low-free (l
ow free) A golf ball selected from the group consisting of isocyanate monomers and mixtures thereof. 7. The golf ball according to claim 1, wherein the polyol is polytetramethylene ether glycol,
Polyoxypropylene glycol, polyethylene adipate glycol, polyethylene propylene adipate glycol and polybutylene adipate glycol, ortho-phthalate-1,6-hexanediol polyester polymer, diethylene glycol-initiated polycaprolactone, trimethyllolpropane-initiated polycaprolactone, neopentyl glycol-initiated Polycaprolactone,
1,4-butanediol-initiated polycaprolactone,
1,6-hexanediol-initiated polycaprolactone,
A golf ball selected from the group consisting of saturated and unsaturated hydrocarbon polyols, hydroxy-terminated liquid isoprene rubber, hydroxy-terminated polybutadiene, copolymers of the above polyols and mixtures thereof. 8. The golf ball of claim 7, wherein the polyol has a molecular weight of about 200-4000. 9. The golf ball of claim 1, wherein the polyol is polytetramethylene ether glycol,
A golf ball selected from the group consisting of polyethylene adipate glycol, polybutylene adipate glycol, diethylene glycol initiated polycaprolactone and mixtures thereof. 10. The golf ball of claim 1, wherein the polyol is present in an amount of about 70 to 98 weight percent of the diisocyanate and the polyol, wherein the diisocyanate is the diisocyanate and the polyol. A golf ball wherein the amount is between about 2 and 30 weight percent and the diol hardener is between 10 and 110 weight percent of the diisocyanate and the polyol. 11. The golf ball of claim 10, wherein said diisocyanate is present in an amount of about 2.5 to 12 weight percent of said diisocyanate and said polyol. 12. The golf ball of claim 1, wherein said thermoplastic polyurethane composition further comprises at least one secondary diamine curing agent. 13. The golf ball of claim 12, wherein the secondary diamine curing agent is 4,4'-bis-sec-butylamino-diphenylmethane, 1,4-bis-sec-
Butylamino-benzene, 1,2-bis-sec-butylamino-benzene, derivatives of 4,4'-bis-sec-butylamino-diphenylmethane, 1,4-bis-sec-
Butylamino-cyclohexane, 1,2-bis-sec-
Butylamino-cyclohexane, 4,4'-bis-sec-butylamino-diclohexylmethane, 4,4'-
A golf ball selected from the group consisting of derivatives of bis-sec-butylamino-dicyclohexylmethane, and mixtures thereof. 14. The golf ball of claim 1, wherein the thermoplastic polyurethane composition comprises a reaction product of 4,4'-diphenylmethane diisocyanate, polytetramethylene ether glycol, and 1,3-bis- (2 -Hydroxyethoxy) benzene and 1,3- [bis- (2
-Hydroxyethoxy)]-diethoxybenzene. 15. A golf ball according to claim 1, wherein said cover is made of said thermoplastic polyurethane composition. 16. The golf ball of claim 1, wherein said ball includes at least one of said intermediate layers, and
A golf ball wherein at least one of the intermediate layers comprises a thermoplastic polyurethane composition. 17. The golf ball of claim 1, wherein the center is a fluid-filled center, a solid center, a gel center, or a hollow center. 18. The golf ball of claim 1, wherein said thermoplastic polyurethane composition further comprises a density modifying filler. 19. A golf ball comprising a center, a cover, and optionally at least one intermediate layer disposed between said center and said cover, wherein at least one of said cover and said at least one intermediate layer is at least one. A golf ball formed of a thermoplastic polyurethane composition comprising a reaction product of one polyol and at least one diisocyanate and a curing agent comprising a secondary diamine. 20. The golf ball of claim 19, wherein said thermoplastic polyurethane composition comprises at least two curing agents. 21. The golf ball according to claim 19, wherein the diisocyanate is 4,4'-diphenylmethane diisocyanate, polymer 4,4'-diphenylmethane diisocyanate, liquid 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 3 '
-Dimethyl-4,4'-biphenylene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, p-tetramethyl xylene diisocyanate, m-tetramethyl xylene diisocyanate, naphthalene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, A golf ball selected from the group consisting of m-phenylene diisocyanate, low-free isocyanate monomers and mixtures thereof. 22. The golf ball according to claim 19, wherein said polyol is polytetramethylene ether glycol, polyoxypropylene glycol, polyethylene adipate glycol, polyethylene propylene adipate glycol, polybutylene adipate glycol, ortho-phthalate-polyol. 1,6-hexanediol polyester polyol, diethylene glycol-initiated polycaprolactone, trimethyllolpropane-initiated polycaprolactone, neopentyl glycol-initiated polycaprolactone, 1,4-butanediol-initiated polycaprolactone, 1,6-hexanediol-initiated poly Caprolactone, saturated and unsaturated hydrocarbon polyols, hydroxy-terminated liquid isoprene rubber, hydroxy-terminated polybutadiene polyol, Golf ball is selected from the group consisting of copolymers and mixtures thereof serial polyol. 23. The golf ball of claim 19, wherein the polyol is selected from the group consisting of polytetramethylene ether glycol, polyethylene adipate glycol, polybutylene adipate glycol, diethylene glycol initiated polycaprolactone, and mixtures thereof. ball. 24. The golf ball of claim 22, wherein the polyol has a molecular weight of about 200 to 4000. 25. The golf ball of claim 22, wherein said polyol is present in an amount of said diisocyanate and said polyol of about 70 to 98 percent by weight, said diisocyanate being said diisocyanate and said polyol. The secondary diamine curing agent is present in an amount of about 2 to 30 weight percent and the secondary diamine curing agent is present in an amount of 10 to 1
Golf ball present in 10 weight percent. 26. The golf ball of claim 25, wherein the diisocyanate is present in an amount of about 2.5 to 12 weight percent of the diisocyanate and the polyol. 27. The golf ball of claim 19, wherein said secondary diamine curing agent is 4,4'-bis-sec-butylamino-diphenylmethane, 1,4-bis-sec-
Butylamino-benzene, 1,2-bis-sec-butylamino-benzene, derivatives of 4,4′-bis-sec-butylamino-diphenylmethane, 1,4-bis-sec-
Butylamino-cyclohexane, 1,2-bis-sec-
Butylamino-cyclohexane, 4,4'-bis-sec-butylamino-diclohexylmethane, 4,4'-
A golf ball selected from the group consisting of derivatives of bis-sec-butylamino-dicyclohexylmethane, and mixtures thereof. 28. The golf ball of claim 19, wherein the thermoplastic polyurethane composition comprises a reaction product of 4,4'-dicyclohexylmethane diisocyanate, a copolymer of polytetramethylene ether glycol and polycaprolactone, and A golf ball comprising 4'-bis- (sec-butylamino) -dicyclohexylmethane. 29. The golf ball of claim 19, wherein said cover comprises a thermoplastic polyurethane composition. 30. The golf ball of claim 19, wherein the ball comprises at least one of the intermediate layers, and wherein at least one of the intermediate layers comprises a thermoplastic polyurethane composition. 31. The golf ball of claim 19, wherein said center is a fluid-filled center, a solid center, a gel center, or a hollow center. 32. The golf ball of claim 19, wherein said thermoplastic polyurethane composition further comprises a density modifying filler.