JP5602337B2 - Highly neutralized thermoplastic copolymer center for improved multilayer core golf balls - Google Patents

Description

  The present invention relates generally to golf balls, and more specifically, the present invention is directed to golf balls having a multilayer core that covers a relatively soft, low compression inner core with a relatively hard outer core and cover. It has been. The golf ball may include an intermediate core layer.

  Dual-layer golf balls are typically manufactured by wrapping a single solid core with a cover. These balls are generally the most popular among amateur golfers because they are durable and provide maximum distance. Typically, the solid core is made from polybutadiene crosslinked with zinc diacrylate and / or similar crosslinking agents. The cover material may be one or more materials known as ionomers, such as SURLYN ™, sold commercially by DuPont, FORMION ™, sold commercially by Schulman, or both Dow. PRIMACOR (TM) or DOWLEX (TM), a strong, cut-resistant blend, commercially sold by Chemical.

  Other multilayer golf balls may comprise a plurality of core layers, a plurality of intermediate layers, and / or a plurality of cover layers. They tend to improve some of the unfavorable characteristics of conventional bilayer balls, such as hard feeling and difficulty in controlling, while maintaining favorable properties such as increased initial speed and distance. However, especially for more advanced players, it is desirable for a multi-layer ball to have a “feel” similar to a pin wound ball.

  In addition, the spin rate of the golf ball affects the overall control of the ball depending on the skill level of the player. A golf ball with a lower spin rate improves distance, but is difficult to control for short shots, such as approaching the green. On the other hand, if the spin rate is large, the skilled player can easily control, but the driving distance becomes small. Additional layers, such as an intermediate layer, outer core layer, and inner cover layer, are often added to solid core golf balls that improve the play characteristics of the ball to balance the spin rate and play characteristics of the golf ball. Is done.

  The patent literature discloses a number of multi-layer golf balls. U.S. Patent Publication No. 2005-0130767A1, which is related to the applicant's application and is incorporated herein by reference, is directed to an improved multilayer golf ball with a predetermined spin profile. Yes. The ball has a generally rigid thermosetting polybutadiene outer core that surrounds a relatively soft, low compression inner core. The hardness of the inner core is smaller than the hardness of the outer core, and the specific gravity of the inner core is less than or equal to the specific gravity of the outer core. The inner and outer cores are adjusted so that the combined overall core compression is greater than about 50.

  U.S. Patent No. 6,685,579, which is related to the applicant's application and is incorporated herein by reference, has three or more layers: an inner cover layer, an outer cover layer, and The present invention is directed to a golf ball having a cover including an intermediate cover layer. The outer cover layer has a composition made from a reactive liquid material and the combined thickness of the cover layer is about 0.125 inches. A golf ball prepared in this manner can have a compressive or flexural modulus that is substantially the same or greater than that of a golf ball having a normal structure, while achieving substantially the same coefficient of restitution (“COR”). The resulting golf ball typically achieves a COR of about 0.7 or greater and has an Atti compression of at least about 40. As used herein, the term rebound coefficient of a golf ball is defined as the ratio of the rebound speed to the input speed when the ball is fired on a rigid plate. A discussion of COR and a suitable test method for measuring COR can be found, for example, in US Pat. No. 6,547,677, the contents of which are incorporated herein by reference.

  U.S. Patent Publication No. 2004-0082407 A1 is also related to the applicant's application and is incorporated herein by reference, but is directed to a golf ball having an inner core, an outer core and a cover. . At least one layer of the golf ball is made of a low compression, high COR material and supported by a low strain, high compression layer. The resulting golf ball achieves high COR at high and low impact speeds, and low compression suitable for controlled green side play.

  The material, density, or specific gravity is varied across the various layers of the golf ball to control the spin rate of the golf ball. For example, the weight can be redistributed from the outer layer to the inner layer of the golf ball to reduce the moment of inertia of the golf ball, thereby increasing the spin rate and vice versa. This is discussed in US Pat. No. 6,494,795B2.

Accordingly, there remains a need for multilayer golf balls with improved distance and feel for low swing speed players.
US Patent Publication No. 2005-0130767 US Pat. No. 6,685,579 US Pat. No. 6,547,677 US Patent Publication No. 2004-0082407 US Pat. No. 6,494,795

  The present invention is directed to a multilayer golf ball having an inner core, a cover layer, and at least one intermediate layer between the inner core and the cover layer. The ball layer changes its properties according to its gradient. The slope of the coefficient of restitution from the inner core to the cover layer is from low to high, or the slope of the initial velocity from the inner core to the cover layer is from slow to fast. Similarly, the flexural modulus increases from the inner core to the outer cover layer, as does the compression and hardness of the layer. With these features, a golf ball with improved distance and feeling is realized for a player with a low swing speed.

According to the present invention, the compression of the inner core is less than about 60, more preferably less than about 40, and most preferably less than about 30. The intermediate layer is harder than the inner core, its hardness is greater than about 55 Shore D, and its specific gravity is greater than the specific gravity of the inner core. The flexural modulus of the intermediate layer is also preferably larger than the inner core. The cover layer thereof ksi (1ksi = 6.89MPa) Display of bending ratio obtained by dividing a Shore D hardness of less than 1.0 in elastic modulus, more preferably less than 0.9, and most such that preferably less than 0.8 Built in.

  In another aspect of the invention, the specific gravity of the inner core is less than 1.15, preferably less than 1.05. The specific gravity of the intermediate layer is greater than 1.15, preferably greater than 1.20, and most preferably greater than 1.25.

  In yet another aspect of the invention, the ball cover has a hardness of at least 60 Shore D, more preferably at least 65 Shore D, a flexural modulus of at least 413 MPa (60 ksi), and a thickness of 0 0.03 to 0.5 inches. The cover contains an acrylic acid ionomer, the acid component of which is between 13% and 16%, and the ionomer is neutralized by cations.

  The invention also includes an inner core, at least one intermediate layer having a specific gravity greater than that of the inner core, at least one outer core layer having a specific gravity greater than that of the intermediate layer, and a cover having a specific gravity smaller than that of the outer core layer. It is aimed at the golf ball. The volume of the inner core layer is preferably greater than the volume of the outer core layer, and the volume of the outer core layer is greater than the volume of the cover layer. The cover is harder than the outer core layer, and the outer core layer is harder than the inner core layer.

  In another aspect of the invention, a multi-layer golf ball with a gradient in hardness and specific gravity is constructed such that at least one of the core layers has a highly neutralized thermoplastic ionomer (HNP). Preferably, the inner core has unfilled HNP with a specific gravity of less than 0.95.

  The accompanying drawings constitute a part of the specification and are taken together with the specification. In each drawing, like reference numerals are used to indicate like parts.

  The present invention is directed to a multilayer golf ball having a core, a cover layer, and at least one intermediate layer between the core and the cover layer. The core, intermediate layer and cover layer may be constructed to have various properties. Several embodiments of the invention are described below.

One embodiment of the invention is a multilayer golf ball having an inner core, an outer core layer surrounding the inner core, and a cover layer surrounding the core layer. An optional intermediate core layer may be present inside the outer core layer, but this surrounds the inner core. Preferably, the specific gravity of the inner core is small, its flexural modulus is small, and its hardness is small. Preferably, the specific gravity of the outer core layer is larger than that of the inner core, its flexural modulus is large, and its hardness is large. The value of the flexural modulus of the cover is at least equal to or greater than that of the outer core layer . Further, the cover is constructed such that the ratio of the cover hardness (Shore D) divided by the flexural modulus (in ksi) is less than 1.0. In this embodiment, the inner core is preferably made from polybutadiene and the cover is preferably made from an ionomer, such as an acrylic acid ionomer, with an acid component of about 13% to 16%. Other materials suitable for the core and cover layers are discussed below. Preferred properties of the various layers of the multilayer golf ball of this example are specified in the following table.

  Another embodiment of the present invention is a golf ball substantially similar to the first embodiment. However, in the second embodiment, there is a COR gradient from slow to fast. For example, the COR value of the inner core is small, the COR value of the outer core layer is large, and the COR value of the cover layer is equally large.

  The third embodiment is also substantially similar to the first embodiment. However, in a third embodiment, at least one core layer is a highly neutralized thermoplastic ionomer (HNP), preferably the inner core of the golf ball is unfilled with a specific gravity of about 0.95. HNP.

  Yet another embodiment of the invention is directed to a multi-layer golf ball having an inner core, at least one intermediate core layer, an outer core layer, and a cover layer. In this embodiment, there is a decreasing volume gradient, for example, the inner core volume is greater than the intermediate core layer volume, the intermediate core layer volume is greater than the outer core volume, and the outer core volume is greater than the cover volume. . There may be a hardness reduction gradient, resulting in a hard inner core, a slightly soft intermediate core layer, a slightly soft outer core layer, as well as a soft cover layer. There may be a gradient of specific gravity, increasing from a lower specific gravity inner core to a higher specific gravity outer core. However, in this embodiment, the specific gravity of the outer core layer is preferably greater than the specific gravity of the cover layer, so the gradient does not advance to the cover layer as well.

  These features can provide a golf ball that can provide high speed, low spin, and high launch angle, and that can provide relatively small or fairly small compression. By combining the characteristics, it can be made particularly suitable for general amateur golfers with small swing speeds to improve distance and feel, and the present invention is expected to realize the golf ball currently required in the market.

  For example, the preferred cover layer of the present invention allows an amateur golfer to launch from a tee with low spin (and therefore farther), yet with greater spin (and thus more control when hitting the green approach shot) ) With respect to the flexural modulus of elasticity. Reducing the compression of the ball provides a softer feel and is extremely beneficial when chipping or putting around the green.

  As generally shown in FIGS. 1 and 2, reference numerals 10 and 20 indicate golf balls according to the present invention. As depicted in FIG. 1, some example golf balls 10 include an inner core 12, at least one intermediate core layer 14, an outer core layer 16, and a cover layer 18. Other embodiments may include only an inner core 22, an outer core layer 24, and a cover layer 26, as shown by the golf ball 20 in FIG. If the inner core is surrounded by multiple layers as shown in FIGS. 1 and 2, the multiple layers increase in physical / mechanical properties, eg hardness, from the outermost to the innermost layer Or preferably from the outermost to the innermost layer. In addition to hardness, other characteristic gradients can be brought about by the molding process and the use of layers, including speed, coefficient of restitution, etc.

  Any or all of the inner core, intermediate core layer, and outer core layer of the multi-layer golf ball 10 or 20 are thermoset or thermoplastic materials such as polyurethane, polyurea, partially or fully neutralized Ionomers, thermoset polydiene rubbers such as polybutadiene, polyisoprene, ethylene propylene diene monomer rubber, ethylene propylene rubber, natural rubber, balata, butyl rubber, holobutyl rubber, styrene butadiene rubber, or any styrene block copolymer such as styrene Metallocene or other single site catalyzed polyolefins such as ethylene butadiene styrene rubber, polyurethane copolymers such as those with silicones and can be employed as long as the above gradient criteria are met.

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

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

  Suitable ionomer polymers for use in the core layer (ie copolymer, or terpolymer type ionomer) include alpha-olefin / unsaturated-carboxylic acid copolymer type ionomer resins or terpolymer resins. Copolymer ionomers are obtained by neutralizing at least some of the carboxyl groups in a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms with a metal ion. Examples of suitable α-olefins are ethylene, propylene, 1-butene, and 1-hexene. Examples of suitable unsaturated carboxylic acids are acrylic, methacrylic, ethacryl, α-chloroacrylic, croton, malein, fumaric, and itaconic acid. The acid content of the copolymer ionomer and the degree of neutralization vary, and the neutralization is performed with monovalent or divalent cations, which will be discussed below.

  The terpolymer ionomer is a carboxyl in a copolymer of an α-olefin, an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and an α, β-unsaturated carboxylate having 2 to 22 carbon atoms. Obtained by neutralizing at least part of the group with metal ions. Examples of suitable α-olefins are ethylene, propylene, 1-butene, and 1-hexene. Examples of suitable unsaturated carboxylic acids are acrylic, methacrylic, ethacryl, α-chloroacrylic, croton, malein, fumaric, and itaconic acid. The acid content of the terpolymer ionomer and the degree of neutralization vary, and the neutralization is performed by the monovalent or divalent cation described above. Examples of suitable ionomer resins are manufactured under the trade name “SURLYN” of EI DuPont de Nemours & Co., Wilmington, DE or as IOTEK of Exxon, Texas Irving. Including what is.

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

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

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

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

  Other suitable materials for the core include, but are not limited to:

(1) Polyurethanes, for example, prepared from polyols and diisocyanates or polyisocyanates and disclosed in US Pat. Nos. 5,334,673, 6,506,851 and US Pat. No. 6,663,564 thing.
(2) Polyureas such as those disclosed in US Pat. No. 5,484,870 and US Pat. No. 6,835,794.
(3) A polyurethane-urea hybrid, blend or copolymer comprising urethane or urea segments.

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

  Golf ball cores and optional layers can also be made from highly neutralized polymers ("HNP"). The acid portion of HNP is typically an ethylene-based ionomer, preferably more than about 70%, more preferably more than about 90%, and most preferably at least about 100% neutralized. HNP can also be blended with the second polymer component, and if this component contains acid groups, it can be neutralized according to conventional methods, with organic fatty acids of the present invention, or both. . The second polymer component may be partially or fully neutralized, preferably ionomer copolymers and ionomer terpolymers, ionomer precursors, thermoplastics, polyamides, polycarbonates, polyesters, polyurethanes, polyureas, heat Includes plastic elastomers, polybutadiene rubber, balata, metallocene catalyzed polymers (grafted and ungrafted), single site polymers, highly crystalline acid polymers, cationic ionomers, and the like. The material hardness of the HNP polymer is typically between about 20 and about 80 Shore D, and the flexural modulus is between about 3 ksi and about 200 ksi.

In one embodiment of the invention, the HNP is an ionomer and / or an acid precursor thereof, which is preferably fully or partially neutralized with an organic acid copolymer or salt thereof. The acid copolymer is preferably an α-olefin, such as ethylene, a C _3-8 α, β-ethylenically unsaturated carboxylic acid, such as an acrylic or methacrylic acid copolymer. These may include softening monomers such as alkyl acrylates and alkyl methacrylates. Here, the alkyl group comprises 1 to 8 carbon atoms.

The acid copolymer can be described as an E / X / Y copolymer, where E is ethylene, X is an α, β-ethylenically unsaturated carboxylic acid, and Y is a softening comonomer. In a preferred embodiment, X is acrylic acid or methacrylic acid and Y is a C _1-8 alkyl acrylate or methacrylate ester. X is preferably present in an amount of from about 1 to about 35% by weight of the polymer, more preferably from about 5 to about 30% by weight of the polymer, and most preferably from about 10 to about 20% by weight of the polymer. Y is preferably present in an amount of from about 0 to about 50% by weight of the polymer, more preferably from about 5 to about 25% by weight of the polymer, and most preferably from about 10 to about 20% by weight of the polymer.

  Specific acid-containing ethylene copolymers include, but are not limited to, ethylene / acrylic acid / n-butyl acrylate, ethylene / methacrylic acid / n-butyl acrylate, ethylene / methacrylic acid / iso-butyl acrylate, ethylene / acrylic acid / Iso-butyl acrylate, ethylene / methacrylic acid / methyl acrylate, ethylene / methacrylic acid / n-butyl methacrylate, ethylene / acrylic acid / methyl methacrylate, ethylene / acrylic acid / methyl acrylate, ethylene / methacrylic acid / methyl acrylate, ethylene / methacrylic Acid / methyl methacrylate and ethylene / acrylic acid / n-butyl methacrylate. Preferred acid-containing ethylene copolymers are ethylene / methacrylic acid / n-butyl acrylate, ethylene / acrylic acid / n-butyl acrylate, ethylene / methacrylic acid / methyl acrylate, ethylene / acrylic acid / ethyl acrylate, ethylene / methacrylic acid / ethyl acrylate. And ethylene / acrylic acid / methyl acrylate copolymers. The most preferred acid-containing ethylene copolymers are ethylene / (meth) acrylic acid / n-butyl acrylate, ethylene / (meth) acrylic acid / ethyl acrylate, and ethylene / (meth) acrylic acid / methyl acrylate copolymers.

  The ionomer is typically neutralized by a metal cation such as lithium, sodium, potassium, magnesium, calcium or zinc. By adding enough organic acid or salt of organic acid, along with an appropriate base, to the acid copolymer or ionomer, the ionomer is neutralized to a much higher level relative to the metal cation without sacrificing processability. The Preferably, the acid moiety is neutralized about 80% or more, preferably 90-100% neutralized, most preferably 100% neutralized. However, workability is not impaired. This involves melt blending an α, β-ethylenically unsaturated carboxylic acid copolymer with, for example, an organic acid or a salt of an organic acid, and then adding a sufficient amount of cation source to add all acid moieties (acid copolymer and organic acid). Of the acid moiety) is increased by more than 90% (preferably more than 100%).

  The organic acids of this invention are aliphatic, mono- or multi-functional (saturated, unsaturated, or polyunsaturated) organic acids. These organic acid salts can also be used. The salt of the organic acid of the present invention is barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin, or calcium. Salts, salts of fatty acids, in particular salts of stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid or dimerized derivatives thereof. The organic acids and salts of the present invention must be relatively non-migratory (do not cause blooming on the surface of the polymer under normal pressure) and be non-volatile (do not evaporate at the temperature required for melt blending). preferable.

  The ionomers of this invention may also be partially neutralized with metal cations. The acid portion of the acid copolymer may be from about 1 to about 100%, preferably at least about 40, depending on the cation, such as lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum, or mixtures thereof. About 100%, more preferably at least about 90 to about 100% neutralized to produce an ionomer.

  The acid copolymers of this invention may be prepared by “direct” acid copolymer, a copolymer that has been polymerized with all monomers added simultaneously, or by grafting an acid-containing Momomer to an existing polymer.

  Thermoplastic polymer components such as copolyetheresters, copolyesteresters, copolyetheramides, elastomeric polyolefins, styrene diene block copolymers and their hydrogenated derivatives, copolyesteramides, thermoplastic polyurethanes such as copolypolyether urethanes, copolyester urethanes Before neutralizing the acid moiety, copolyurea urethane, copolyurea uretania, epoxy base polyurethane, polycaprolactone base polyurethane, polyurea, and polycarbonate base polyurethane filler, and other ingredients (if included), You may blend with thermoplastic polyurethane on the way and after that.

単鎖ユニットはつぎの式で表される。

ここで、Ｇは、約４００−８０００の分子量で炭素の酸素に対する比が２．０−４．３のポリ（アルキレンオキシド）グリコールから末端ヒドロキシル基を除去したのちに残っている二価のラジカルであり；Ｒは、約２５０未満の分子量のジオールからからヒドロキシル基を除去したのちに残っている二価のラジカルであり；単鎖エステルユニットの量が上記コポリエーテルエステルの約１５−９５重量％であるとする。好ましい、コポリエーテルエステルポリマーは、ポリエーテルセグメントがテトラヒドロフランの重合により得られ、ポリエステルセグメントがテトラメチレングリコールおよびフラル酸の重合により得られたものである。この発明では、エーテル：エステルのモル比は９０：１０から１０：８０に変化して良く、好ましくは８０：２０から６０：４０である。ショアＤ硬度は７０未満であり、好ましくは約４０未満である。 The copolyetherester has a plurality of repeating long-chain units and single-chain units, which are head-to-tail linked by an ester bond, and the long-chain unit is represented by the formula

The single chain unit is represented by the following formula.

Where G is a divalent radical remaining after removal of terminal hydroxyl groups from poly (alkylene oxide) glycol having a molecular weight of about 400-8000 and a carbon to oxygen ratio of 2.0-4.3. Yes; R is a divalent radical remaining after removal of the hydroxyl group from a diol having a molecular weight of less than about 250; the amount of single chain ester units is about 15-95% by weight of the copolyetherester Suppose there is. Preferred copolyetherester polymers are those in which the polyether segment is obtained by polymerization of tetrahydrofuran and the polyester segment is obtained by polymerization of tetramethylene glycol and fulleric acid. In this invention, the ether: ester molar ratio may vary from 90:10 to 10:80, preferably from 80:20 to 60:40. The Shore D hardness is less than 70, preferably less than about 40.

ここでＰＡは、４−２０個の炭素原子を有する鎖制約脂肪族カルボン二酸の存在下で、４から１４個の炭素原子を含む炭化水素基を有するラクタムまたはアミノ酸から、または、脂肪族Ｃ_６−Ｃ_８ジアミンから生成された線形の飽和脂肪族ポリアミドシーケンスであり；このポリアミドは３００から１５０００の平均分子量を有し；ＰＢは、線形または分岐脂肪族ポリオキシアルキレングリコール、それらの混合物、またはそれらから誘導したコポリエーテルから生成したポリオキシアルキレンシーケンスであり、このポリオキシアルキレングリコールは６０００以下の分子量を有し；ｎは、ポリエーテルアミドコポリマーの本来の粘度が約０．６から約２．０５になるために十分な繰り返しユニットの数である。これらポリエーテルアミドを準備するために、ジカルボン酸ポリアミド、鎖端にあるＣＯＯＨ基を、鎖端でヒドロキシル化されたポリオキシアルキレングリコールで、一般式Ｔｉ（ＯＲ）_ｘのテトラ−アルキルオルトチタンのような触媒の下で、反応させるステップを行う。ここで、Ｒは、１から２４個の炭素原子を具備する線形分岐脂肪族炭化水素基である。ここでも、より多くのポリエーテルユニットをコポリエータルアミドに組みこめばそれだけポリマーが柔らかくなる。エーテル：アミドの比は上述のエーテルの場合と同様であり、ショアＤ硬度も同様である。 Polyetheramides consist of linear and regular chains of rigid polyamide segments and flexible polyether segments, which are represented by the general formula:

Where PA is a lactam or amino acid having a hydrocarbon group containing 4 to 14 carbon atoms in the presence of a chain-constrained aliphatic carboxylic diacid having 4 to 20 carbon atoms, or an aliphatic C ₆ -C ₈ be linear saturated aliphatic polyamide sequence generated from a diamine; average have a molecular weight of the polyamide is from 300 15000; PB is linear or branched aliphatic polyoxyalkylene glycols, mixtures thereof, or Polyoxyalkylene sequences generated from copolyethers derived therefrom, the polyoxyalkylene glycols having a molecular weight of 6000 or less; n is the inherent viscosity of the polyetheramide copolymer from about 0.6 to about 2. The number of repeating units sufficient to be 05. To prepare these polyetheramides, dicarboxylic acid polyamides, polyoxyalkylene glycols hydroxylated at the chain ends with COOH groups at the chain ends, such as tetra-alkylortho titaniums of the general formula Ti (OR) _x The reaction step is performed under a suitable catalyst. Here, R is a linear branched aliphatic hydrocarbon group having 1 to 24 carbon atoms. Again, the more the polyether units are incorporated into the copolyetheramide, the softer the polymer. The ether: amide ratio is the same as in the ether described above, and the Shore D hardness is the same.

  Elastomeric polyolefins are polymers consisting of ethylene and higher order main olefins such as propylene, hexene, octene and optionally 1,4-hexadiene and / or ethylidene, norbornene, or norbornadiene. The elastomeric polyolefin may optionally be functionalized with maleic anhydride, epoxy, hydroxy, amine, carboxylic acid, sulfonic acid, or thiol groups.

  Thermoplastic polyurethane is a linear or chain-branched polymer and is composed of a hard block and a soft elastomer block. These are made by reacting a soft hydroxy-terminated elastomeric polyether or polyester with a diisocyanate, such as methylene diisocyanate ("MDI"), p-phenylene diisocyanate ("PPDI"), or toluene diisocyanate ("TDI"). . These can be chain extended with glycols, secondary diamines, diacids, or aminoalcohols. The reaction product of isocyanate and alcohol is called urethane and these blocks are relatively hard and highly melted. These high melting blocks are responsible for the thermoplastic properties of polyurethane.

  Block styrene diene copolymers and their hydrogenated derivatives consist of polystyrene units and polydiene units. These may be functionalized with moieties such as OH, NH2, epoxy, COOH and anhydride groups. The polydiene unit is derived from polybutadiene, polyisoprene or copolymers thereof. In the case of a copolymer, it is possible to hydrogenate the polyolefin to form a saturated rubbery backbone segment. These materials are commonly referred to as SBS, SIS or SEBS thermoplastic elastomers and can be functionalized with maleic anhydride.

ただし、Ｒ_１は水素、分岐または直鎖アルキル例えばメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、およびオクチル、カルボサイクリックまたは芳香族；Ｒ_２は水素、Ｃ_１−Ｃ_５を含む低次のアルキル、カルボサイクリックまたは芳香族；Ｒ_３は水素、Ｃ_１−Ｃ_５を含む低次のアルキル、カルボサイクリックまたは芳香族；Ｒ_４はＨ，ＣｎＨ２ｎ＋１（ただしｎ＝１〜１８）、およびフェニルからなるグループから選択され、Ｒ_４中の０から５個の水素が置換体ＣＯＯＨ、ＳＯ_３Ｈ、ＮＨ_２、Ｆ，Ｃｌ、Ｂｒ、Ｉ、ＯＨ、ＳＨ、シリコーン、低次のアルキルエステルおよび低次のアルキルエーテルにより置換することができ、ただし、Ｒ_３およびＲ_４は二環のリングを形成できるものとし；Ｒ_５は水素、Ｃ_１−Ｃ_５を含む低次のアルキル、カルボサイクリックまたは芳香族；Ｒ_６は水素、Ｃ_１−Ｃ_５を含む低次のアルキル、カルボサイクリックまたは芳香族；ｘ、ｙおよびｚは各コ−モノマーの相対パーセントである。ｘは、約１から約９９パーセントの範囲であってよく、より好ましくは、約１０から約７０パーセントの範囲で良く、最も好ましくは約１０から約５０パーセントの範囲であって良い。ｙは、９９から１パーセントであってよく、好ましくは、９０から３０パーセントであってよく、最も好ましくは、９０から５０パーセントであってよい。ｚは、約０から約４９パーセントの範囲でよい。当業者は、酸部分が上述のポリマー中の配位子として働く場合には、上述のとおり有機脂肪酸により１００％まで中和できることを理解するであろう。 Grafted metallocene catalyst polymers are also suitable for blending with the HNP of this invention. The grafted metallocene catalyst polymer is usually neutralized with a metal cation, but may be partially or fully neutralized with an organic acid or salt thereof and a suitable base. Grafted metallocene catalyst polymers useful for the golf balls of the present invention include, for example, U.S. Pat. Nos. 5,703,166, 5,824,746, 5,981,658, and 6,02, No. 5442, which is incorporated by reference, which is a range of experimental quantities from DuPont from SURLYN ™ NMO 525D, SURLYN ™ NMO 524D and SURLYN ™ NMO 499D, previously known as the FUSABOND ™ family, and a post-polymerization reaction of a non-grafted metallocene catalyst polymer with the desired one or more side groups grafted metallocene catalyst A polymer may be realized. Examples of metallocene catalyst polymers capable of grafting functional groups for use in this invention include, but are not limited to, ethylene homopolymers and ethylene and second olefins, preferably propylene, butene, pentene, hexene, heptene, octene. It is a copolymer of norbornene. In general, this invention relates to golf balls having at least one layer having at least one grafted metallocene catalyst polymer or polymer blend, wherein the grafted metallocene catalyst polymer is a metallocene catalyst polymer having the formula: It is formed by grafting a functional group to

Where R ₁ is hydrogen, branched or straight chain alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, carbocyclic or aromatic; R ₂ is hydrogen, low including C ₁ -C ₅ The following alkyl, carbocyclic or aromatic; R ₃ is hydrogen, lower alkyl, including C ₁ -C ₅ , carbocyclic or aromatic; R ₄ is H, CnH 2n + 1 (where n = 1-18), And 0 to 5 hydrogens in R ₄ are substituted COOH, SO ₃ H, NH ₂ , F, Cl, Br, I, OH, SH, silicone, lower alkyl esters selected from the group consisting of and phenyl and low for the following alkyl ether can be substituted, provided that, R ₃ and R ₄ shall be able to form a ring bicyclic; R ₅ is hydrogen, Low order alkyl containing ₁ -C _5, carbocyclic or aromatic; _{R 6} is _hydrogen, C 1 -C low order alkyl containing _5, carbocyclic or aromatic; x, y and z are each co -Relative percent of monomer. x may range from about 1 to about 99 percent, more preferably from about 10 to about 70 percent, and most preferably from about 10 to about 50 percent. y may be from 99 to 1 percent, preferably from 90 to 30 percent, and most preferably from 90 to 50 percent. z may range from about 0 to about 49 percent. One skilled in the art will appreciate that when the acid moiety acts as a ligand in the polymer described above, it can be neutralized to 100% with organic fatty acids as described above.

  The metallocene catalyst copolymer or terpolymer may be random or block and may be isotactic, syndiotactic or atactic. Select a side group that forms an isotactic, syndiotactic, or atactic polymer to determine the interaction between the various polymer chains that form the resin, golf ball cover, center, or intermediate Control the final properties of the resin used in the layer. As will be apparent to those skilled in the art, the grafted metallocene catalyst polymer produced from a metallocene-catalyzed random or block copolymer or terpolymer and useful for this invention is also a random or block copolymer or terpolymer, and the backbone of the metallocene catalyst polymer. Have the same stereoregularity.

  As used herein, the term “phrase branched or straight chain alkyl” means any substituted or unsubstituted acyclic carbon-containing compound. Examples of alkyl groups are lower order alkyls such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or t-butyl; higher order alkyls such as octyl, nonyl, decyl And lower alkylenes such as ethylene, propylene, pentene, hexene, octene, norbornene, nonene, decene and the like.

  Further, such alkyl groups may include various substituents in which one or more hydrogens are replaced with functional groups. Functional groups include, but are not limited to, hydroxyl, amino, carboxyl, sulfonamide, ester, phosphate, thiol, nitro, silane, and halogen (fluorine, chlorine, bromine and elements) but need to talk a lot There will be no.

  Here, the term “substituted or unsubstituted carbocyclic” means a cyclic carbon-containing compound including, but not limited to, cyclopentyl, cyclohexyl, cyclopeptyl and the like. Such cyclic groups may include various substituents in which one or more hydrogens are replaced with functional groups. Functional groups include those described above and also include lower alkyl groups of 1 to 28 carbon atoms. The cyclic group of this invention may contain a hetero atom.

As described above, R ₁ and R ₂ are alkyl, carbocyclic or aryl groups such as 1-cyclohexylpropyl, benzylcyclohexylmethyl, 2-cyclohexylpropyl, 2,2-methylcyclohexylpropyl, 2,2-methylphenylpropylene. And any combination of 2,2-methylphenylbutyl.

  Non-grafted metallocene catalyst polymers useful for this invention are commercially available from Dow Chemical and DuPont-Dow, respectively, under the trade names AFFINITY ™ polyolefin plastomer and ENGAGE ™ polyolefin elastomer. Other commercially available metallocene catalyst polymers can also be utilized. For example, EXACT (TM) commercially available from Exxon and INSIGHT (TM) commercially available from Dow. EXACT and INSIGHT series polymers have new hydrodynamic and other properties resulting from the use of metallocene catalyst technology. Metallocene-catalyzed polymers are readily available as a compressible foam sheet from Sentinel Products, Hyannis, Massachusetts.

  Monomers useful for this invention include, but are not limited to, functional groups such as sulfonic acid, sulfonic acid derivatives such as chlorosulfonic acid, vinyl ethers, primary, secondary and tertiary amines, monocarboxylic acids, dicarboxylic acids, A finned monomer having partially or fully ester-derived mono- and dicarboxylic acids, anhydrides of dicarboxylic acids, and cyclic imides of dicarboxylic acids.

  Furthermore, the metallocene catalyst polymer may be functionalized by sulfonation, carboxylation or addition of amine or hydroxy groups. By sulfonation, carboxylation or addition of hydroxy groups, the functionalized metallocene catalyst polymer can be converted to an anionic ionomer by reacting with a base. Similarly, metallocene catalyst polymers functionalized by addition of amines can be converted to cationic anion ionomers by reaction with alkyl halides, acids or acid derivatives.

  The most preferred monomer is maleic anhydride, which is once coupled to the metallocene catalyst polymer by a post polymerization reaction and further reacted to form a grafted metallocene catalyst polymer containing other side groups or functional groups. be able to. For example, reacting with water to convert anhydrides to dicarboxylic acids; reacting with ammonia, alkyl or aromatic amines to form amides; reacting with alcohols to form esters; reacting with bases to anionic ionomers Is generated.

  The HNP of the present invention may be blended with single site and metallocene catalysts and polymers produced therefrom. Here, the “single site catalyst” is as disclosed in US Pat. No. 6,150,462, which is incorporated herein by reference, which is a steerable and electronic property of the polymerization site. Refers to a catalyst containing an auxiliary ligand that affects the formation of secondary polymerization species. The term “metallocene catalyst” is a single site catalyst in which the auxiliary ligand comprises a substituted or unsubstituted cyclopentadienyl group, and the term “non-metallocene catalyst” refers to a single site catalyst other than a metallocene catalyst.

ここでＭはニッケルまたはパラジウムであり；ＲおよびＲ’は独立な水素、ヒドロカルビル、または置換ヒドロカルビル；Ａｒは（ＣＦ_３）_２Ｃ_６Ｈ_３であり、Ｘはアルキル、メチル、水素化物、またはハロゲン化物である。 Non-metallocene catalysts include, but are not limited to: First, the Brookhart catalyst has the following structural formula.

Where M is nickel or palladium; R and R ′ are independent hydrogen, hydrocarbyl or substituted hydrocarbyl; Ar is (CF ₃ ) ₂ C ₆ H ₃ and X is alkyl, methyl, hydride, or halogen It is a monster.

ここで、Ｍはチタンまたはジルコンである。 Next, it is a McConville catalyst and has the following structural formula.

Here, M is titanium or zircon.

ここで、Ｍは金属であり、Ｒは水素、アルキルまたはヒドロカルビルである。 Next, iron (II) and cobalt (II) complexes having a 2,6-bis (imino) polydyl ligand have the following structural formula.

Here, M is a metal and R is hydrogen, alkyl or hydrocarbyl.

ここで、Ｍは金属原子であり；ｍおよびｎは独立に１〜４であり、芳香族環に結合された置換基の数を示し；Ｒ_ｍおよびＲ_ｎは独立して水素またはアルキルであり；Ｘはハロゲン化物またはアルキルである。 A titanium or zircon complex comprising pyrrole as a ligand also acts as a single site catalyst. These complexes have the following structural formula:

Where M is a metal atom; m and n are independently 1 to 4 and indicate the number of substituents attached to the aromatic ring; R _m and R _n are independently hydrogen or alkyl. X is a halide or alkyl.

ここで、Ａｒは芳香族、Ｍは金属、Ｘはハロゲン化物またはアルキルである。 Another example is a diimide complex of nickel and palladium, which has the following structural formula:

Here, Ar is aromatic, M is a metal, and X is a halide or alkyl.

ここで、Ｂはホウ素であり、Ｍは金属原子である。 Bolatabenzene complexes of Group IV or Group V metals also act as single site catalysts. These have the following structural formula:

Here, B is boron and M is a metal atom.

  As used herein, the term “single site catalyst polymer” refers to any polymer, copolymer, or terpolymer polymerized using a single site catalyst, particularly any polyolefin. The term “non-metallocene catalyst polymer” refers to any polymer, copolymer, or terpolymer, especially any polyolefin, polymerized using a single site catalyst other than a metallocene catalyst. The above-described catalyst is an example of a non-metallo-sensing lucite catalyst. The term “metallocene-catalyzed polymer” refers to any polymer, copolymer, or terpolymer polymerized using a metallocene catalyst, particularly any polyolefin.

  As used herein, the term “single site catalyst polymer blend” refers to any blend of a single site catalyst polymer and any other type of polymer, particularly an ionomer, as well as a single site catalyst polymer and another single site catalyst polymer. Refers to any blend. This includes, but is not limited to, metallocene catalyst polymers.

  The terms “grafted single-site catalyst polymer” and “grafted single-site catalyst polymer blend” refer to any single polymer in which a single-site catalyst polymer has been post-polymerized to graft at least one functional group onto the single-site catalyst polymer. Refers to a site catalyst polymer or a single site catalyst polymer blend. A “post polymerization reaction” is any reaction that occurs after a polymer is produced by a polymerization reaction.

  Single site catalyst polymers can be grafted and blended with polymers such as ungrafted single site catalyst polymers, grafted single site catalyst polymers, ionomers, and thermoplastic elastomers. Preferably the single site catalyst polymer is blended with at least one ionomer of this invention.

ただし、Ｒ_１は水素、分岐または直鎖アルキル例えばメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、およびオクチル、カルボサイクリック、芳香族、またはヘテロ環式化合物であり；Ｒ_２、Ｒ_３、Ｒ_５およびＲ_６は水素、Ｃ_１−Ｃ_５を含む低次アルキル、カルボサイクリック、芳香族、またはヘテロ環式化合物であり；Ｒ_４はＨ、Ｃ_ｎＨ_２ｎ＋１（ただしｎ＝１〜１８）、およびフェニルからなるグループから選択され、Ｒ_４中の０から５個の水素が置換体ＣＯＯＨ、ＳＯ_３Ｈ、ＮＨ_２、Ｆ，Ｃｌ、Ｂｒ、Ｉ、ＯＨ、ＳＨ、シリコーン、低次のアルキルエステルおよび低次のアルキルエーテルにより置換することができ、ただし、Ｒ_３およびＲ_４は二環のリングを形成できるものとし；Ｒ_５は水素、Ｃ_１−Ｃ_５を含む低次のアルキル、カルボサイクリックまたは芳香族；Ｒ_６は水素、Ｃ_１−Ｃ_５を含む低次のアルキル、カルボサイクリックまたは芳香族；ｘ、ｙおよびｚは各コ−モノマーの相対パーセントである。ｘは、約１から約１００パーセントの範囲であってよく、より好ましくは、約１から約７０パーセントの範囲で良く、最も好ましくは約１から約５０パーセントの範囲であって良い。ｙは、約９９から約０パーセントであってよく、好ましくは、約９から約３０パーセントであってよく、最も好ましくは、約９から約５０パーセントであってよい。ｚは、約０から約５０パーセントの範囲でよい。当業者は、酸部分が上述の構造中の配位子として働く場合には、上述のとおり有機脂肪酸により１００％まで中和できることを理解するであろう。 The grafted single site catalyst polymer useful in the golf ball of the present invention provides a grafted single site catalyst polymer having the desired one or more side groups by post-polymerizing the ungrafted single site catalyst polymer. Examples of single site catalytic polymers that can be grafted with functional groups for use in this invention include, but are not limited to, homopolymers of ethylene and propylene, and ethylene and secondary olefins, preferably propylene, butene, pentene, A copolymer of hexene, heptene, octene, and norbornene. Monomers useful for this invention include, but are not limited to, sulfonic acids, sulfonic acid derivatives such as chlorosulfonic acid, vinyl ethers, vinyl esters, primary, secondary and tertiary amines, epoxies, isocyanates, monocarboxylic acids, dicarboxylic acids. Acids, partially or fully ester-derived mono- and dicarboxylic acids, anhydrides of dicarboxylic acids, and cyclic imides of dicarboxylic acids. In general, this embodiment of the invention is a golf ball having at least one layer comprising at least one grafted single site catalyst polymer or polymer blend, the grafted single site catalyst polymer having the following functional groups: Manufactured by grafting to a single site catalyst polymer having the structural formula.

Where R ₁ is hydrogen, branched or straight chain alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, carbocyclic, aromatic, or heterocyclic compounds; R ₂ , R ₃ , R ₅ and R ₆ are hydrogen, lower alkyl including C ₁ -C ₅ , carbocyclic, aromatic, or heterocyclic; R ₄ is H, C _n H _{2n + 1} (where n = 1 to 18), and from the group consisting of phenyl, 0 to 5 hydrogens in R ₄ are substituted COOH, SO ₃ H, NH ₂ , F, Cl, Br, I, OH, SH, silicone, lower order alkyl via an ester and a low order alkyl ethers can be substituted, provided that, R ₃ and R ₄ shall be able to form a ring bicyclic; R ₅ is hydrogen, Low order alkyl containing ₁ -C _5, carbocyclic or aromatic; _{R 6} is _hydrogen, C 1 -C low order alkyl containing _5, carbocyclic or aromatic; x, y and z are each co -Relative percent of monomer. x may range from about 1 to about 100 percent, more preferably from about 1 to about 70 percent, and most preferably from about 1 to about 50 percent. y may be from about 99 to about 0 percent, preferably from about 9 to about 30 percent, and most preferably from about 9 to about 50 percent. z may range from about 0 to about 50 percent. One skilled in the art will appreciate that when the acid moiety acts as a ligand in the above structure, it can be neutralized to 100% with organic fatty acids as described above.

  The HNP of the present invention is a highly crystalline acid copolymer and its derivatives (which may be neutralized with conventional metal cations or organic fatty acids and salts thereof) or a highly crystalline acid copolymer and its ionomer derivative and at least one addition May be blended with conventional materials, preferably blends of acid copolymers and their ionomer derivatives. Here, the term “highly crystalline acid copolymer” is defined as “product-by-process”, which is produced from an ethylene / carboxylic acid copolymer containing from about 5 to about 35 weight percent acrylic or methacrylic acid. An acid copolymer or an ionomer derivative thereof. However, the copolymer is polymerized at a temperature of about 130 ° C. to about 200 ° C. and a pressure of about 20000 psi, preferably greater than 25000 psi, and up to about 70 percent, preferably up to 100 percent of the acid groups are metal ions, organic fatty acids, And a salt thereof, or a mixture thereof. The melt index (“MI”) of the copolymer is from about 20 to about 300 g / 10 minutes, preferably from about 20 to about 200 g / 10 minutes, and when the copolymer is neutralized, the resulting acid copolymer and its ionomer derivative The MI is about 0.1 to about 30.0 g / 10 min.

  Suitable highly crystalline acid copolymers and their ionomer derivative compositions and methods for their production are disclosed in US Pat. No. 5,580,927, incorporated herein by reference.

  The highly crystalline acid copolymer and its ionomer derivative employed in this invention is preferably from about 5 to about 35 percent, more preferably from about 9 to about 18 percent, and most preferably from about 10 to about 13 percent by weight. It is produced from a copolymer containing acid groups. However, up to about 75 percent, most preferably up to about 60 percent, of the acid groups are neutralized with organic fatty acids, salts thereof, or metal ions such as sodium, lithium, magnesium or zinc ions.

  In general, highly crystalline acid copolymers and their ionomer derivatives are produced by polymerizing the base polymer at low temperatures, but the pressure is equivalent to the pressure used to produce ordinary acid copolymers and their ionomer derivatives. Conventional acid copolymers are typically polymerized at a polymerization temperature of at least about 200 ° C. to about 270 ° C., preferably about 220 ° C., and a pressure of about 23 to about 30 ksi. In contrast, the highly crystalline acid copolymer and its ionomer derivative employed in this invention have a polymerization temperature of less than about 200 ° C, preferably from about 130 ° C to about 200 ° C, and a pressure of about 20 to about 50 psi. From the acid copolymer produced in

または、つぎのような式の構造を有する。

ここで、Ｒ_１−Ｒ_９は、直鎖または分岐鎖のアルキル、カルボサイクリック、または芳香族の有機部分であり；Ｚは、アルキル化および／または四級化に続いて生成される負電荷共役イオンである。カチオンアイオノマーは上述した有機脂肪酸により１００％まで四級化されてよい。 The HNPs of this invention may be blended with cationic ionomers such as those disclosed in US Pat. No. 6,193,619. The contents of which are incorporated herein by reference. Specifically, the cationic ionomer has the following formula:

Or it has the structure of the following formula | equation.

Where R ₁ -R ₉ is a linear or branched alkyl, carbocyclic, or aromatic organic moiety; Z is a negative charge generated following alkylation and / or quaternization It is a conjugated ion. Cationic ionomers may be quaternized to 100% with the organic fatty acids described above.

  Further, such alkyl groups may include various substituents in which one or more hydrogens are replaced with functional groups. Functional groups are, but not limited to, hydroxyl, amino, carboxyl, amide, ester, ether, sulfone group, siloxane, siloxyl, silane, sulfonyl and halogen.

  Here, substituted and unsubstituted carbocyclic groups having up to about 20 carbon atoms mean cyclic carbon-containing compounds such as, but not limited to, cyclopentyl, cyclohexyl, cycloheptyl and the like. Such a cyclic group may include various substituents in which one or more hydrogens are substituted with a functional group. Such functional groups include those described above, and further include the lower order alkyl groups described above. The cyclic group of this invention may further contain a heteroatom.

ここで、Ａ＝Ｒ−Ｚ⁻Ｍ^＋ｘ；Ｒは直鎖または分岐脂肪族基、置換の直鎖または分岐脂肪族基、または芳香族または置換芳香族基；Ｚは、ＳＯ_３ ⁻、ＣＯ_２ ⁻、またはＨＰＯ_３ ⁻；ＭはＩＡ、ＩＢ、ＩＩＡ、ＩＩＢ、ＩＩＩＡ、ＩＩＩＢ、ＩＶＡ、ＩＶＢ、ＶＡ、ＶＢ、ＶＩＡ、ＶＩＢ、ＶＩＩＢまたはＶＩＩＩＢの金属；ｘ＝１〜５；Ｂは、直鎖または分岐脂肪族基、置換の直鎖または分岐脂肪族基、または芳香族または置換芳香族基；ｎ＝１〜１００である。好ましくは、Ｍ^＋ｘは、Ｌｉ^＋、Ｎａ^＋、Ｋ^＋、Ｍｇ^＋２、Ｚｎ^＋２、Ｃａ^＋２、Ｍｎ^＋２、Ａｌ^＋３、Ｔｉ^＋ｘ、Ｗ^＋ｘ、またはＨｆ^＋ｘの１つである。 The HNP of this invention may be blended with polyurethane and polyurea ionomers. This is an anionic moiety or group, such as that disclosed in US Pat. No. 6,207,784, incorporated herein by reference. Typically, such groups are incorporated into the diisocyanate or diisocyanate component of a polyurethane or polyurea ionomer. Anionic groups may be bound to the polyol or amine component of the polyurethane or polyurea ionomer. Preferably, the anionic group is based on a sulfone, carboxyl or phosphate group. One or more anionic groups may also be incorporated into the polyurethane or polyurea. An example of an anionic polyurethane ionomer having an anionic group attached to the diisocyanate moiety has a chemical structure of the following formula:

^{Here, A = R-Z - M} + x; R is a linear or branched aliphatic group, a substituted linear or branched aliphatic group or an aromatic or substituted aromatic group,; Z _is, ^SO 3 -, CO ₂ ^-, or HPO ₃ ^-; M is IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIB or VIIIB metal; x = 1~5; B is a straight-chain Or a branched aliphatic group, a substituted linear or branched aliphatic group, or an aromatic or substituted aromatic group; n = 1-100. Preferably, M ^{+ x} is one of Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺² , Zn ⁺² , Ca ⁺² , Mn ⁺² , Al ⁺³ , Ti ^{+ x} , W ^{+ x} , or Hf ^{+ x} .

Examples of anionic polyurethane ionomers in which an anionic group is bonded to the polyol component of the polyurethane are characterized by the structural formula above, where A is a linear or branched aliphatic group, a substituted linear or branched aliphatic group, or aromatic or substituted aromatic group; B = R-Z - M + x; R is a linear or branched aliphatic group, a substituted linear or branched aliphatic group or an aromatic or substituted aromatic group,; Z is SO ₃ ⁻ , CO ₂ ⁻ , or HPO ₃ ⁻ ; M is a metal of IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIB, or VIIIB; x = 1-5 N = 1-100. Preferably, M ^{+ x} is one of Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺² , Zn ⁺² , Ca ⁺² , Mn ⁺² , Al ⁺³ , Ti ^{+ x} , W ^{+ x} , or Hf ^{+ x} .

ここで、Ａ＝Ｒ−Ｚ⁻Ｍ^＋ｘ；Ｒは直鎖または分岐脂肪族基、置換の直鎖または分岐脂肪族基、または芳香族または置換芳香族基；Ｚは、ＳＯ_３ ⁻、ＣＯ_２ ⁻、またはＨＰＯ_３ ⁻；ＭはＩＡ、ＩＢ、ＩＩＡ、ＩＩＢ、ＩＩＩＡ、ＩＩＩＢ、ＩＶＡ、ＩＶＢ、ＶＡ、ＶＢ、ＶＩＡ、ＶＩＢ、ＶＩＩＢまたはＶＩＩＩＢの金属；ｘ＝１〜５；Ｂは、直鎖または分岐脂肪族基、置換の直鎖または分岐脂肪族基、または芳香族または置換芳香族基；ｎ＝１〜１００である。好ましくは、Ｍ^＋ｘは、Ｌｉ^＋、Ｎａ^＋、Ｋ^＋、Ｍｇ^＋２、Ｚｎ^＋２、Ｃａ^＋２、Ｍｎ^＋２、Ａｌ^＋３、Ｔｉ^＋ｘ、Ｗ^＋ｘ、またはＨｆ^＋ｘの１つである。 A suitable anionic polyurea ionomer having an anionic group attached to the diisocyanate component has a chemical structure according to the following chemical structural formula:

^{Here, A = R-Z - M} + x; R is a linear or branched aliphatic group, a substituted linear or branched aliphatic group or an aromatic or substituted aromatic group,; Z _is, ^SO 3 -, CO ₂ ^-, or HPO ₃ ^-; M is IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIB or VIIIB metal; x = 1~5; B is a straight-chain Or a branched aliphatic group, a substituted linear or branched aliphatic group, or an aromatic or substituted aromatic group; n = 1-100. Preferably, M ^{+ x} is one of Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺² , Zn ⁺² , Ca ⁺² , Mn ⁺² , Al ⁺³ , Ti ^{+ x} , W ^{+ x} , or Hf ^{+ x} .

A suitable anionic polyurea ionomer having an anionic group attached to the amine component of the polyurea is characterized by the chemical structure described above, where A is a linear or branched aliphatic group, a substituted linear or branched aliphatic group. or aromatic or substituted aromatic group; B = R-Z - M + x; R is a linear or branched aliphatic group, a substituted linear or branched aliphatic group or an aromatic or substituted aromatic group,; Z is , SO ₃ ⁻ , CO ₂ ⁻ , or HPO ₃ ⁻ ; M is a metal of IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIB, or VIIIB; x = 1 to 5; n = 1 to 100. Preferably, M ^{+ x} is one of Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺² , Zn ⁺² , Ca ⁺² , Mn ⁺² , Al ⁺³ , Ti ^{+ x} , W ^{+ x} , or Hf ^{+ x} . Anionic polyurethanes and polyurea ionomers may also be neutralized to 100% with the organic fatty acids described above.

  Useful anionic polymers for this invention are those disclosed in US Pat. No. 6,221,960, incorporated herein by reference, which can be neutralized hydroxyl and / or dealkylated Any homopolymer, copolymer or terpolymer having an ether group, wherein at least some of the neutralizable or dealkylatable groups are neutralized or dealkylated by metal ions.

  Here, a “neutralizable” or “dealkylatable” group is a hydroxyl or ether group pendant from the polymer chain and is neutralized with a metal ion, preferably a base of a metal ion. Refers to what can be or can be dealkylated. These neutralized polymers improve characteristics important to the performance of the golf ball, such as elasticity, impact strength, durability and rub resistance. Suitable metal bases include metal cations and base ions. Examples of such bases are hydroxides, carbonates, acetates, oxides, sulfides and the like.

  The specific base is employed depending on the nature of the hydroxyl or ether compound to be neutralized or dealkylated and can be readily determined by one skilled in the art. Preferred anionic bases are hydroxides, carbonates, oxides and acetates.

  The metal ion may be any metal ion that forms an ionic compound with an anionic base. The metal is not specifically limited, but an alkali metal, preferably lithium, sodium, or potassium; an alkaline earth metal, preferably magnesium or calcium; a transition metal, preferably titanium, zircon, or zinc; Group III and Group IV metals. The metal ion may have a charge of +1 to +5. Most preferably, the metal is lithium, sodium, potassium, zinc, magnesium, titanium, tungsten, or calcium and the base is a hydroxide, carbonate, or acetate.

ここで、Ｒ_１はＯＨ、ＯＣ（Ｏ）Ｒ_ａ、Ｏ−Ｍ^＋Ｖ、（ＣＨ_２）_ｎＲ_ｂ、（ＣＨＲ_ｚ）_ｎＲ_ｂ、またはアリールであり、ｎは少なくとも１、Ｒ_ａは低次のアルキル、Ｍは金属イオン、Ｖは１〜５の整数、Ｒ_ｂはＯＨ、ＯＣ（Ｏ）Ｒ_ａ、Ｏ−Ｍ^＋Ｖ、Ｒ_ｚは低次のアルキルまたはアリールであり、Ｒ_２、Ｒ_３およびＲ_４は同様に置換される。好ましくは、ｎは１〜１２であり、より好ましくは１〜４である。 Anionic polymers useful for this invention are those containing neutralizable hydroxyl and / or dealkylatable ether groups. Exemplary polymers are ethylene vinyl alcohol copolymer, polyvinyl alcohol, polyvinyl acetate, poly (p-hydroxymethylene styrene), and p-methoxy styrene to name a few. One skilled in the art can readily appreciate that there are many such polymers available for use in the compositions of the present invention. In general, anionic polymers are described by the following chemical structure:

Here, R ₁ is OH, OC (O) R _a , OM ^{+ V} , (CH ₂ ) _n R _b , (CHR _z ) _n R _b , or aryl, n is at least 1, and R _a is low Next alkyl, M is a metal ion, V is an integer of 1 to 5, R _b is OH, OC (O) R _a , OM ^{+ V} , R _z is a lower alkyl or aryl, R ₂ , R ₃ and R ₄ are similarly substituted. Preferably, n is 1-12, more preferably 1-4.

  The term “substituted” here means that one or more hydrogen atoms are replaced by a functional group. Functional groups include, but are not limited to, hydroxyl, amino, carboxyl, sulfone, amide, ether, ether, phosphoric acid, thiol, nitro, silane, and halogen, and many other functions that are familiar to those skilled in the art. It is a group.

  The term “alkyl” or “lower-order alkyl” here refers to a group containing 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms.

In the anionic polymers useful for this invention, at least some of the neutralizable or dealkylatable groups of R ₁ are correspondingly neutralized or dealkylated with organic fatty acids, salts thereof, metal bases or mixtures thereof. Form an anionic moiety. The portion of the neutralizable or dealkylatable group that is neutralized or dealkylated is between about 1 and 100 weight percent, preferably between about 50 and 100 weight percent, more preferably between about 90 and about 100. It may be.

  Neutralization or dealkylation is performed by first dissolving the polymer and then adding metal ions into the extruder. The degree of neutralization or dealkylation is controlled by adjusting the amount of metal ion added. Any neutralization or dealkylation technique that can be employed by those skilled in the art may be appropriately employed.

In one embodiment, the anionic polymer repeats as a unit any one of the three homopolymer units of the chemical structure described above. In a preferred embodiment, R ₂ , R ₃ and R ₄ are hydrogen and R ₁ is hydroxyl. That is, this anionic polymer is a polyvinyl alcohol homopolymer in which a part of hydroxyl groups is neutralized with a metal base. In another preferred embodiment, R ₂ , R ₃ and R ₄ are hydrogen, R ₁ is OC (O) R _a , and R _a is meryl. That is, this anionic polymer is a polyvinyl acetate homopolymer in which a part of the methyl ether group is dealkylated with a metal ion.

    The anionic polymer may be a copolymer consisting of two different repeating units with different substituents, or a terpolymer consisting of three different repeating units. The unit is described by the above structural formula. In this example, the polymer may be a random copolymer, alternating copolymer, or block copolymer. The term “copolymer” here also includes terpolymers.

In other examples, the anionic polymer is a copolymer, provided that R ₅ , R ₆ , R ₇ and R ₈ are each independently selected from the group defined for R ₂ above. The first unit of the copolymer may comprise from about 1 to about 99 weight percent of the polymer, preferably from about 5 to about 50 weight percent, and the second unit comprises from about 99 to about 1 weight percent of the polymer, preferably May comprise from about 95 to about 50 weight percent. In one example, the anionic polymer is a random, alternating or block copolymer of units (Ia) and units (Ib), where R ₁ is hydroxyl and each of the remaining R groups is hydrogen. That is, the polymer is a copolymer of ethylene and vinyl alcohol. In other examples, the anionic polymer is a random, alternating or block copolymer of unit (Ia) and unit (Ib), wherein R ₁ is OC (O) R ₅ and R ₅ is methyl. Each of the remaining R groups is hydrogen. That is, the polymer is a copolymer of ethylene and vinyl acetate.

In other examples, the anionic polymer is an anionic polymer having ether groups that can be neutralized or dealkylated as in the chemical structure above, where R _1-9 and R _b and R _z are as described above. R _10-11 is individually selected from the group defined for R2 above; R ₁₂ is OH or OC (O) R ₁₃ and R ₁₃ is lower alkyl; x, y, and z indicate the relative weight percent of the different units. x can range from about 99 to about 50 weight percent, y can range from about 1 to about 50 weight percent, and z can range from about 0 to about 50 weight percent. At least a portion of the neutralizable group R ₁ is neutralized. When z is greater than zero, part of the group R ₁₀ can be completely or partially neutralized as desired.

  Specifically, the anionic polymer and blends thereof may include compatible blends of anionic polymers and ionomers, such as the ionomers and erylene acrylic methacrylate ionomers described above and their terpolymers. It is commercially available from DuPont and Exxon under the brand names SURLYN ™ and IOTEK ™. Anionic polymer blends useful for the golf balls of this invention include other polymers such as polyvinyl alcohol, copolymers of ethylene and vinyl alcohol, poly (ethylethylene), poly (heptylethylene), poly (hexyldecylethylene), poly ( Isopentylethylene), poly (butyl acrylate), poly (2-ethylbutyl acrylate), poly (heptyl acrylate), poly (2-methylbutyl acrylate), poly (3-methylbutyl acrylate), poly (N-octadecylamide) ), Poly (octadecyl methacrylate), poly (butoxyethylene), poly (methoxyethylene), poly (pentyloxyethylene), poly (1,1-dichloroethylene), poly (4-[(2-butoxyethoxy) methyl] styrene , Poly [oxy (ethoxymethyl) ethylene], poly (oxyethylethylene), poly (oxytetramethylene), poly (oxytrimethylene), poly (silane) and poly (silazane), polyamide, polycarbonate, polyester, styrene block Copolymers, polyether amides, polyurethanes, main chain heterocyclic polymers, and poly (furantetracarboxylic diimides) and the class of polymers to which they belong.

The flexural modulus of the anionic polymer composition of this invention is typically from about 0.5 ksi to about 300 ksi, preferably from about 2 to about 200 ksi. The material hardness of the anionic polymer composition is typically at least about 15 Shore A, preferably about 30 Shore A to 80 Shore D, and more preferably about 50 Shore A to 60 Shore D. The loss tangent or dissipation factor of the anionic polymer composition is the ratio of the loss modulus to the dynamic shear storage modulus, typically less than about 1, and preferably about 0. Less than 01, more preferably less than about 0.001. However, it measured at about 23 degreeC. The specific gravity of the anionic polymer composition is typically about o. Greater than 7, preferably greater than about 1. The dynamic shear accumulation coefficient or accumulation coefficient of the anionic polymer composition at about 23 ° C. is typically at least about 10,000 dyn / cm ² .

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

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

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

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

  The golf ball center of the present invention may include various structures. Although the materials used for each layer are similar or substantially the same as described above, the characteristics and properties of each layer can be changed as appropriate according to the embodiment of the present invention.

  The cover layer may comprise one or more homopolymer or copolymer materials, such as:

(1) Vinyl resins, such as those produced by polymerization of vinyl chloride, or those produced by copolymerization of vinyl chloride with vinyl acetate, acrylic esters or vinylidene chloride;
(2) using polyolefins such as polyethylene, polypropylene, polybutylene and copolymers such as ethylene methyl acrylate, ethylene ethyl acrylate, ethylene vinyl acetate, ethylene methacrylic acid or ethylene acrylic acid or propylene acrylic acid and single site or metallocene catalysts Copolymers and homopolymers produced;
(3) Polyurethanes, such as those made from polyols and diisocyanates or polyisocyanates and those disclosed in US Pat. No. 5,334,673;
(4) polyureas, such as those described in US Pat. No. 5,484,870;
(5) Polyamides such as those made from poly (hexamethylene adipamide) and other diamines and dibasic acids, and those made from amino acids such as poly (caprolactam), and polyamides and SURLYN, polyethylene, ethylene copolymers, Blends with ethyl-propylene-nonconjugated diene terpolymers and the like;
(6) acrylic resins and blends of these resins with polyvinyl chloride, elastomers, and the like;
(7) thermoplastics such as urethane; olefinic thermoplastic rubbers such as blends of polyolefins with ethylene-propylene-nonconjugated diene terpolymers; block copolymers of styrene and butadiene, isoprene or ethylene-butylene rubber; or copoly (ether- Amide), for example PEBAX commercially available from ELF Atchem of Philadelphia, PA;
(8) Polyphenylene oxide resin or a blend of polyphenylene oxide and high impact polystyrene, commercially available under the trademark NORYL by General Electric Company of Pittsfield, MA;
(9) Thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / glycol modified and elastomers under the trade name HYTREL by EI DuPont de Neumours & Co. of Wilmington, DE. And also marketed under the name LOMOD by General Electric Company of Pittsfield, MA;
(10) Blends containing acrylonitrile butadiene styrene, polybutylene terephthalate, polyethylene terephthalate, styrene maleic anhydride, polyethylene, elastomers and similar polycarbonates, and acrylonitrile butadiene styrene or ethylene vinyl acetate or other elastomeric polyvinyl chloride. And (11) blends of thermoplastic rubber with polyethylene, propylene, polyacetal, nylon, polyester, cellulose ester, and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

ここで、繰り返し単位の数ｘ及びｚは組み合わせて約３．６〜約８の値を有し、繰り返し単位ｙは約９〜約５０の範囲の値を有し、Ｒは−（ＣＨ_２）_ａ−であり、式中ａは約１〜約１０の繰り返し単位であってもよい。 In other examples, the polyetheramine has the following general structure:

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

ここで、Ｒは−（ＣＨ_２）_ａ−であり、式中ａは約１〜約１０の繰り返し単位であってもよい。 In yet another embodiment, the polyetheramine has the following general structure:

Wherein, R represents - _{(CH 2) a} - a and, a in the formula may be a repeating unit of from about 1 to about 10.

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

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

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

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

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

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

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

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

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

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

  Suitable saturated amine-terminated curing agents include, but are not limited to, ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; tetrahydroxypropyleneethylenediamine; 2,2,4- and 2,4,4. -Trimethyl-1,6-hexanediamine; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (sec -Butylamino) -cyclohexane; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane derivatives; 4,4'-dicyclohexylmethanediamine; 1,4-cyclohexane-bis- (methylamine); 3-cyclohexane-bis- (methylamine); diethylene glycol di- ( 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamine; imido-bis-propyl Amines; monoethanolamines, diethanolamines; triethanolamines; monoisopropanolamines, diisopropanolamines; isophoronediamines; triisopropanolamines; and mixtures thereof. In one example, the amine-curing agent has a molecular weight of about 64 or greater. In addition, any of the above polyether amines can be used as a curing agent to react with the polyurea prepolymer.

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

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

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

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

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

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

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

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

  The cover can also be made from an ionomer polymer or blend thereof as described above.

  It has been found by this invention that a castable, reactive material that can be applied in fluid form can form a very thin cover layer on a golf ball. In particular, it has been found that a castable, reactive material that reacts to form a urethane elastomer material provides the desired thin outer cover layer.

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

  The cover is preferably formed around the core by mixing the materials and guiding them to the mold. It is important to measure the viscosity over that time. With this measurement, the subsequent steps of filling each mold half, introducing the core into one half, and closing the mold are done at the right time, and the core and cover halves are fused. The core alignment is realized, and the whole unity is achieved. It has been found that the viscosity range of a cured urethane mix suitable for introducing the core into the mold is between about 2000 cP and about 30000 cP, with a preferred range between about 8000 pC and 15000 cP.

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

  A ball cup holds the core of the ball by reduced pressure (or partial vacuum). After gelling for about 40 to about 80 seconds, place the core on both halves of the mold, release the vacuum and release the core. The mold half having the core and solidified cover half is removed from the centering fixture, inverted to fit the second mold half, and the selected amount introduced into the second mold The reactive polyurea prepolymer and curing agent of the gel begin to gel at an appropriate time before being combined. Similarly, both US Pat. No. 5,006,297 and US Pat. No. 5,334,673 are suitable and can be used to apply the castable reactive liquid used in this invention. A molding technique is disclosed. In addition, US Pat. Nos. 6,180,040 and 6,180,722 disclose a method for preparing a dual core golf ball. These are incorporated individually by reference. Note that the method of the present invention is not limited to these techniques.

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

  Referring again to FIG. 2, in one embodiment, the multi-layer golf ball 20 has at least three pieces: an inner core 22, an outer core layer 24, and a cover 26. The inner core 22 has a diameter of about 1.40 inches and its Atti compression is less than 60, preferably less than 45, and most preferably less than 40. This compression is preferably a number in the range of about 5 to about 60, more preferably a number in the range of about 10 to about 50, and most preferably a number in the range of about 15 to about 40. The specific gravity of the inner core 22 is smaller than that of the outer core layer, preferably less than 1.15, and most preferably less than 1.10.

  Accordingly, the specific gravity of the outer core layer 24 is greater than that of the inner core 22, preferably greater than 1.15, preferably greater than 1.20, and most preferably greater than 1.25. The outer core layer 24 has a Shore D hardness of at least 55, and the flexural modulus of the outer core layer 24 is greater than the flexural modulus of the inner core 22. The thickness of the outer core layer 24 is about 0.10 inches.

The cover layer 26 has a thickness of at least about 0.04 inches, the cover layer 26 comprises a rigid ionomer blend, and its Shore D hardness is at least 60, preferably at least 65. The flexural modulus of the cover 26 is preferably at least 60 ksi. A preferable relationship between the Shore D hardness and the flexural modulus of the cover layer 26 is as follows when the flexural modulus is measured by ksi and is at least 58 ksi.
Preferably: 1.0> (Shore D _cover ) / (Bending elastic modulus _cover )
More preferably: 0.9> (Shore D _cover ) / (Bending elastic modulus _cover )
Most preferably: 0.8> (Shore D _cover ) / (Bending elastic modulus _cover )
These relationships realize a golf ball that has a low spin when launched from a tee and yet has an increased spin on approach shots to the green. For unskilled golfers, the drive distance will be longer, while better players will be able to control the ball around the green easily.

  In a preferred embodiment, cover layer 26 includes an acrylate ionomer (Dow or Schulman type) with an acid component between about 13% and 16%. However, as will be readily appreciated by those skilled in the art and as described above, the ionomer type and the range of acid components can be varied. The ionomer is preferably neutralized by cations of sodium (Na), lithium (Li), zinc (Zn), magnesium (Mg), or calcium (Ca), which are again readily understood by those skilled in the art. As such, the cations used can vary.

  In other embodiments, the inner core 22, the outer core layer 24, and the cover 26 are all substantially similar to the preceding embodiments, but the COR gradient is slow to fast by selecting materials, properties, and dimensions. Like that. For example, the COR of the inner core 22 is smaller than the COR of the subassembly including the inner core 22 and the outer core layer 24, and the COR of the subassembly includes the inner core 22, the outer core layer 24, and the cover 26 as a whole. It is smaller than the COR of the golf ball 20. This slow to fast COR gradient allows the ball to have a higher initial velocity, a lower spin when launched from the tee, and a higher spin when hitting the approach shot to the green. As a result, a more permissive drive that provides a longer distance is possible for players who are not very good at slow swing speeds, and more control and accuracy is achieved for players who are good at swing speeds.

  Other embodiments of the golf ball of the present invention are substantially similar to the previous embodiments, but the core layer, i.e., inner core 22 or outer core layer 24, has HNP. In this embodiment, it is preferred that the inner core 22 comprises unfilled HNP and the specific gravity of the inner core is less than 1.0, most preferably about 0.95. By reducing the specific gravity of the center of the ball with unfilled HNP, the moment of inertia of the ball is increased. As a result, the spin caused by the moment of impact is reduced, and the distance when launched from the tee is increased.

  Referring again to FIG. 1, in another embodiment, the multi-layer golf ball 10 has an inner core 12, at least one intermediate core layer 14, an outer core layer 16, and a cover layer 18, so that at least four pieces are included. It has. In this embodiment, the core assembly includes three pieces, which form two separate subassemblies. One is an inner subassembly made from the inner core 12 and at least one intermediate core layer 14, and the other includes the inner core 12, the intermediate layer 14, and the outer cover layer 16. . Other embodiments may have multiple intermediate layers 14 such that there are multiple subassemblies each surrounding successive intermediate layers. In the three-piece core embodiment, the specific gravity of the inner core 12 is smaller than the specific gravity of the intermediate core layer 14, and the specific gravity of the intermediate core layer 14 is smaller than the specific gravity of the outer core layer 16. The specific gravity of the cover layer 18 is also smaller than the specific gravity of the outer core layer 16. The volume of the inner core 12 in the embodiment shown in FIG. 1 is larger than the volume of the outer core layer 16, both of which are larger than the volume of the cover layer 18. However, the relationship between the volume of each layer and the hardness of each layer is opposite. The cover layer 18 has a Shore D hardness greater than that of the outer core layer 16, and the outer core layer 16 has a hardness greater than that of the inner core 12. When multiple intermediate core layers are added, each successive intermediate core layer has a greater specific gravity, greater Shore D hardness, and smaller than the preceding layer close to the inner core 12. Have a volume. The outer portion of the golf ball 10, such as the outer core layer 16 and the cover layer 18, is beneficial for unskilled players due to the comfortable sound and improved flight distance provided upon striking, but reduces the hardness inside the ball. Is important for advanced players to enhance improved feel and control similar to traditional wound balls.

  The intermediate layer 14 comprises a thermosetting polybutadiene or other diene rubber-based formulation, thermoplastic or thermosetting polyurethane, polyurea, partially or fully neutralized HNP, metallocene or other single site catalyst polymer. Polymers including polyolefins, silicones, materials such as polyamides, polyesters, polyether amides, polyester amides, and other materials known in the art may be included. The intermediate layer 14 may be any layer d between the innermost core and the outermost layer, and there may be a plurality of intermediate layers 14.

  As employed herein, the following terms are defined as follows:

  Coefficient of restitution (COR): The ratio of the relative velocity after a collision to the relative velocity between the two objects before the direct collision of the two objects. As a result, CoR takes a value from 0 to 1.0. A CoR value of 1.0 corresponds to fully elastic collision, and a CoR value of zero corresponds to complete inelastic collision. Since Bor's CoR directly affects the initial velocity and distance of the ball after hitting the club, golf ball manufacturers are interested in this feature when designing and testing golf balls.

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

  Compression: In the past, compression was used to describe the quality of a golf ball according to the winding tension around the three-piece ball core. For solid core golf balls, compression simply indicates how much the ball “deforms” under compressive force. Compression is measured using a manual instrument ("Atti Gauge") from Atti Engineering Company of Union City, New Jersey, applying a spring load force to the golf ball center, golf ball core, or golf ball to be measured. The The instrument is equipped with a Federal Dial Gauge Model D81-C and uses a calibration spring under a known load. The sphere to be inspected receives a force of 0.2 inches (5 mm) against this spring. If the spring is compressed by 0.2 inches, the compression is evaluated as 100, and if the spring is compressed by 0.1 inches, the compression value is evaluated as zero. To explain more clearly, a soft material has a smaller Atti compression value than a material that is hard and hard to shrink.

  Flexural Modulus: The ratio of flexural stress to flexural strain (measured in the flex mode) within the elastic limit and is similar to the tensile modulus. This property represents the flexural strength of the material and is measured by ASTM Test Method D790.

  Hardness: A property of a fixed material that represents resistance to permanent deformation. This can be measured at various scales, but all hardness data in this application is measured using a Shore D durometer. The test is performed according to ASTM Test Method D2240. The result of this test is a useful measure of the relative resistance of the various grades of polymer to indentations.

  Ionomer: A polymer, especially a polyelectrolyte, having a copolymer containing both electrically neutral repeating units and a small amount of ionic units (usually 15% or less). Ionomers have unique physical properties due to the interaction of ions in discrete regions of the material.

  Specific gravity: The ratio of the density of a substance to the density of another substance, typically water. Since the density of water is 1 g / cc, the specific gravity of the material is usually equal to the density. However, the unit is canceled and is dimensionless. Specific gravity is measured by ASTM Test Method D792.

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

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

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

1 is a cross-sectional view of a golf ball manufactured according to a first embodiment of the present invention. It is sectional drawing of the golf ball manufactured according to 2nd Example of this invention.

Explanation of symbols

10, 20 Golf ball 12, 22 Inner core 14 Intermediate core layer 16, 24 Outer core layer 18, 26 Cover

Claims (2)

An inner core with an Atti compression of less than 40;
At least one intermediate layer surrounding the inner core having a hardness of at least 55 Shore D and a specific gravity greater than the specific gravity of the inner core;
A cover surrounding the intermediate layer,
The hardness of the inner core is less than the hardness of the intermediate layer, the flexural modulus of the cover (ksi display .1ksi = 6.89MPa) in obtained by dividing a Shore D hardness of the cover ratio be less than 0.8 ,
The flexural modulus of the intermediate layer is greater than the flexural modulus of the inner core, the flexural modulus of the cover is greater than or equal to the flexural modulus of the intermediate layer, and
A golf ball characterized in that a coefficient of restitution (COR) of the inner core is smaller than a connection COR of an assembly composed of the inner core and the intermediate layer, and the connection COR is smaller than a COR of a completed golf ball. The golf ball of claim 1, wherein the intermediate layer has a specific gravity greater than 1.20.

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