Negative hardness gradient outer core layer for dual core golf ball

The present invention relates to a golf ball with a core in general, and more specifically to a double core golf ball in which the hardness of the outer surface of the outer core layer is smaller than the hardness of the inner surface thereof.

A solid golf ball is typically manufactured from a solid core enclosed by a cover, both the solid core and the cover may have multiple layers, for example a double core comprising a solid center and an outer core layer. Also, the multilayer cover has an inner layer. Generally, golf ball cores and / or centers are constructed from thermosetting rubber, typically polybutadiene-based compositions. The core is usually heated and crosslinked to achieve certain properties, such as greater or less compression, which affects the spin rate and / or better "feel" of the ball. These features and other features may be fine-tuned according to the needs of golfers of various skills. From the golf ball manufacturer's point of view, it is desired that the core provide a wide range of properties, such as elasticity, durability, spin, and "feel". This allows manufacturers to manufacture and sell many different types of golf balls adapted to different levels of workmanship.

Traditionally, many single-core golf balls are known as "positive hardness gradients" with a conventional hardness gradient that goes from hard to soft from the surface of the core to the center of the core. The patent literature includes a number of documents that examine the hardness gradient from a hard surface to a soft center across a golf ball.

U.S. Pat. No. 4,650,193 (Molitor et al., Patent Document 1) surface-treats curable elastomer slag with a curing modifier, and then molds the slag into a core to create a hardness gradient on the surface layer of the core. I am considering bringing it. It is claimed that this treatment brings two regions of different composition to the core, the first part is the central part of the core, which is hard and elastic, which remains untreated and the first Part 2 is the outer layer of the core, which is soft and deformable, which has been treated with a core modifier. The two "layers" or regions of the core are one with each other, resulting in the effect of a gradient from a soft surface to a hard center.

U.S. Pat. No. 3,784,209 (Berman et al., Patent Document 2) generally discloses a hardness gradient from soft to hard. This "209" patent discloses a non-uniform molded golf ball with a core made of a "mixed" elastomer. The uncured central sphere is surrounded by a compatible but different uncured elastomer. The two layers of elastomer are simultaneously exposed to the curing agent and unite with each other, thereby forming a mixed core. The center of this core is harder with a higher density of the first elastomeric material than the outer layer. One of the drawbacks of this manufacturing method is the time-consuming process of forming a first elastomer, then a second elastomer, and then molding the two together. ..

Other patents are looking at cores that accept surface treatments to achieve a soft "epidermis." However, since the inner parts of these cores are untreated, they carry a gradient from a hard surface to a soft center similar to conventional cores. For example, US Pat. No. 6,113,831 (Nesbitt et al., Patent Document 3) discloses a generally idiomatic core and a separate soft epidermis that wraps around this core. This soft skin is formed by exposing the base metal slag to the stream during the molding process so that the maximum molding temperature exceeds the stream set temperature and further controls the heat generation molding temperature during molding. This epidermis has the outermost 1/32 to 1/4 inch in the radial direction of the spherical core. U.S. Pat. Nos. 5,976,443 and 5,733,206 (both Nesbitt et al., Patent Documents 4 and 5) disclose that a mist of water is applied to the surface of the slag to form a soft skin prior to molding. Allegedly, water delays the cross-linking of the core surface, thereby forming a softer epidermis around the hard central part, thereby softening the compression of the core.

In addition, many patents disclose multi-layer golf ball cores, where each core layer has a different hardness, which forms a hardness gradient from one core layer to the other.

However, it is possible to realize a single-layer core with a gradient that becomes softer to harder (a "negative" gradient) from the surface to the center, and to realize an inexpensive and efficient method for manufacturing such a core. Still desired. Cores with such properties allow golf ball designers to manufacture products with a unique combination of compression, "feeling", and spin.<patcit num="1"><text>U.S. Pat. No. 4,650,193</text></patcit><patcit num="2"><text>U.S. Pat. No. 3,784,209</text></patcit><patcit num="3"><text>U.S. Pat. No. 6,113,831</text></patcit><patcit num="4"><text>U.S. Pat. No. 5,976,443</text></patcit><patcit num="5"><text>U.S. Pat. No. 5,733,206</text></patcit>

One aspect of the invention is a second, with a first outer surface and geometric center, with an inner core manufactured entirely from a first substantially uniform formulation, and a second outer and inner surfaces. It has an outer core layer and a cover produced as a whole from a substantially uniform formulation of, with the geometric center, the first and second outer surfaces, and the inner surface each having hardness, the first The hardness of the outer surface of 1 is smaller than the hardness of the geometric center to form a negative hardness gradient, and the hardness of the second outer surface is smaller than the hardness of the inner surface to form a negative hardness gradient. The hardness of the inner surface of the outer core layer is the hardness of the first outer surface.<u style="single">Degree</u>It relates to a golf ball characterized by being large.

Other aspects of the invention include a first outer surface and geometric center, an inner core manufactured as a whole from a first substantially uniform formulation, and a second outer and inner surfaces. It has an outer core layer and a cover produced as a whole from a substantially uniform formulation of 2, the geometric center, the first and second outer surfaces, and the inner surface, each with hardness, said The hardness of the first outer surface is smaller than the hardness of the geometric center to form a negative hardness gradient, and the hardness of the second outer surface is smaller than the hardness of the inner surface to form a negative hardness gradient. The hardness of the inner surface of the outer core layer is the hardness of the first outer surface.<u style="single">Degree</u>It relates to a golf ball characterized by being small.

Yet another aspect of the invention is with a first outer surface and geometric center, with an inner core manufactured entirely from a first substantially uniform formulation, and a second outer and inner surfaces. It has an outer core layer and a cover produced as a whole from a second substantially uniform formulation, with the geometric center, the first and second outer surfaces, and the inner surface each associated with hardness. The hardness of the first outer surface is smaller than the hardness of the geometric center to form a negative hardness gradient, and the hardness of the second outer surface is smaller than the hardness of the inner surface to form a negative hardness gradient. , The hardness of the inner surface of the outer core layer is the hardness of the first outer surface.<u style="single">Degree and</u>With respect to golf balls characterized by being substantially equal.

Yet another aspect of the invention is with a first outer surface and geometric center, with an inner core manufactured entirely from a first substantially uniform formulation, and a second outer and inner surfaces. It has an outer core layer and a cover produced as a whole from a second substantially uniform formulation, with the geometric center, the first and second outer surfaces, and the inner surface each associated with hardness. The hardness of the first outer surface is larger than the hardness of the geometric center to form a positive hardness gradient, and the hardness of the second outer surface is smaller than the hardness of the inner surface to form a negative hardness gradient. , The hardness of the inner surface of the outer core layer is the hardness of the first outer surface.<u style="single">Degree</u>It relates to a golf ball characterized by being large.

A few technical features different from the present invention will be described. This technical feature is the inner core, which includes the first outer surface and geometric center, and is substantially uniform throughout so that its hardness is in the range of 35 shore C to 85 shore C. It is aimed at golf balls, including those manufactured from the formulation of. The outer core layer is formed around the inner core layer and has a second outer and inner surface, which is substantially uniform throughout so that its hardness is in the range of 55 shore C to 90 shore C. Manufactured from the second formulation. The cover layer is arranged around the outer core layer to form a golf ball. The cover layer may be a single layer or may consist of a plurality of layers, for example an inner cover layer and an outer cover layer. The hardness of the first outer surface is greater than the hardness of the geometric center to form a "positive hardness gradient", and the hardness of the second outer surface is substantially equal to or less than the hardness of the inner surface. A "negative hardness gradient" is formed.

The inner core contains a metal salt of carboxylic acid in an amount of about 15 phr to about 30 phr, and the outer core layer contains a metal salt of carboxylic acid in an amount of about 30 phr to about 45 phr, and the oxidation of the outer core layer to the initiator. The ratio of the inhibitor is about 0.40 or more, preferably about 0.50 or more when normalized to 100% activity. Initiators are typically present in amounts of about 0.25 phr to about 5.0 phr under 100% activity, and antioxidants are present in amounts of about 0.2 phr to about 1 phr.

In one example of this technical feature, the hardness of the first outer surface is 55 shore C to 80 shore C, the hardness of the geometric center is 45 shore C to 62 shore C, and the magnitude of the positive gradient is 10. From 20. In other examples, the hardness of the second outer surface is 58 shore C to 82 shore C, the hardness of the inner surface is 62 shore C to 89 shore C, and the magnitude of the negative gradient is from about 0 to-. It is 10. Preferably, the outer diameter of the inner core is 0.75 "to 1.4" and the outer diameter of the outer core layer is 1.5 "to 1.59". In a specifically preferred embodiment, the cover layer has an inner cover layer and an outer cover layer. Generally, the inner and outer core layers are made from a diene rubber composition and optionally include softening and accelerating agents (soft and fasting agents).

This technical feature is also an inner core, including a first outer surface and geometric center, and is substantially uniform throughout so that its hardness is in the range of 60 shore C to 90 shore C. It is aimed at golf balls, including those manufactured from the first formulation. The outer core layer is formed around the inner core layer and has a second outer and inner surface, which is substantially uniform throughout so that its hardness is in the range of 45 shore C to 70 shore C. Manufactured from the second formulation. The cover layer is arranged around the outer core layer, and this cover layer has one or more layers. The hardness of the first outer surface is greater than the hardness of the geometric center to form a "positive hardness gradient", and the hardness of the second outer surface is substantially equal to or less than the hardness of the inner surface. A "negative hardness gradient" is formed.

The inner core contains a metal salt of carboxylic acid in an amount of about 25 phr to about 35 phr, and the outer core layer contains a metal salt of carboxylic acid in an amount of about 10 phr to about 25 phr, and the oxidation of the outer core layer to the initiator. The ratio of the inhibitor is about 0.50 or less, preferably about 0.40 or less when normalized to 100% activity. Initiators are typically present in amounts of about 0.25 phr to about 5.0 phr under 100% activity, and antioxidants are present in amounts of about 0.2 phr to about 1 phr.

In one example of this technical feature, the hardness of the first outer surface is 65 shore C to 85 shore C, the hardness of the geometric center is 55 shore C to 80 shore C, and the magnitude of the "positive gradient". Is 10 to 20. In another embodiment, the hardness of the second outer surface is 49 shore C to 63 shore C, the hardness of the inner surface is 52 shore C to 68 shore C, and the magnitude of the "negative gradient" is about 0. From -10. Preferably, the outer diameter of the inner core is 0.75 "to 1.4" and the outer diameter of the outer core layer is 1.5 "to 1.59". In a specifically preferred embodiment, the cover layer has an inner cover layer and an outer cover layer. The inner and outer core layers are typically made from a diene rubber composition and optionally include a softening / accelerating agent.

This technical feature is also an inner core, including a first outer surface and geometric center, which is substantially uniform throughout so that its hardness is in the range of 30 shore C to 80 shore C. It is aimed at golf balls, including those manufactured from the first formulation. The outer core layer is formed around the inner core layer and has a second outer and inner surface, which is substantially uniform throughout so that its hardness is in the range of 60 shore C to 90 shore C. Manufactured from the second formulation. A cover layer comprising at least two layers is formed around the outer core layer.

Is the hardness of the first outer surface typically greater than the hardness of the geometric center forming a "positive hardness gradient" and is the hardness of the second outer surface substantially the same as the hardness of the inner surface? , Forming a "negative hardness gradient" smaller than that, and the hardness of the inner surface and the first outer surface is substantially equal to or less than the hardness of the geometric center and the hardness of the second outer surface. large. The inner and outer core layers are typically made from a diene rubber composition and optionally include a softening / accelerating agent.

<figref num="1">It is a graph which shows the hardness of the core according to the distance from the center about the core of the technical feature which concerns on this invention, and the core of a comparative example.</figref><figref num="2">It is a graph which shows the preferable hardness range about the example of "low spin" of the technical feature which concerns on this invention.</figref><figref num="3">FIG. 6 is a graph showing a preferred hardness range for an example of "high spin" of technical features related to the present invention.</figref>

The golf ball of the present invention may include a multi-layer golf ball, eg, a core and a golf ball with a cover surrounding the core, but preferably a solid center (also known as an inner core), and an outer core layer. Manufactured from a core, an inner cover layer, and an outer cover layer. Of course, either the core and / or the cover layer may include multiple layers. In a preferred embodiment, the core is manufactured from the inner and outer cores, and the inner and outer core layers are the innermost part of each element from the outer surface (ie, the center of the inner core or the inner surface of the outer core layer). Although there is a "soft to hard" hardness gradient ("negative" hardness gradient) inward in the radial direction, alternative examples can be envisioned in which the direction or combination of hardness gradients between the core elements is changed. (For example, a "negative" gradient in the center, but a "positive" gradient in the outer core layer, or vice versa).

The center of the core may be a liquid-filled or hollow sphere surrounded by one or more intermediate and / or cover layers, or a solid or liquid around which a tensioned elastic material is wrapped. It may be a center. Any layer arranged around these alternative centers may be accompanied by a hardness gradient (ie, "negative") of the core of the present invention. The cover layer may be formed from a single layer or, for example, a plurality of layers, specifically an inner cover layer and an outer cover layer.

As briefly discussed earlier, in the core of the present invention, the hardness gradient is a hardness measurement on the surface of the inner core (or outer core layer), and radial to the center of the inner core, typically 2 mm. Defined by hardness measurements made in increments of. As used herein, the terms "negative" and "positive" are the innermost parts of the element being measured (eg, the center of the inner core in a solid or double core structure; the inner surface of the core layer; etc. ) Is subtracted from the hardness value of the outer surface of the element to be measured (eg, the outer surface of the solid core; the outer surface of the inner core in the double core; the outer surface of the outer core layer in the double core, etc.). Refers to the result. For example, if the hardness value of the outer surface of a solid core is less than the center (ie, the surface is softer than the center), the hardness gradient is considered a "negative" gradient (small number-large number = negative number). The core of the present invention preferably has a zero or negative hardness gradient, more preferably between zero (0) and -10, and most preferably between 0 and -5.

Preferably, the core layer (inner core or outer core layer) is made from a composition comprising at least one thermosetting base rubber, eg, a polybutadiene rubber, which is at least one peroxide and at least one reactive. Hardened by a coagent, which may be a metal salt of an unsaturated carboxylic acid, such as acrylic acid or methacrylic acid, a non-metallic coagent, or a mixture thereof. Preferably, a suitable antioxidant is included in the composition. Optional softening and accelerating agents (and often cis-to-trans catalysts), such as organic sulfur or metal-containing organic sulfur or rods, may also be included in the core formulation.

Other inclusions known to those of skill in the art may be used, including but not limited to density adjusting fillers, treatment aids, plasticizers, foaming agents or foaming agents, sulfur accelerators, and / or non-peroxides. It can be understood that it includes a physical radical source.

The thermosetting rubber of the base may be blended with other rubbers and polymers and typically includes natural or synthetic rubbers. A preferred base rubber is 1,4-polybutadiene with at least 40%, preferably more than 80%, and even more preferably more than 90% cis structure.

Examples of desired polybutadiene rubbers are BUNA CB22 and BUNA CB23 commercially available from LANXESS; UBEPOL 360L and UBEPOL 360L commercially available from UBE Industry in Tokyo, Japan. UBEPOL 150L and UBEPOL-BR Rubber; KINEX 7245, available from Goodyear in Akron, Ohio; SE BR-1220 and TAKTENE 1203G1, 220, commercially available from Dow Chemical. And 221; Europrene NEOCIS BR40 and BR60; commercially available from Polimeri Europa; and BR 01, BR 730, BR 11, and BR 51; commercially available from Japan Synthetic Rubber. Includes PETROFLEX BRNd-40; and KABOCHEM ND40, ND45, and ND60 commercially available from Karbochem.

The base rubber may have a Mooney viscous or medium viscosity rubber, or a blend thereof. The "Moony" unit refers to the unit used to measure the plasticity of raw or non-vulcanized rubber. Mooney unit plasticity is equal to the torque applied to a disc in a container that contains rubber at a temperature of 100 ° C and rotates twice a minute, measured on any scale. Measurements of Mooney viscosity are specified in ASTM D-1646.

The range of Mooney viscosity is preferably greater than about 40, more preferably in the range of about 40 to about 80, and even more preferably in the range of about 40 to about 60. Polybutadiene rubber having a higher Mooney viscosity may be used. However, the condition is that the viscosity of polybutadiene does not reach a level at which high-viscosity polybutadiene is clogged or other adverse effects on the manufacturing machine. It can be understood that polybutadiene having a viscosity of less than 65 Mooney can be adopted in this invention.

In one embodiment of the invention, a golf ball core made of a polybutadiene material from medium to high Mooney viscosity achieves great elasticity (and therefore a large distance) without increasing the hardness of the ball. Such cores are soft, i.e. compression is less than about 60, more specifically in the range of about 50-55. Cores with compressions in the range of about 30 to about 50 are also within the range of such preferred embodiments.

Commercial resources for suitable medium or high Mooney viscosity polybutadienes include Bayer AG CB23 (Nd catalyst) and Shell 1220 (cocatalyst), the former with a Mooney viscosity of around 50 and a linear vegetable polybutadiene in hardness. Is. When desired, the polybutadiene may be mixed with other elastomers known in the art, such as other polybutadiene rubbers, natural rubbers, styrene butadiene rubbers, and / or isoprene rubbers to modify the properties of the core. When using a mixture of elastomers, the amount of other components in the core composition is typically based on 100 parts by weight of the total amount of the elastomeric mixture.

In one example, the base rubber has Nd-catalyzed polybutadiene, rare earth-catalyzed polybutadiene rubber, or a blend thereof. When desired, the polybutadiene may be mixed with other elastomers known in the art, such as natural rubber, polyisoprene rubber, and / or styrene butadiene rubber to modify the properties of the core. Other suitable base rubbers include thermocurable materials such as ethylene propylene diene monomer rubber, ethylene propylene rubber, butyl rubber, halobutyl rubber, hydrogenated nitrile butadiene rubber, nitrile rubber, and silicone rubber.

The thermoplastic elastomer (TPE) may be mixed with the base thermosetting rubber to modify the properties of the core layer or uncured core layer stock. These PTEs can be natural or synthetic rubber, or high trans-polyisoprene, high trans-polybutadiene, or any styrene block copolymers such as styrene ethylene butadiene styrene, styrene-isoprene-styrene, metallocene or other single site catalytic polyolefins. Includes, for example, styrene-octene, or ethylene-butene, or thermoplastic polyurethane (TPU), which includes, for example, a copolymer with silicone. Other TPEs suitable for mixing with thermosetting rubbers of the present invention are believed to have polyetheramide copolymers, PEBAX , polyether ester copolymers, thermoplastic urethanes, HYTEL®. ), And KRATON , which is believed to have a styrene block copolymer elastomer. Both of the TPEs and TPUs mentioned above contain functional groups suitable for grafting and contain maleic acid or maleic anhydride.

An additional polymer may be optionally incorporated into the base rubber. Such examples are not limited to, but are not limited to, thermocurable elastomers such as core riglind, thermoplastic vultures, copolymerized ionomers, terpolymeric ionomers, polycarbonates, polyamides, copolymerized polyamides, polyesters, polyvinyl alcohols, acrylonitrile-butadiene-. Styrene copolymer, polyarylate, polyacrylate, polyphenylene ether, collision-modified polyphenylene ether, high-impact polystyrene, diallyl phthalate polymer, styrene-acrylonitrile polymer (SAN) (including olefin-modified SAN and acrylonitrile-styrene-acrylonitrile polymer) , Styrene-maleic acid anhydride copolymer, styrene copolymer, functional styrene copolymer, functional styrene terpolymer, styrene terpolymer, cellulose polymer, liquid crystal polymer, ethylene-vinyl acetate copolymer, polyurea, and polysiloxane or metalrosene of these kinds. It is a catalytic polymer.

Polyamides suitable for use as additional polymeric materials for compositions within the scope of the present invention include resins obtained as follows. As (1), (a) dicarboxylic acid such as oxalic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, or 1,4-cyclohexanedicarboxylic acid is (b) diamine such as ethylenediamine, tetraethylenediamine, pentamethylenediamine, hexamethylene. Concentrate with diamine, or decamethylenediamine, 1,4-cyclohexamethylenediamine or m-xylylenediamine. As (2), ring-opening polymerization of cyclic lactam, for example, epsilon caproactam or omega laurolactam. As (3), aminocarboxylic acid such as 6-aminocaproic acid, 9-aminocaproic acid, 11-aminocaproic acid or 12-aminocaproic acid is polymerized. Alternatively, as (4), the cyclic lactam is copolymerized with a dicarboxylic acid and a diamine. Specific examples of suitable polyamides are NYLON6, NYLON66, NYLON610, NYLON11, NYLON12, copolymers NYLON, NYLONMXD6 and NYLON46.

Suitable peroxide initiators are dicumyl peroxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; 2,5-dimethyl-2,5-di (t-butylperoxy) hexin. 2,5-dimethyl-2,5-di (benzoylperoxy) hexane; 2,2'-bis (t-butylperoxy) -di-iso-propylbenzene; 1,1-bis (t-butylperoxy)- 3,3,5-trimethylcyclohexane; n-butyl-4,4-bis (t-butylperoxy) valerate; t-butylperbenzoate; benzoyl peroxide; n-butyl-4,4'-bis (butylperoxy) valerate Di-t-butyl peroxide; or 2,5-di- (t-butylperoxy) -2,5-dimethylhexane, lauryl peroxide, t-butyl hydroperoxide, α-α bis (t-butylperoxy) diisopro Includes propylbenzene, di (2-t butyl-peroxyisopropyl) benzene and di-t-butyl peroxide. Preferably, the rubber composition comprises from about 0.25 to about 5.0 parts by weight (phr) of peroxide per 100 parts by weight of rubber, more preferably from 0.5 phr to 3 phr, most preferably from 0.5 phr to 1.5 phr. Contains oxides. In the most preferred embodiment, the peroxide is about 0. There are only 8phrs. These ranges of peroxides are given under the assumption that the peroxides are 100% active and do not consider any carriers that may be present. Since many commercially available peroxides are sold with carrier compounds, the actual abundance of active peroxide must be calculated. Commercially available peroxide initiators are the DICUP family of dicumyl peroxides (DICUP R, DICUP 40C and DICUP 40KE) available from Cropton (Geo Specialty Chemicals). )including. Similar initiators are available from AkroChem, Laxess, Flexsys / Haewick, and RT Vanderbilt. Another commercially available and preferred initiator is TRIGONOX 265-50B from Akzo Nobel, which is 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, and Di (2-t-butylperoxyisopropyl) benzene. TRIGONOX peroxides are sold with carrier compounds.

Suitable reactive coagents include, but are not limited to, metal salts of diacrylate, dimethacrylate, and monomethacrylate, and suitable for use in the present invention are metals such as zinc, manganese, calcium, barium. It is tin, aluminum, lithium, sodium, potassium, iron, zirconium, and bismuth. Although zinc diacrylate (ZDA) is preferred, the invention is not limited thereto. ZDA gives the golf ball a large initial velocity. DZA may be of various purity grades. In order to realize the object of the present invention, the smaller the amount of zinc stearate present in ZDA, the higher the ZDA purity. ZDA containing less than about 10% zinc stearate is preferred. Further preferred is ZDA, which contains only about 4-8% zinc stearate. Suitable commercially available zinc diacrylates include those available from Sartmer. The preferred concentration of ZDA available is from about 10 phr to about 40 phr, more preferably from about 20 phr to about 35 phr, and most preferably from about 25 phr to about 35 phr. In a specific preferred embodiment, the reactive coagent is present in an amount of about 29 phr to about 31 phr.

Additional preferred coagents that may be utilized alone or in combination with those described above include, but are not limited to, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and the like. Those skilled in the art will appreciate that when the coagent is liquid at room temperature, it is advantageous to disperse these compounds on suitable carriers to facilitate integration into the rubber mixture. ..

Antioxidants are compounds that prevent the oxidative destruction of elastomers and / or the reactions facilitated by oxygen radicals. Some exemplary antioxidants available in the present invention include, but are not limited to, quinoline-type antioxidants, amine-type antioxidants, and phenol-type antioxidants. A preferred antioxidant is 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), which is available from RT Vanderbilt as VANOX MBPC. Other polyphenolic antioxidants include VANOX T, VANOX L, VANOX SKT, VANOX SWP, VANOX 13, and VANOX 1290.

Suitable antioxidants are, but are not limited to, alkylene-bis-alkyl substituted cresols such as 4,4'-methylene-bis (2,5-xylenol); 4,4'-ethylidene-bis- (6- Ethyl-m-cresol); 4,4'-butylidene-bis- (6-t-butyl-m-cresol); 4,4'-decylidene-bis- (6-methyl-m-cresol); 4,4 '-Methylene-bis- (2-amyl-m-cresol); 4,4'-propylidene-bis- (5-hexyl-m-cresol); 3,3'-decylidene-bis- (5-ethyl-p) -Cresol); 2,2'-butylidene-bis- (3-n-hexyl-p-cresol); 4,4'-(2-butylidene) -bis- (6-t-butyl-m-cresol); 3,3'-4 (decylidene) -bis- (5-ethyl-p-cresol); (2,5-dimethyl-4-hydroxyphenyl) (2-hydroxy-3,5-dimethylphenyl) methane; (2 -Methyl-4-hydroxy-5-ethylphenyl) (2-ethyl-3-hydroxy-5-methylphenyl) methane; (3-methyl-5-hydroki-6-t-butylphenyl) (2-hydroxy-4 -Methyl-5-decylphenyl) -n-butylmethane; (2-hydroxy-4-ethyl-5-methylphenyl) (2-decyl-3-hydroxy-4-methylphenyl) butylamylmethane; (3-ethyl- 4-Methyl-5-hydroxyphenyl)-(2,3-dimethyl-3-hydroxy-phenyl) nonylmethane; (3-methyl-2-hydroki-6-ethylphenyl)-(2-isopropyl-3-hydroxy-5) -Methyl-phenyl) cyclohexylmethane; (2-methyl-4-hydroki-5-methylphenyl) (2-hydroxy-3-methyl-5-ethylphenyl) dicyclohexylmethane; and others.

Other suitable antioxidants are, but are not limited to, substituted phenols such as 2-tart-butyl-4-methoxyphenol; 3-tart-butyl-4-methoxyphenol; 3-tart-octyl-4-. Methoxyphenol; 2-methyl-4-methoxyphenol; 2-stearyl-4-n-butoxyphenol; 3-t-butyl-4-steariloxyphenol; 3-lauryl-4-ethoxyphenol; 2,5-di- t-butyl-4-methoxyphenol; 2-methyl-4-methoxyphenol; 2- (1-methylcyclohexyl) -4-methoxyphenol; 2-t-butyl-4-dodecyloxyphenol; 2- (1-methyl) Benzyl) -4-methoxyphenol; 2-t-octyl-4-methoxyphenol; methyl gallate; n-propyl gallate; n-butyl gallate; lauryl gallate; myristyl gallate; stearyl gallate; 2,4,5-trihydroxyacet Phenol; 2,4,5-trihydroxy-n-butyrophenol; 2,4,5-trihydroxystearophenol; 2,6-ditat-butyl-4-methylphenol; 2,6-ditate-oxyl- 4-Methylphenol; 2,6-Ditate-Butyl-4-stearylphenol; 2-Methyl-4-methyl-6-Tart-Butylphenol; 2,6-Distearyl-4-methylphenol; 2,6-Dilauryl- 4-Methylphenol; 2,6-di (n-octyl) -4-methylphenol; 2,6-di (n-hexadecyl) -4-methylphenol; 2,6-di (1-methylundecyl)- 4-Methylphenol; 2,6-di (1-methylheptadecyl) -4-methylphenol; 2,6-di (trimethylhexyl) -4-methylphenol; 2,6-di (1,1,3, 3-Tetramethyloctyl) -4-methylphenol; 2-n-dodecyl-6-tartbutyl-4-methylphenol; 2-n-dodecyl-6- (1-methylundecyl) -4-methylphenol; 2- n-Dodecyl-6- (1,1,3,3-Tetramethyloctyl) -4-methylphenol; 2-n-dodecyl-6-n-octadecyl-4-methylphenol; 2-n-dodecyl-6-n-octyl-4-methylphenol; 2-methyl- 6-n-octadecyl-4-methylphenol; 2-n-dodecyl-6- (1-methylheptadecyl) -4-methylphenol; 2,6-di (1-methylbenzyl) -4-methylphenol; 2 , 6-di (1-methylcyclohexyl) -4-methylphenol; 2,6- (1-methylcyclohexyl) -4-methylphenol; 2- (1-methylbenzyl) -4-methylphenol; and related substitutions Contains phenol.

More suitable antioxidants are, but are not limited to, alkylene bisphenols such as 4,4'-butylidenebis (3-methyl-6-t-butylphenol); 2,2-butylidenebis (4,6-dimethylphenol). 2,2'-butylidenebis (4-methyl-6-t-butylphenol); 2,2'-butylidenebis (4-t-butyl-6-methylphenol); 2,2'-ethylidenebis (4-methyl- 6-t-butylphenol); 2,2'-methylidenebis (4,6-dimethylphenol); 2,2'-methylenebis (4-methyl-6-t-butylphenol); 2,2'-methylenebis (4-ethyl) -6-t-butylphenol); 4,4'-methylenebis (2,6-di-t-butylphenol); 4,4'-ethylenebis (2-methyl-6-t-butylphenol); 4,4'- Methylenebis (2,6-dimethylphenol); 2,2'-Methylenebis (4-t-butyl-6-phenylphenol); 2,2'-Dihydroxy-3,3', 5,5'-Tetramethylstilben; 2,2'-Isopropylidenebis (4-methyl-6-t-butylphenol); ethylenebis (beta-naphthol); 1,5-hydroxynaphthalene; 2,2'-ethylenebis (4-methyl-6-propyl) Phenol); 4,4'-methylenebis (2-propyl-6-t-butylphenol); 4,4'-ethylenebis (2-methyl-6-propylphenol); 2,2'-methylenebis (5-methyl-) 6-t-butylphenol); and 4,4'-butylidenebis (6-t-butyl-3-methylphenol).

Suitable antioxidants are further, but not limited to, alkylenetriphenols such as 2,6-bis (2'-hydroxy-3'-t-butyl-5'-methylbenzyl) -4-methylphenol. 2,6-bis (2'-hydroxy-3'-t-ethyl-5'-butylbenzyl) -4-methylphenol; and 2,6-bis (2'-hydroxy-3'-t-butyl- Contains 5'-mepropylbenzyl) -4-methylphenol.

Antioxidants are typically present in an amount of about 0.1 phr to about 5 phr, preferably in an amount of about 0.1 to about 2 phr, and even more preferably in an amount of about 0.1 to about 1 phr. In a specific preferred embodiment, the antioxidant is present in an amount of about 0.4 phr.

In an alternative embodiment, the amount of antioxidant must be present in an amount that ensures that the hardness gradient of the core of the present invention is negative. Preferably, the antioxidant is a formulation of the core layer (inner core or outer core layer) of about 0.2 phr to about 1 phr, more preferably about 0.3 phr to about 0.8 phr, most preferably about 0.4 phr to about 0.7 phr. Is added to. Preferably, when calculated as 100% activity, about 0.25 phr to about 1.5 phr of peroxide may be added to the core formulation, more preferably from about 0.5 phr to about 1.2 phr, most preferably from about 0.7. About 1.0 phr may be added from phr. The amount of ZDA may vary to suit the desired compression, spin and feel of the golf ball produced. Curing curing involves a temperature range of about 290 ° F (143 ° C) to about 335 ° F (168 ° C), more preferably about 300 ° F (149 ° C) to about 325 ° F (163 ° C). The stock is kept at that temperature for at least about 10 to about 30 minutes.

The thermosetting composition of the present invention may include an optional softening / accelerating agent. "Soft and fast" as used here The agent) should 1) make the core softer (smaller compression) under a constant COR, or 2) have a larger COR with equal compression, compared to when prepared without a softening / accelerating agent. Means any compound or blend thereof, or any combination thereof. Preferably, the composition of the present invention contains from about 0.05 phr to about 10.0 phr of a softening / accelerating agent. In one example, the softening / accelerating agent is present in the range of about 0.05 phr to about 3.0 pr, preferably about 0.05 phr to about 2.0 phr, more preferably about 0.05 phr to about 1.0 phr. In other examples, the softening / accelerating agent is present in the range of about 2.0 phr to about 5.0 pr, preferably about 2.35 phr to about 4.0 phr, more preferably about 2.35 phr to about 3.0 phr. In alternative high concentration examples, the softening / accelerating agent is present in the range of about 5.0 phr to about 10.0 pr, more preferably about 6.0 phr to about 9.0 phr, most preferably about 7.0 phr to about 8.0 phr. To do. In the most preferred embodiment, the softening / accelerating agent is present in an amount of about 2.6 phr.

Suitable softening and accelerating agents include, but are not limited to, organic sulfur or metal-containing organic sulfur compounds, inorganic sulfur compounds, Group VIA compounds, or mixtures thereof, and organic sulfur compounds are mono, di, and , And polysulfides, thiols, or mercapto compounds. The softening / accelerating agent compound may be a blend of an organic sulfur compound and an inorganic sulfur compound.

Appropriate softening / accelerating agents of the present invention include, but are not limited to, those having the following general formulas.<chemistry num="1"><img id="000002" he="26" wi="147" file="JP6068552B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

In the formula, R₁~ R₅Can be in any order, C₁~ C₈And these zinc salts. Preferably the halogenated organosulfur compound is pentachlorothiophenol, which is available on the market in pure form or is a sulfur compound with 45% pentachlorothiophenol added (corresponding to 2.4 parts of PCTP). It is available under the trade name of STRUKTOL®, a clay-based carrier that contains. STRUKTOL is commercially available from the Struktol Company of America in Stowe, Ohio. PCTP is commercially available in pure form from eChinachem in San Francisco, California, and in salt form from eChinachem in San Francisco. Most preferably, the halogenated organosulfur compound is a zinc salt of pentachlorothiophenol, which is commercially available from eChinachem in San Francisco.

As used herein in reference to the present invention, the term "organosulfur compound" refers to any compound containing carbon, hydrogen and sulfur, where sulfur is directly on at least one carbon. Combine with. As used herein, the term "sulfur compound" means a compound that is an elemental sulfur, a polymeric sulfur, or a combination thereof. Furthermore, "elemental sulfur" is S₈It should be understood that the "polymeric sulfur" is a structure containing at least one additional sulfur with respect to the elemental sulfur.

5-dibromophenyl) disulfide; bis (3,5-dibromophenyl) disulfide; bis (2-chloro-5-bromophenyl) disulfide; bis (2,4,6-trichlorophenyl) disulfide; bis (2,3, 4,5,6-pentachlorophenyl) disulfide; bis (4-cyanophenyl) disulfide; bis (2-cyanophenyl) disulfide; bis (4-nitrophenyl) disulfide; bis (2-nitrophenyl) disulfide; 2,2 '-Dithiobenzoic ethyl; 2,2'-dithiobenzoic methyl; 2,2'-dithiobenzoic acid; 4,4'-dithiobenzoic ethyl; bis (4-acetylphenyl) disulfide; bis (2-acetyl) Phenyl) disulfide; bis (4-formylphenyl) disulfide; bis (4-carbamoylphenyl) disulfide; 1,1'-dinaphthyl disulfide; 2,2'-dynaphthyl disulfide; 1,2'-dynaphthyl disulfide; 2 , 2'-bis (1-chlorodinaphthyl) disulfide; 2,2'-bis (1-bromonaphthyl) disulfide; 1,1'-bis (2-chloronaphthyl) disulfide; 2,2'-bis (1) There are -cyanonaphthyl) disulfides; 2,2'-bis (1-acetylnaphthyl) disulfides, etc .; or mixtures thereof. Preferred organic sulfur compounds are diphenyl disulfide, 4,4'-ditril disulfide, or 2,2'-benzamide diphenyl disulfide, or mixtures thereof. A more preferred organic sulfur compound is 4,4'-ditrildisulfide. In other examples, metal-containing organic sulfur compounds may be used according to the present invention. Suitable metal-containing organosulfur compounds are, but are not limited to, cadmium, copper, lead, and tellurium analogs of diethyldithiocarbamate, diamyldithiocarbamate, and dimethyldithiocarbamate, or mixtures thereof. Bis (2-chloro-5-bromophenyl) disulfide; bis (2,4,6-trichlorophenyl) disulfide; bis (2,3,4,5,6-pentachlorophenyl) disulfide; bis (4-cyanophenyl) Disulfide; bis (2-cyanophenyl) disulfide; bis (4-nitrophenyl) disulfide; bis (2-nitrophenyl) disulfide; 2,2'-dithiobenzoic ethyl; 2,2'-dithiobenzoic methyl; 2 , 2'-dithiobenzoic acid; 4,4'-dithiobenzoic ethyl; bis (4-acetylphenyl) disulfide; bis (2-acetylphenyl) disulfide; bis (4-formylphenyl) disulfide; bis (4-carbamoyl) Phenyl) disulfide; 1,1'-dinaphthyl disulfide; 2,2'-dinaphthyl disulfide; 1,2'-dinaphthyl disulfide; 2,2'-bis (1-chlorodinaphthyl) disulfide; 2,2' -Bis (1-bromonaphthyl) disulfide; 1,1'-bis (2-chloronaphthyl) disulfide; 2,2'-bis (1-cyanonaphthyl) disulfide; 2,2'-bis (1-acetylnaphthyl) There are; or mixtures thereof, such as disulfides. Preferred organic sulfur compounds are diphenyl disulfide, 4,4'-ditril disulfide, or 2,2'-benzamide diphenyl disulfide, or mixtures thereof. A more preferred organic sulfur compound is 4,4'-ditrildisulfide. In other examples, metal-containing organic sulfur compounds may be used according to the present invention. Suitable metal-containing organosulfur compounds are, but are not limited to, diethyldithiocarbamate, diamyldithiocarbamate, and cadmium, copper, lead, and tellurium analogs of dimethyldithiocarbamate, or mixtures thereof. Bis (2-chloro-5-bromophenyl) disulfide; bis (2,4,6-trichlorophenyl) disulfide; bis (2,3,4,5,6-pentachlorophenyl) disulfide; bis (4-cyanophenyl) Disulfide; bis (2-cyanophenyl) disulfide; bis (4-nitrophenyl) disulfide; bis (2-nitrophenyl) disulfide; 2,2'-dithiobenzoic ethyl; 2,2'-dithiobenzoic methyl; 2 , 2'-dithiobenzoic acid; 4,4'-dithiobenzoic ethyl; bis (4-acetylphenyl) disulfide; bis (2-acetylphenyl) disulfide; bis (4-formylphenyl) disulfide; bis (4-carbamoyl) Phenyl) disulfide; 1,1'-dinaphthyl disulfide; 2,2'-dinaphthyl disulfide; 1,2'-dinaphthyl disulfide; 2,2'-bis (1-chlorodinaphthyl) disulfide; 2,2' -Bis (1-bromonaphthyl) disulfide; 1,1'-bis (2-chloronaphthyl) disulfide; 2,2'-bis (1-cyanonaphthyl) disulfide; 2,2'-bis (1-acetylnaphthyl) There are; or mixtures thereof, such as disulfides. Preferred organic sulfur compounds are diphenyl disulfide, 4,4'-ditril disulfide, or 2,2'-benzamide diphenyl disulfide, or mixtures thereof. A more preferred organic sulfur compound is 4,4'-ditrildisulfide. In other examples, metal-containing organic sulfur compounds may be used according to the present invention. Suitable metal-containing organosulfur compounds are, but are not limited to, diethyldithiocarbamate, diamyldithiocarbamate, and cadmium, copper, lead, and tellurium analogs of dimethyldithiocarbamate, or mixtures thereof. Bis (2-cyanophenyl) disulfide; Bis (4-nitrophenyl) disulfide; Bis (2-nitrophenyl) disulfide; 2,2'-dithiobenzoic ethyl; 2,2'-dithiobenzoic methyl; 2,2 '-Dithiobenzoic acid; 4,4'-Dithiobenzoic ethyl; bis (4-acetylphenyl) disulfide; bis (2-acetylphenyl) disulfide; bis (4-formylphenyl) disulfide; bis (4-carbamoylphenyl) Disulfide; 1,1'-Dinaphthyl disulfide; 2,2'-Dinaphthyl disulfide; 1,2'-Dinaphthyl disulfide; 2,2'-bis (1-chlorodinaphthyl) disulfide; 2,2'-bis (1-Bromonaphthyl) disulfide; 1,1'-bis (2-chloronaphthyl) disulfide; 2,2'-bis (1-cyanonaphthyl) disulfide; 2,2'-bis (1-acetylnaphthyl) disulfide, etc. Of; or a mixture of these. Preferred organic sulfur compounds are diphenyl disulfide, 4,4'-ditril disulfide, or 2,2'-benzamide diphenyl disulfide, or mixtures thereof. A more preferred organic sulfur compound is 4,4'-ditrildisulfide. In other examples, metal-containing organic sulfur compounds may be used according to the present invention. Suitable metal-containing organosulfur compounds are, but are not limited to, diethyldithiocarbamate, diamyldithiocarbamate, and cadmium, copper, lead, and tellurium analogs of dimethyldithiocarbamate, or mixtures thereof. Bis (2-cyanophenyl) disulfide; Bis (4-nitrophenyl) disulfide; Bis (2-nitrophenyl) disulfide; 2,2'-dithiobenzoic ethyl; 2,2'-dithiobenzoic methyl; 2,2 '-Dithiobenzoic acid; 4,4'-Dithiobenzoic ethyl; bis (4-acetylphenyl) disulfide; bis (2-acetylphenyl) disulfide; bis (4-formylphenyl) disulfide; bis (4-carbamoylphenyl) Disulfide; 1,1'-Dinaphthyl disulfide; 2,2'-Dinaphthyl disulfide; 1,2'-Dinaphthyl disulfide; 2,2'-bis (1-chlorodinaphthyl) disulfide; 2,2'-bis (1-Bromonaphthyl) disulfide; 1,1'-bis (2-chloronaphthyl) disulfide; 2,2'-bis (1-cyanonaphthyl) disulfide; 2,2'-bis (1-acetylnaphthyl) disulfide, etc. Of; or a mixture of these. Preferred organic sulfur compounds are diphenyl disulfide, 4,4'-ditril disulfide, or 2,2'-benzamide diphenyl disulfide, or mixtures thereof. A more preferred organic sulfur compound is 4,4'-ditrildisulfide. In other examples, metal-containing organic sulfur compounds may be used according to the present invention. Suitable metal-containing organosulfur compounds are, but are not limited to, cadmium, copper, lead, and tellurium analogs of diethyldithiocarbamate, diamyldithiocarbamate, and dimethyldithiocarbamate, or mixtures thereof. Bis (4-carbamoylphenyl) disulfide; 1,1'-dinaphthyl disulfide; 2,2'-dinaphthyl disulfide; 1,2'-dinaphthyl disulfide; 2,2'-bis (1-chlorodinaphthyl) disulfide 2,2'-bis (1-bromonaphthyl) disulfide; 1,1'-bis (2-chloronaphthyl) disulfide; 2,2'-bis (1-cyanonaphthyl) disulfide; 2,2'-bis ( There are 1-acetylnaphthyl) disulfides and the like; or mixtures thereof. Preferred organic sulfur compounds are diphenyl disulfide, 4,4'-ditril disulfide, or 2,2'-benzamide diphenyl disulfide, or mixtures thereof. A more preferred organic sulfur compound is 4,4'-ditrildisulfide. In other examples, metal-containing organic sulfur compounds may be used according to the present invention. Suitable metal-containing organosulfur compounds are, but are not limited to, diethyldithiocarbamate, diamyldithiocarbamate, and cadmium, copper, lead, and tellurium analogs of dimethyldithiocarbamate, or mixtures thereof. Bis (4-carbamoylphenyl) disulfide; 1,1'-dinaphthyl disulfide; 2,2'-dinaphthyl disulfide; 1,2'-dinaphthyl disulfide; 2,2'-bis (1-chlorodinaphthyl) disulfide 2,2'-bis (1-bromonaphthyl) disulfide; 1,1'-bis (2-chloronaphthyl) disulfide; 2,2'-bis (1-cyanonaphthyl) disulfide; 2,2'-bis ( There are 1-acetylnaphthyl) disulfides and the like; or mixtures thereof. Preferred organic sulfur compounds are diphenyl disulfide, 4,4'-ditril disulfide, or 2,2'-benzamide diphenyl disulfide, or mixtures thereof. A more preferred organic sulfur compound is 4,4'-ditrildisulfide. In other examples, metal-containing organic sulfur compounds may be used according to the present invention. Suitable metal-containing organosulfur compounds are, but are not limited to, diethyldithiocarbamate, diamyldithiocarbamate, and cadmium, copper, lead, and tellurium analogs of dimethyldithiocarbamate, or mixtures thereof. It is 4'-ditril disulfide. In other examples, metal-containing organic sulfur compounds may be used according to the present invention. Suitable metal-containing organosulfur compounds are, but are not limited to, diethyldithiocarbamate, diamyldithiocarbamate, and cadmium, copper, lead, and tellurium analogs of dimethyldithiocarbamate, or mixtures thereof. It is 4'-ditril disulfide. In other examples, metal-containing organic sulfur compounds may be used according to the present invention. Suitable metal-containing organosulfur compounds are, but are not limited to, cadmium, copper, lead, and tellurium analogs of diethyldithiocarbamate, diamyldithiocarbamate, and dimethyldithiocarbamate, or mixtures thereof.

Suitable substituted or unsubstituted aromatic organic components containing no sulfur or metal include, but are not limited to, 4,4'-diphenylacetylene, azobenzene, or mixtures thereof. The aromatic organic group is preferably C in its size.₆~ C₂₀Is in the range, and more preferably C₆~ C₁₀It is in the range of Suitable inorganic sulfide components include, but are limited to, titanium sulfide, manganese sulfide, and similar sulfides of iron, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, tin, and bismuth. Not done.

Substituted or unsubstituted aromatic organic compounds are also softening / accelerating agents. Suitable substituted or unsubstituted aromatic organic components include, but are not limited to, the formula (R).₁)_x-R₃-MR₄-(R₂)_yThere is a component with, in the formula, R₁And R₂Are hydrogen, or substituted or unsubstituted C, respectively.₁~ C₂₀Linear, branched or cyclic alkyl, alkoxy or alkylthio groups, or monocyclic, polycyclic or condensed ring C₆~ C₂₄It is an aromatic group; x and y are integers from 0 to 5, respectively; R₃And R₄Is a monocyclic, polycyclic or condensed ring C, respectively.₆~ C₂₄Selected from aromatic groups; M is an azo group or metallic component. R₃And R₄Are each preferably C₆~ C₁₀It is selected from aromatic groups, more preferably from phenyl, benzyl, naphthyl, benzamide and benzothiazil. R₁And R₂Are preferably substituted or unsubstituted C, respectively.₁~ C₁₀Linear, branched or cyclic alkyl, alkoxy or alkylthio groups, or C₆~ C₁₀Selected from aromatic groups. R₁, R₂, R₃Or R₄Where is substituted, the substituents can be one or more of the following substituents: hydroxy and its metal salts; mercapto and its metal salts; halogens; amino, nitro, cyano and amides; esters, Carboxyls including acids and metal salts thereof; silyls; acrylates and metal salts thereof; sulfonyls or sulfonamides; and phosphates and phosphites. If M is a metallic component, M can be any suitable elemental metal available to those skilled in the art. Typically, the metal is a transition metal, preferably tellurium or selenium. It can be included in the cis-trans-conversion catalyst. In one example, the aromatic organic compound is substantially free of metal, while in the other embodiment, the aromatic organic compound is completely metal free.

The softening / accelerating agent can also contain Group VIA components. Elemental sulfur and polymer sulfur are commercially available, for example, from Elastochem, Chardon, Ohio. Examples of sulfur-catalyzed compounds include PB (RM-S) -80 elemental sulfur and PB (CRST) -65 polymer sulfur, each of which is available from Elastochem. An example of a tellurium catalyst with the trade name "TELLOY" and an example of a selenium catalyst with the trade name "VANDEX" are available commercially from RT Vanderbilt.

Other suitable softening and accelerating agents include, but are not limited to, hydroquinone, benzoquinone, quinhydrone, catechol, and resorcinol.

The hydroquinone compound is selected from the compounds represented by the following chemical formulas and their hydrates.<chemistry num="2"><img id="000003" he="24" wi="129" file="JP6068552B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

Where R₁, R₂, R₃And R₄Each of hydrogen; halogen; alkyl; carboxyl; its metal salt and its ester; acetate and its ester; formyl; acyl; acetyl group; halide carbonyl; sulfo and its ester; halogenated sulfonyl; sulfino; alkyl sulfinyl; carbamoyl Haloalkanes; cyano; alkoxy; hydroxy and metal salts thereof; amino; nitro; aryl; aryloxy; arylalkyl; nitroso; acetamide; or vinyl.

Examples of other suitable hydroquinone compounds are, but are not limited to, hydroquinone; tetrachlorohydroquinone; 2-chlorohydroquinone; 2-bromohydroquinone; 2,5-dichlorohydroquinone; 2,5-dibromohydroquinone; tetrabromohydroquinone; Includes 2-methylhydroquinone; 2-t-butylhydroquinone; 2,5-di-t-amylhydroquinone; and 2- (2-chlorophenyl) hydroquinone hydrate.

More suitable hydroquinone compounds include compounds represented by the following chemical formulas and their hydrates.<chemistry num="3"><img id="000004" he="24" wi="129" file="JP6068552B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

Where R₁, R₂, R₃And R₄Each of these is a metal salt of carboxyl; acetate and its ester; hydroxy; metal salt of hydroxy; amino; nitro; aryl; aryloxy; arylalkyl; nitroso; acetamide; or vinyl.

Suitable benzoquinone compounds include compounds represented by the following chemical formulas and their hydrates.<chemistry num="4"><img id="000005" he="26" wi="135" file="JP6068552B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

Where R₁, R₂, R₃And R₄Each of hydrogen; halogen; alkyl; carboxyl; its metal salt and its ester; acetate and its ester; formyl; acyl; acetyl group; halide carbonyl; sulfo and its ester; halogenated sulfonyl; sulfino; alkyl sulfinyl; carbamoyl Haloalkanes; cyano; alkoxy; hydroxy and metal salts thereof; amino; nitro; aryl; aryloxy; arylalkyl; nitroso; acetamide; or vinyl.

Other suitable benzoquinone compounds include one or more compounds represented by the following chemical formulas and their hydrates.<chemistry num="5"><img id="000006" he="26" wi="135" file="JP6068552B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

Where R₁, R₂, R₃And R₄Each of these is a metal salt of carboxyl; acetate and its ester; hydroxy; metal salt of hydroxy; amino; nitro; aryl; aryloxy; arylalkyl; nitroso; acetamide; or vinyl.

Suitable quinhydrones include one or more compounds represented by the following chemical formulas and their hydrates.<chemistry num="6"><img id="000007" he="25" wi="131" file="JP6068552B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

Where R₁, R₂, R₃, R₄, R₅, R₆, R₇And R₈Each of hydrogen; halogen; alkyl; carboxyl; metal salt of carboxyl and its ester; acetate and its ester; formyl; acyl; acetyl; carbonyl halide; sulfo and its ester; sulfonyl halide; sulfino; alkyl sulfinyl; carbamoyl Haloalkanes; cyano; alkoxy; hydroxy and metal salts thereof; amino; nitro ;, aryl; aryloxy; arylalkyl; nitroso; acetamide; or vinyl.

Other suitable quinhydrones have the chemical formulas described above. However, R₁, R₂, R₃, R₄, R₅, R₆, R₇And R₈Each of these is a metal salt of carboxyl; acetate and its ester; hydroxy; metal salt of hydroxy; amino; nitro; aryl; aryloxy; arylalkyl; nitroso; acetamide; or vinyl.

Suitable catechols include one or more compounds represented by the following chemical formulas and their hydrates.<chemistry num="7"><img id="000008" he="23" wi="138" file="JP6068552B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

Where R₁, R₂, R₃And R₄Each of hydrogen; halogen; alkyl; carboxyl; its metal salt and its ester; acetate and its ester; formyl; acyl; acetyl group; halide carbonyl; sulfo and its ester; halogenated sulfonyl; sulfino; alkyl sulfinyl; carbamoyl Haloalkanes; cyano; alkoxy; hydroxy and metal salts thereof; amino; nitro; aryl; aryloxy; arylalkyl; nitroso; acetamide; or vinyl.

Suitable resorcinols include one or more compounds represented by the following chemical formulas and their hydrates.<chemistry num="8"><img id="000009" he="22" wi="134" file="JP6068552B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

Where R₁, R₂, R₃And R₄Each of hydrogen; halogen; alkyl; carboxyl; its metal salt and its ester; acetate and its ester; formyl; acyl; acetyl group; halide carbonyl; sulfo and its ester; halogenated sulfonyl; sulfino; alkyl sulfinyl; carbamoyl Haloalkanes; cyano; alkoxy; hydroxy and metal salts thereof; amino; nitro; aryl; aryloxy; arylalkyl; nitroso; acetamide; or vinyl.

Fillers may also be added to the thermosetting composition of the core to adjust the density of the composition upwards or downwards. Fillers are typically tungsten, zinc oxide, barium sulphate, silica, calcium carbonate, zinc carbonate, metals, metal oxides and salts, riglind (recycled core material, typically about 30 mesh particles. Includes high Mooney viscosity rubber riglind, trans-riglind core material (recycled core material containing high trans-isomer of polybutadiene) and the like. In the presence of trans-riglind, the amount of trans-isomer is preferably between about 10% and about 60%. In a preferred example of the invention, the core comprises polybutadiene having a cis-isomer with a content content of greater than about 95% and a trans-riglind material (already sulfurized) as a filler. A trans-riglind core material of any particle size is sufficient, but preferably less than about 125 μm.

Fillers added to one or more parts of a golf ball typically include treatment aids or compounds that affect rheological and mixed properties, density adjusting fillers, tear strength or strengthening fillers, and the like. Fillers are generally inorganic and suitable fillers contain a large number of metals or metal oxides, such as zinc oxide and tin oxide, as well as barium sulphate, zinc sulphate, calcium carbonate, barium carbonate, clay, tungsten, tungsten carbide, silica. Includes arrays and mixtures thereof. Fillers can also contain various foaming agents or blowing agents, which can be readily selected by those skilled in the art. The filler may be polymer, ceramic or metal, and the glass microspheres may be solid or hollow and may or may not be filled. Fillers are also typically added to one or more parts of the golf ball to adjust its density to meet uniform golf ball standards. Fillers can also be used to adjust the mass of at least one additional layer for the center or special ball, for example a low mass ball is preferred for players with low swing speeds.

Like tungsten, zinc oxide, barium sulphate, silica, calcium carbonate, zinc carbonate, metals, metal oxides and salts, riglind (recycled core material, typically ground into about 30 mesh particles). The material is also a suitable filler.

Polybutadiene and / or any other base rubber or elastomer system can also be filled with foamed or hollow microspheres or expandable microspheres that expand at a set temperature during the curing process to any low specific gravity level. You can. Other ingredients, such as sulfur accelerators, specifically tetramethylthiuram, di, tri, or tetrasulfide, and / or metal-containing organic sulfur accelerators may be used in accordance with the present invention. Suitable metal-containing organosulfur accelerators include, but are not limited to, diethyldithiocarbamate, diamyldithiocarbamate and dimethyldithiocarbamate or mixtures thereof, including cadmium, copper, lead, and ruthenium analogs. Other ingredients, such as treatment aids, specifically fatty acids and / or metal salts thereof, treatment oils, dyes and pigments, and other additives well known to those of skill in the art, for which they are used by the present invention. May be used in sufficient quantity to achieve.

There are three preferred embodiments defined by the present invention, preferably golf balls containing a "double core", in which both the inner core and the outer core layer are accompanied by a "negative" hardness gradient. , Optional zero gradient. In the first preferred embodiment, the "low spin" embodiment, the inner surface of the outer core layer is harder than the outer surface of the inner core. In the second preferred embodiment, the "high spin" embodiment, the inner surface of the outer core layer is softer than the outer surface of the inner core. In a third preferred embodiment, the hardness of the inner surface of the outer core layer is substantially consistent with the hardness of the outer surface of the inner core, extending from the outer surface of the outer core layer to the center of the inner core, a continuous "negative" Effectively realize the gradient of.

In the "low spin" example, the hardness of the inner core (surface, center, or any other point) is 30 shore C to 80 shore C, more preferably 40 shore C to 75 shore C, most preferably 45. It ranges from Shore C to 70 Shore C. At the same time, the hardness of the outer core layer (surface, inner surface, or any other point) is 60 shore C to 95 shore C, more preferably 60 shore C to 90 shore C, most preferably 65 shore C to 80 shore. It is in the range of C.

In the "high spin" example, the hardness of the inner core ranges from 60 shore C to 95 shore C, more preferably 60 shore C to 90 shore C, most preferably 65 shore C to 80 shore C. At the same time, the hardness of the outer core layer ranges from 30 shore C to 80 shore C, more preferably 40 shore C to 75 shore C, and most preferably 45 shore C to 70 shore C.

The outer core layer and the inner core interface (ie, the area where the two elements meet) are realized for either "low spin" or "high spin" embodiments in embodiments with substantially the same hardness. The range is also sufficient. However, the "negative" hardness gradient must be maintained and the hardness value of the inner surface of the outer core layer must be approximately equal to the hardness value of the outer surface of the inner core.

Representative graphs showing the hardness regions where the "negative" hardness gradients disclosed herein are present are shown in FIGS. 2 and 3. Specifically, as in the above embodiment, the "negative" slope is accompanied by any slope (ie, deep slope, shallow slope, or substantially flatness). In a given embodiment, even if one or more points measured along a "negative" gradient are above or below the gradient and the line that matches the outermost and innermost points. Good. In an alternative preferred embodiment, the hardest point along a specific "negative" gradient is greater than the innermost point of the outer core (geometric center) or the innermost point of the outer core layer (inner surface). May be good. If the outermost point (ie, the outer surface of the inner core) is approximately the same as or smaller than the innermost point (ie, the geometric center of the inner core), the "negative" gradient remains.

There are a number of suitable and alternative "low spin" examples, each of which varies the performance characteristics of a golf ball. In each of the following three examples, the outer diameter of the inner core is preferably about 1.00 inches and the outer diameter of the core (combination of inner and outer core layers) is preferably about 1.53 inches. Any of the cover materials listed above is considered appropriate and may or may not have an inner cover. Preferably, there is an inner cover layer, which consists of an ionomer-based material, such as a hardness-neutralized ionomer, preferably the outer cover is made from a urethane or urea material.

A golf ball with a core manufactured from an inner core and an outer core layer. The hardness of the center of the inner core is about 42 shore C and the hardness of the surface is about 37 shore C, achieving the "negative" hardness gradient of the present invention. The hardness of the inner surface of the outer core layer is about 79 shore C and the hardness of the outer surface is about 73 shore C, again achieving the "negative" hardness gradient of the present invention. The Atti compression of this core is preferably about 60 and the COR is about 0.790. For antioxidants (AOs), the initiator ratio of the inner core is about 0.5 and the ZDA level is about 8-10 phr. For antioxidants, the initiator ratio of the outer core layer is about 0.4 and the ZDA level is about 32-34 hpr. Curing temperatures and times for both the inner and outer core layers are approximately 315 ° F (157 ° C) and 11 minutes.

b. A golf ball with a core manufactured from an inner core and an outer core layer. The hardness of the center of the inner core is about 56 shore C and the hardness of the surface is about 55 shore C, achieving the "negative" hardness gradient of the present invention. The hardness of the inner surface of the outer core layer is about 89 shore C and the hardness of the outer surface is about 82 shore C, again achieving the "negative" hardness gradient of the present invention. The Atti compression of this core is preferably about 70 and the COR is about 0.805. For antioxidants, the initiator ratio of the inner core is about 0.5 and the ZDA level is about 10-12 phr. For antioxidants, the initiator ratio of the outer core layer is about 0.5 and the ZDA level is about 34-36 hpr. Curing temperatures and times for both the inner and outer core layers are approximately 320 ° F (160 ° C) and 11 minutes.

c. A golf ball with a core manufactured from an inner core and an outer core layer. The hardness of the center of the inner core is about 46 shore C and the hardness of the surface is about 44 shore C, achieving the "negative" hardness gradient of the present invention. The hardness of the inner surface of the outer core layer is about 62 shore C and the hardness of the outer surface is about 58 shore C, again achieving the "negative" hardness gradient of the present invention. The Atti compression of this core is preferably about 65 and the COR is about 0.800. For antioxidants, the inner core initiator ratio is about 0.4 and the ZDA level is about 8-10 phr. For antioxidants, the initiator ratio of the outer core layer is about 0.3 and the ZDA level is about 26-28 hpr. Curing temperatures and times for both the inner and outer core layers are approximately 315 ° F (157 ° C) and 11 minutes.

There are a number of suitable and alternative "high spin" examples, each of which variates performance characteristics that differ from the golf ball performance characteristics achieved by the "low spin" embodiment. Similar to the above, in each of the following three examples, the outer diameter of the inner core is preferably about 1.00 inches and the outer diameter of the core (combination of inner and outer core layers) is preferably about 1.53 inches. is there.

A golf ball with a core manufactured from an inner core and an outer core layer. The hardness of the center of the inner core is about 74 shore C and the hardness of the surface is about 71 shore C, achieving the "negative" hardness gradient of the present invention. The hardness of the inner surface of the outer core layer is about 68 shore C and the hardness of the outer surface is about 63 shore C, again achieving the "negative" hardness gradient of the present invention. The Atti compression of this core is preferably about 68 and the COR is about 0.790. For antioxidants, the inner core initiator ratio is about 0.5 and the ZDA level is about 28-30 phr. For antioxidants, the initiator ratio of the outer core layer is about 0.4 and the ZDA level is about 12-14 hpr. The curing temperature and time of the inner core is about 320 ° F (160 ° C) and 14 minutes, and the curing temperature and time of the outer core layer is about 320 ° F (160 ° C) and 11 minutes.

b. A golf ball with a core manufactured from an inner core and an outer core layer. The hardness of the center of the inner core is about 86 shore C and the hardness of the surface is about 83 shore C, achieving the "negative" hardness gradient of the present invention. The hardness of the inner surface of the outer core layer is about 61 shore C and the hardness of the outer surface is about 57 shore C, again achieving the "negative" hardness gradient of the present invention. The Atti compression of this core is preferably about 74 and the COR is about 0.800. For antioxidants, the initiator ratio of the inner core is about 0.4 and the ZDA level is about 33-35 phr. For antioxidants, the initiator ratio of the outer core layer is about 0.5 and the ZDA level is about 11-13 hpr. The curing temperature and time of the inner core is about 320 ° F (160 ° C) and 14 minutes, and the curing temperature and time of the outer core layer is about 315 ° F (157 ° C) and 11 minutes.

c. A golf ball with a core manufactured from an inner core and an outer core layer. The hardness of the center of the inner core is about 65 shore C and the hardness of the surface is about 61 shore C, achieving the "negative" hardness gradient of the present invention. The hardness of the inner surface of the outer core layer is about 52 shore C and the hardness of the outer surface is about 49 shore C, again achieving the "negative" hardness gradient of the present invention. The Atti compression of this core is preferably about 62 and the COR is about 0.785. For antioxidants, the initiator ratio of the inner core is about 0.5 and the ZDA level is about 22-27 phr. For antioxidants, the initiator ratio of the outer core layer is about 0.5 and the ZDA level is about 9-11 hpr. The curing temperature and time of the inner core is about 315 ° F (157 ° C) and 14 minutes, and the curing temperature and time of the outer core layer is about 315 ° F (157 ° C) and 11 minutes.

In alternative embodiments, the outer surface of the inner core has an overall hardness in the range of 55 shore C to 80 shore C, and the geometric center of the inner core has an overall hardness of 45 shore C to 62 shore C. Includes golf balls with a "positive hardness gradient" of size 10 to 20. In this example, the hardness of the outer surface of the outer core layer is in the range of 58 shore C to 82 shore C as a whole, and the hardness of the inner surface of the outer core layer is in the range of 62 shore C to 89 shore C as a whole. The "negative hardness gradient" goes from 0 to -10.

In addition, the outer surface of the inner core has a hardness in the range of 65 shore C to 85 shore C, and the geometric center of the inner core has a hardness of 55 shore C to 80 shore C, with a "positive hardness gradient" of 10 to. It can be as large as 20. In this embodiment, the hardness of the outer surface of the outer core layer is in the range of 49 shore C to 63 shore C as a whole, and the hardness of the inner surface of the outer core layer is in the range of 52 shore C to 68 shore C as a whole. The "negative hardness gradient" goes from 0 to -10.

The above embodiments may be adapted to meet predetermined performance characteristics. For example, alternative embodiments include those having an inner core having an outer diameter of about 0.250 inches to about 1.550 inches, preferably about 0.500 inches to about 1.500 inches, more preferably about 0.750 inches to about 1.400 inches. In a preferred embodiment, the outer diameter of the inner core is about 1.000 inches, 1.200 inches, or 1.300 inches, with the most preferred outer diameter being 1.130 inches. The outer diameter of the outer core layer (total double core) is from about 1.30 inches to about 1.620 inches, preferably from about 1.400 inches to about 1.600 inches, more preferably from about 1.500 inches to about 1.590 inches. In a preferred embodiment, the outer diameter of the outer core layer is about 1.510 inches, 1.530 inches, and most preferably 1.550 inches.

A large number of cores are produced based on the formulation and curing cycles described in Table 1 below, and their core hardness values are reported in Table 2 below and plotted in FIG.<tables num="1"><img id="000010" he="131" wi="148" file="JP6068552B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>(*) VANOX MBPC: 2,2'-methylene-bis- (4-methyl-6-t-butylphenol) available from RT Vanderbilt (**) TRIGONOX 265-50B: 50% active 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane and di (2-t) on inactive carriers available from Akzo Nobel -Butylperoxyisopropyl) Benzene mixture (***) Perkadox BC-FF: Dicumyl peroxide available from Akzo Nobel (99% -100% active) (+) SR-526: ZDA available from Sartomer<tables num="2"><img id="000011" he="90" wi="148" file="JP6068552B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

The surface hardness of the core is taken from the average of a number of measurements taken from the opposing hemispheres of the core, and care is taken not to make measurements on the core's separation lines or surface defects, such as holes or protrusions. Hardness measurements are made according to ASTM D-2240, "Durometer Rubber and Plastic Indentation Hardness". Since the core is curved, it is necessary to handle the core so that it is centered directly below the durometer indenter before the surface hardness can be read. One calibrated digital durometer capable of reading up to 0.1 units was used for all hardness measurements and was set to obtain the hardness reading 1 second after the maximum reading was obtained. The digital durometer must have its legs parallel and mounted on the base of the automatic stand so that the weight and attack speed on the durometer are compatible with ASTM D-2240.

To prepare for the hardness gradient measurement of the core, gently push the core into a hemispherical holder whose internal diameter is slightly smaller than the diameter of the core, and the core is held stationary in the hemispherical part of the holder, while at the same time the geometric center plane of the core. Make it exposed. The core is fixed in the holder by friction to prevent it from moving during the cutting and polishing steps. However, the friction should not be excessive and the natural shape of the core should not be deformed. Fix the core so that the separation line of the core is approximately parallel to the top of the holder. Before fixing the core, measure the diameter of the core at 90 ° to this coordination. It also measures the distance from the bottom of the holder to the top of the core to obtain a reference point for future calibration. Roughly cut with a band saw or other suitable cutting tool, slightly above the exposed geometric center of the core, preventing the core from moving within the holder during this step. The rest of the core, which is still held in the holder, is fixed to the base plate of the surface grinding machine. The exposed "coarse" core surface is polished to a smooth, flat surface to reveal the geometric center of the core, which can be verified by measuring the height from the bottom of the holder to the exposed surface of the core. .. This ensures that exactly half of the core's original height has been removed within the range of + -0.004 inches.

Hold the core in the holder, find the center of the core with a centering ruler, mark it carefully, and measure the hardness with this center mark. Hardness measurements at any distance from the center of the core are made by drawing a line extending radially outward from the center and measuring and marking the distance from the center, typically in increments of 2 mm. When all hardness measurements are performed on a surface passing through the center of geometry, the core is still in the holder, its coordination is not disturbed, and the measurement surface is always parallel to the bottom of the holder. .. The hardness difference from any predetermined point on the core is calculated by subtracting the hardness of the center of the core from the average surface hardness and an appropriate reference point, for example, for a single solid core, and the core surface softer than the center is negative. Have a hardness gradient of.

Referring to Tables 1 and 2, in Example 1, the surface is 10 shore C smaller than the center hardness and 12 shore C smaller than the highest hardness point in the core. In Example 3, the surface is 5 shore C smaller than the center hardness and 8 shore C smaller than the highest hardness point in the core. In Example 2, the hardness values of the center and the surface are equal, and the softest point in the core is 10 shore C smaller than the surface.

In the examples of the invention presented in Table 1, the curing temperature varies from 305 ° F (152 ° C) to 320 ° F (160 ° C) and the curing time varies from 11 to 16 minutes. The core compositions of Example 1 and Example 2 are the same, only the curing cycle is modified. In Example 3, the amount of antioxidant is the same as in Example 1 and Example 2, but the other components and the curing cycle are modified. In addition, the ratio of the antioxidant to the initiator varies from 0.50 to 0.57 in Example 1, Example 2 and Example 3.

The ratio of antioxidant to initiator is one factor that controls the surface hardness of the core. The data shown in Table 2 show that the hardness gradient depends, at least, on the amounts of antioxidants and peroxides, their ratios, and the curing cycle. It should be noted that the higher the amount of antioxidant, the more peroxide initiator is required to achieve the desired compression.

In FIG. 1, the cores of Comparative Examples 1 to 3 are compared with the cores of the present invention. The composition of the core of Comparative Example 1 is shown in Table 1 and was cured using a normal core cycle with a curing temperature of 350 ° F (177 ° C) and a curing time of 11 minutes. The cores of the present invention were manufactured using a curing cycle of 305 ° F (152 ° C), 14 minutes, 315 ° F (157 ° C), 11 minutes. The hardness gradients of these cores are measured and the following observations can be made. For the core of the comparative example, as expected, the usual gradient from the hard surface to the soft center can be clearly found. The gradients of the cores of the present invention have substantially the same shape as each other.

In a preferred embodiment of the present invention, the hardness of the core on the surface is at most about the same as or less than the hardness of the core at the center. Further, the central hardness of the core does not have to be the hardest point in the core, but in all cases it is preferably at least as hard as or harder than the surface. Moreover, it does not have to have the lowest hardness on the surface, either in the core. In some examples, the smallest hardness value is within 6 mm of the core surface. However, as long as the surface hardness is still equal to or less than the center hardness, the smallest hardness value in the core may be at any point from the surface, excluding the surface or center. It should be noted that in the present invention, the formulation is the same throughout the core or core layer and no surface treatment is applied to obtain a favorable surface hardness.

Although the golf ball of the present invention may be made from a variety of different conventional cover materials (both intermediate and outer cover layers), preferred cover materials include, but are not limited to: (1) Prepared from polyurethanes such as polyols or polyamines and diisocyanates or polyisocyanates and / or their prepolymers, and are disclosed in US Pat. Nos. 5,33,4673 and 6,506,851. thing. (2) Polyurea, for example, those disclosed in US Pat. Nos. 5,484,870 and 6,835,794. (3) Polyurethane-urea hybrids, blends or copolymers containing urethane or urea segments. Suitable polyurethane compositions include the reaction product of at least one polyisocyanate and at least one curing agent. The curing agent may include, for example, one or more polyamines, one or more polyols, or a combination thereof. The polyisocyanate may be combined with one or more polyols to form a prepolymer. It is combined with at least one curing agent 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 part of prepolymers and hardeners. Suitable polyurethanes are described in US Patent Application Publication No. 2005/0176526, the contents of which are incorporated herein by reference.

Any polyisocyanate available to those of skill 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").₁₂And mixtures thereof. 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 a mixture thereof, and more preferably the polyisocyanate comprises MDI. As used herein, the term "MDI" means 4,4'-diphenylmethane diisocyanate, polymer MDI, carbodiimide-modified liquid MDI, and mixtures thereof, and the diisocyanate used is a "low free monomer". It should be understood by those skilled in the art that "can be" is an isocyanate group with a low amount of "free" monomer, typically less than about 0.1% of free monomer group. Examples of "low free monomer" diisocyanates are, but are not limited to, low free monomer MDI, low free monomer TDI, and low free monomer PPDI.

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

Any polyol available to those of skill in the art is suitable for use in accordance with the present invention. Examples of polyols are, 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 are, but are not limited to, polytetramethylene ether glycol (PTMEG), polyethylene propylene glycol, polyoxypropylene glycol, and mixtures thereof. Hydrocarbon chains can have saturated or unsaturated bonds and substituted or unsubstituted aromatic and cyclic groups. Preferably, the polyol of the present invention comprises PTMEG.

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

In another example, the polyurethane material of the present invention comprises polycaprolactone polyol. Suitable polycaprolactone polyols are, but are not limited to, 1,6-hexanediol-starting polycaprolactone, diethylene glycol starting polycaprolactone, trimethylolpropane starting polycaprolactone, neopentyl glycol starting polycaprolactone, 1,4-butanediol starting. Polycaprolactone, PTMEG-initiated polycaprolactone, and mixtures thereof. Hydrocarbon chains can have saturated or unsaturated, or substituted or unsubstituted aromatic and cyclic groups.

In yet another embodiment, the polyurethane material of the present invention comprises a polycarbonate polyol. Suitable polycarbonates are, but are not limited to, polyphthalate carbonates and poly (hexamethylene carbonate) glycols. Hydrocarbon chains can have saturated or unsaturated bonds, or substituted or unsubstituted aromatics and cyclic groups. In one example, the molecular weight of the polyol is from about 200 to about 4000.

Polyamine hardeners are also suitable for use in the polyurethane compositions of the present invention and have been found to improve the cutting resistance, shear resistance, and impact resistance of product balls. Preferred polyamine hardeners are, but are not limited to, 3,5-dimethylthio-2,4-toluenediamine and its isomer; 3,5-diethyltoluene-2,4-diamine and this 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'-methylene dianiline ("MDA"); m-phenylenediamine ("MPDA"); 4,4'-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; trimethyleneglycoldi-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 the Albermarle Corporation of Baton Rouge, Inc. of Baton Rouge. Ethacure® 300 available from LA). Suitable polyamine hardeners contain both primary and secondary amines, preferably having a molecular weight in the range of about 64 to about 2000.

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

Both the hydroxy end and the amine curing agent can contain one or more saturated, unsaturated, aromatic, and cyclic groups. In addition, the hydroxy-terminated and amine curing agents can contain one or more halogen groups. Polyurethane compositions can be made by blending or mixing hardeners. However, if desired, the polyurethane composition can be prepared with a single curing agent.

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

In this example, the saturated polyurethanes of the present invention are substantially free of aromatic groups or moieties. Suitable saturated polyurethanes for use in the present invention are reaction products of at least one polyurethane prepolymer and at least one saturated curing agent. Polyurethane prepolymers are reaction products of at least one polyol and at least one saturated diisocyanate. As is well known in the art, catalysts may be used to accelerate the reaction of the curing agent with isocyanates and polyols.

Saturated diisocyanis that can be used is, but is not limited to, ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene-1,4-diisocyanate; 1,6-hexamethylene diisocyanate (HDI); 2,2. , 4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; dicyclohexamethylene diisocyanis; cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanis; cyclohexane-1 , 4-Diisocyanis; 1-Isocyanis-3,3,5-trimethyl-5-Isocyanismethylcyclohexane; Isophoron diisocyanis; Methylcyclohexamethylene diisocyanate; Includes triisocyanate. The most preferred saturated diisocyanates are 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate.

Saturated polyols suitable for use in the present invention are, but are not limited to, polyether polyols such as polytetramethylene ether glycol and poly (oxypropylene) glycol. Suitable saturated polyester polyols are polyethylene adipate glycols, polyethylenepropylene adipate glycols, polybutylene adipate glycols, polycarbonate polyols and polyoxypropylene diols capped with ethylene oxide. Saturated polycaprolactone polyols useful in the present invention are diethylene glycol-initiated polycaprolactone, 1,4-butanediol-initiated polycaprolactone, 1,6-hexanediol-initiated polycaprolactone; trimethylolpropane-initiated polycaprolactone, neopentyl glycol-initiated polycaprolactone, And polycaprolactone with polytetremethyl ether glycol initiation. 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; trimethanolpropane; tetra- (2-hydroxypropyl) -ethylenediamine; isomer isomer of cyclohexyldimethylol. And mixtures, isomers and mixtures of cyclohexanebis (methylamine) isomers; 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, hexamethylenediamine, propylenediamine, 1-methyl-2,4-cyclohexyldiamine, 1-methyl Isomers and mixtures of isomers of -2,6-cyclohexyldiamine, 1,3-diaminopropane, dimethylaminopropylamine, diethylaminopropylamine, imide-bis-propylamine, diaminocyclohexane, monoethanolamine, diethanolamine, triethanolamine, Monoisopropanolamine and diisopropanolamine. The most preferred saturated hardeners are 1,4-butanediol, 1,4-cyclohexyldimethylol and 4,4'-bis- (sec-butylamino) -dicyclohexylmethane.

Alternatively, other suitable polymers include partially or fully neutralized ionomers, metalrosens, or other single-site catalytic polymers, polyesters, polyamides, non-ionomeric thermoplastic elastomers, copolyether-esters, Includes copolyether-amides, polycarbonates, polybutadienes, polyisoprenes, polystyrene block copolymers (eg styrene-butadiene-styrene), styrene-ethylene-propylene-styrene, styrene-ethylene-butylene-styrene and the like, and blends thereof. Thermosetting polyurethane or polyurea is suitable as the outer cover layer of the golf ball of the present invention.

In addition, polyurethane may be replaced or blended with polyurea material. Polyurea, which is clearly different from polyurethane compositions, provides the desired aerodynamic and aesthetic properties when used in golf ball components. Polyurea-based compositions are preferably saturated by their nature.

Without being bound by any particular theory, the long-chain polyol segment in the polyurethane prepolymer is replaced with a long-chain polyetherdiamine oligomer soft segment to form a polyurea prepolymer, which results in shear, cutability and It is currently believed that the impact resilience is improved and the adhesion to other components is improved. Therefore, the polyurea composition of the present invention comprises a reaction product of 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 polyether amine, and at least one diol curing agent or at least one diamine curing agent.

All polyamines available to those of skill in the art are suitable for use in this polyurea prepolymer. Polyetheramines are particularly suitable in prepolymers. Here, the term "polyester amine" means at least a polyoxyalkylene amine containing a primary amino group attached to the end of the main chain of polyether. However, due to the rapid reaction of isocyanates with amines and the insolubility of many urea products, the choice of diamines and polyetheramines is limited to those that allow the formation of polyurea prepolymers. In one example, the main chain of polyether is based on tetramethylene, propylene, ethylene, trimethylolpropane, glycerin, and mixtures thereof.

Suitable polyether amines are, but are not limited to, polytetramethylene ether diamines, polyoxypropylene diamines, poly (ethylene oxide-terminated oxypropylene) ether diamines, triethylene glycol diamines, propylene oxide-based triamines, trimethylolpropane. A triamine based on glycerin, a triamine based on glycerin, and a mixture 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 the polyurea prepolymer ranges from about 100 to about 5000. In one example, the molecular weight of polyetheramine is about 230 or greater. In other examples, the molecular weight of polyetheramine is about 4000 or less. In yet another example, the molecular weight of polyetheramine is about 600 or greater. In yet another example, the molecular weight of polyetheramine is about 3000 or less. In yet another embodiment, the molecular weight of polyetheramine is from about 1000 to about 3000, more preferably from about 1500 to about 2500. If the molecular weight of the polyether amine is low, it tends to form a solid polyurea, so an oligomer having a large molecular weight, for example, JEFFAMINE D2000, is preferable.

As briefly mentioned earlier, 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 one example, the sterically hindered secondary diamine may be suitable for use in prepolymers. Without being bound by any particular theory, amines with a high degree of steric hindrance, such as amines with a third butyl group attached to a nitrogen atom, have a higher kinetics than amines without or less impaired. Is thought to be slow. For example, 4,4'-bis- (sec-butylamino) -dicyclohexylmethane (CLEARLINK 1000) may be suitable for making polyurea prepolymers in combination with isocyanates.

Any isocyanate available to those of skill in the art is suitable for use in polyurea prepolymers. The isocyanate used in the present invention is an aliphatic, alicyclic, aromatic aliphatic, aromatic derivative having 2 or more isocyanate (NCO) groups per molecule, and a combination of these compounds. Including. Isocyanates can be organic polyisocyanate-terminated prepolymers, lower free isocyanates, and mixtures thereof. Reactive components containing isocyanates can include any isocyanate functional monomer, dimer, trimer, or multimer adducts thereof, prepolymers, pseudo-prepolymers, or mixtures thereof. The isocyanate-functional compound 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 = NRN = C = O, where R is preferably cyclic, aromatic, or direct containing about 1 to about 20 carbon atoms. A chain or branched hydrocarbon moiety. The diisocyanate can also further contain one or more cyclic groups or one or more phenyl groups. When polycyclic or aromatic groups are present, linear and / or branched hydrocarbons containing from about 1 to about 10 carbon atoms can be present as spacers between the cyclic or aromatic groups. .. In some cases, the cyclic or aromatic groups may be substituted at the 2-, 3-, and / or 4-positions, or at the ortho-, meta- and / or para-positions, respectively. Substituted groups are, but are not limited to, halogens, first, second, or third hydrocarbon groups, or mixtures thereof.

Examples of diisocyanates that can be used in the present invention are, but are not limited to, substituted and isomer mixtures containing 2,2'-, 2,4'-, and 4,4'-diphenylmethane diisocyanates; 3, 3'-dimethyl-4,4'-biphenylenediisocyanate; toluenediisocyanate; polymer MDI; carbodiimide-modified liquid 4,4'-diphenylmethane diisocyanate; para-phenylenediocyanate; meta-phenylenediisocyanate; triphenylmethane-4,4'- And triphenylmethane-4,4 -triisocyanate; naphthylene-1,5-diisocyanate; 2,4'-, 4,4'-, and 2,2-biphenyldiisocyanate; polyphenylpolymethylene polyisocyanate; with MDI PMDI mixture; PMDI and TDI mixture; ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene-1,2-diisocyanate; tetramethylene-1,3-diisocyanate; tetramethylene-1,4-diisocyanate; 1, 6-Hexamethylene diisocyanate; Octamethylene diisocyanate; Decamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; Dodecane-1,12-diisocyanate; Dicyclohexylmethane diisocyanate; Cyclobutane- 1,3-Diisocyanate; Cyclohexane-1,2-Diisocyanate; Cyclohexane-1,3-Diisocyanate; Cyclohexane-1,4-Diisocyanate; Methyl-cyclohexamethylene diisocyanate; 2,4-Methylcyclohexane diisocyanate; 2,6-Methylcyclohexane Diisocyanate; 4,4'-dicyclohexyldiisocyanate; 2,4'-dicyclohexyldiisocyanate; 1,3,5-cyclohexanetriisocyanate; isocyanatemethylcyclohexaneisocyanate; 1-isocyanate-3,3,5-trimethyl-5-isocyanatemethylcyclohexane; isocyanate ethylcyclohexaneisocyanate; bis (isocyanatemethyl) -cyclohexanediisocyanate; 4,4'-bis (isocyanatemethyl) dicyclohexane; 2,4'-bis (isocyanatemethyl) dicyclohexane; Isophorone diisocyanate; HDI triisocyanate; 2,2,4-trimethyl-1,6-hexanediisocyanate triisocyanate; 4,4'-dicyclohexylmethane diisocyanate; 2,4-hexahydrotoluenediisocyanate; 2,6-hexahydro Toluene diisocyanates; 1,2-, 1,3-, and 1,4-phenylenediocyanates; aromatic aliphatic isocyanates such as 1,2-, 1,3-, and 1,4-xylene diisocyanates; meta-tetramethyl Xylene diisocyanate; para-tetramethylxylene diisocyanate; trimeric isocyanurate of any polyisocyanate, such as toluene diisocyanate isocyanurate, diphenylmethane diisocyanate trimer, tetramethylxylene diisocyanate trimer, hexamethylene diisocyanate isocyanate Nurate, and mixtures thereof; dimerized uresiones of any polyisocyanate, such as uretdione of toluene diisocyanates, uretdiones of hexamethylene diisocyanates, and mixtures thereof; modified polyisocyanates derived from the above isocyanates and polyisocyanates; and It is a mixture of these.4,4'-Dicyclohexylmethane diisocyanate; 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; 1,2-, 1,3-, and 1,4-phenylenediisocyanate; aromatic aliphatic isocyanate , For example 1,2-, 1,3-, and 1,4-xylene diisocyanate; meta-tetramethylxylene diisocyanate; para-tetramethylxylene diisocyanate; trimeric isocyanurate of any polyisocyanate, eg toluene diisocyanate. Isocyanurate, diphenylmethane diisocyanate trimeric, tetramethylxylene diisocyanate trimeric, hexamethylene diisocyanate isocyanurate, and mixtures thereof; dimerized uresione of any polyisocyanate, such as toluene diisocyanate uretdione, hexamethylene. Uletodione of diisocyanates and mixtures thereof; modified polyisocyanates derived from the above isocyanates and polyisocyanates; and mixtures thereof.4,4'-Dicyclohexylmethane diisocyanate; 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; 1,2-, 1,3-, and 1,4-phenylenediisocyanate; aromatic aliphatic isocyanate , For example 1,2-, 1,3-, and 1,4-xylene diisocyanate; meta-tetramethylxylene diisocyanate; para-tetramethylxylene diisocyanate; trimeric isocyanurate of any polyisocyanate, eg toluene diisocyanate. Isocyanurate, diphenylmethane diisocyanate trimeric, tetramethylxylene diisocyanate trimeric, hexamethylene diisocyanate isocyanurate, and mixtures thereof; dimerized uresione of any polyisocyanate, such as toluene diisocyanate uretdione, hexamethylene. Uletodione of diisocyanates and mixtures thereof; modified polyisocyanates derived from the above isocyanates and polyisocyanates; and mixtures thereof.A dimerized uresione of any polyisocyanate, such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, and mixtures thereof; modified polyisocyanates derived from the above isocyanates and polyisocyanates; and mixtures thereof.A dimerized uresione of any polyisocyanate, such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, and mixtures thereof; modified polyisocyanates derived from the above isocyanates and polyisocyanates; and mixtures thereof.

And a mixture of these. Aromatic aliphatic isocyanates can also be used to produce photostable 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). ); Trimeric isocyanurate of any polyisocyanate, eg isocyanurate of toluene diisocyanate, trimer of diphenylmethane diisocyanate, trimeric of tetramethylxylene diisocyanate, isocyanurate of hexamethylene diisocyanate, and mixtures thereof; The dimerized uresione of the polyisocyanate, such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, and mixtures thereof; modified polyisocyanates derived from the above-mentioned isocyanates and polyisocyanates; and mixtures thereof. In addition, aromatic aliphatic isocyanates can be mixed with any of the saturated isocyanates listed above for the purposes of the present invention. And a mixture of these. In addition, aromatic aliphatic isocyanates can be mixed with any of the saturated isocyanates listed above for the purposes of the present invention. And a mixture of these. In addition, aromatic aliphatic isocyanates can be mixed with any of the saturated isocyanates listed above for the purposes of the present invention.

Factors such as the rate of reaction and the hardness of the resulting composition can be controlled by varying the number of unreacted NCO groups in the polyurea prepolymer of isocyanates and polyetheramines. For example, the number of unreacted NCO groups in the polyurea prepolymer of isocyanates and polyetheramines 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 from 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 contain from about 10% to about 20% by weight of the free isocyanate monomer of the prepolymer. As a result, in one example, the free isocyanate monomer may be removed from the polyurea prepolymer. For example, after removal, the prepolymer will contain 1% or less of free isocyanate monomers. In other examples, the prepolymer may contain about 0.5% by weight or less than a deviation of free isocyanate monomer.

Polyether amines can also be blended with additional polyols to form copolymers that can be reacted with excess isocyanate to produce polyurea prepolymers. In one example, less than about 30% by weight of the copolymer is blended with saturated polyetheramine. In another example, less than about 20% by weight of the copolymer, preferably less than about 15% by weight of the copolymer, is blended with the saturated polyether amine. Any saturated polyols available to those of skill in the art, such as polyether polyols, polycaprolactone polyols, polyester polyols, polycarbonate polyols, hydrocarbon polyols, other polyols, and mixtures thereof, are suitable for blending according to the present invention. There is. The molecular weights 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.

The polyurea composition can be prepared by cross-linking the polyurea prepolymer with a single curing agent or a blend thereof. The curing agent used in the present invention is preferably an amine-terminal curing agent, more preferably a second diamine curing agent, which causes the composition to contain only a single urea bond. In one example, the amine-terminal curing agent has a molecular weight of about 64 or greater. In other examples, the amine-terminal curing agent has a molecular weight of about 2000 or less. As mentioned above, a given amine-terminal curing agent may be modified with a compatible amine-terminal freezing point depression agent or a mixture thereof.

6-Diethylene aniline); 4,4'-methylenebis- (2,6-diethylaniline); meta-phenylenediamine; para-phenylenediamine; cyclohexyldimethol; and mixtures thereof. In one example, the amine-terminal curing agent is 4,4'-bis- (sec-butylamino) -dicyclohexylmethane.

Suitable saturated amine-terminal hardeners are, but are not limited to, ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; tetrahydroxypropyleneethylenediamine; 2,2,4- and 2,4,4. -Trimethyl-1,6-hexanediamine; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (sec) -Butylamino) -cyclohexane; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane derivative; 4,4'-dicyclohexylmethanediamine; 1,4-cyclohexane-bis- (methylamine); 1, 3-Cyclohexane-bis- (methylamine); diethylene glycol di- (aminopropyl) ether; 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine;tetraethylenepentamine; propylenediamine; 1,3-diamino Propane; dimethylaminopropylamine; diethylaminopropylamine; imide-bis-propylamine; monoethanolamine, diethanolamine; triethanolamine; monoisopropanolamine, diisopropanolamine; isophoronediamine; triisopropanolamine; and mixtures thereof. In addition, any of the above polyether amines can be used as a curing agent to react with the polyurea prepolymer.

The center of the golf ball and any layer can be made from a highly neutralized polymer (HNP). The acid moiety of the 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 a second polymer component, which, if containing an acid group, according to conventional methods, is an organic fatty acid of the invention. It can be neutralized by acids) or by both. The second polymer component may be partially or completely neutralized, preferably ionomer copolymers and ionomerter polymers, ionomer precursors, thermoplastics, polyamides, polycarbonates, polyesters, polyurethanes, polyureas, heat. Includes plastic elastomers, polybutadiene rubbers, balatas, metallosen-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 3,000 psi and about 200,000.

In one embodiment of the invention, the HNP is an ionomer and / or an acid precursor thereof, which is preferably completely or partially neutralized with an organic acid copolymer or a salt thereof. Acid copolymers are preferably α-olefins such as ethylene, C_3-8 α, β-ethylene unsaturated carboxylic acids, such as acrylic or methacrylic acid copolymers. These may optionally contain softening monomers such as alkyl acrylates and alkyl methacrylates. However, the acrylic group contains 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-ethylene unsaturated carboxylic acid, and Y is a softening comonomer. In a preferred embodiment, X is acrylic acid or methacrylic acid and Y is C._1-8It is an alkyl acrylate or a methacrylate ester. X is preferably present in an amount of about 1 to about 35% by weight of the polymer, more preferably about 5 to about 30% by weight of the polymer, and most preferably about 10 to about 20% by weight of the polymer. Y is preferably present in an amount of about 0 to about 50% by weight of the polymer, more preferably about 5 to about 25% by weight of the polymer, and most preferably about 10 to about 20% by weight of the polymer.

Specific acid-containing ethylene copolymers are not limited to this, but are not limited to ethylene / acrylic acid / n-butyl acrylate, ethylene / methacrylic acid / n-butyl acrylate, ethylene / methacrylic acid / iso-butyl acrylate, and 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 an ethylene / acrylic acid / methyl acrylate copolymer. The most preferred acid-containing ethylene copolymers are ethylene / (meth) acrylate / n-butyl acrylate, ethylene / (meth) acrylate / ethyl acrylate, and ethylene / (meth) acrylate / methyl acrylate copolymer.

Ionomers are typically neutralized with metal cations such as Li, Na, Mg, K, Ca, or Zn. By adding sufficient organic acid or salt of organic acid, along with the appropriate base, to the acid copolymer or ionomer, the ionomer is neutralized to significantly higher levels against metal cations without compromising processability. To. Preferably, the acid moiety is neutralized by about 80% or more, preferably 90-100%, and most preferably 100%. However, the workability is not impaired. It melt-blends α, β-ethylene-based unsaturated carboxylic acid copolymers with, for example, organic acids or salts of organic acids, and then adds a sufficient amount of cation source to all acid moieties (acid copolymers and organic acids). It is achieved by increasing the neutralization level of (including the acid portion of) by more than 90% (preferably more than 100%).

The organic acids of the present invention are aliphatic, mono- or multi-functional (saturated, unsaturated, or polyunsaturated) organic acids. Salts of these organic acids can also be used. The organic acid salts of the present invention are of barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin or calcium. Includes salts of salts, fatty acids, especially those of stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid or dimerized derivatives thereof. The organic acids and salts of the present invention should be relatively non-migrating (no blooming on the surface of the polymer under normal pressure) and non-volatile (not evaporating at the temperature required for melt blending). preferable.

The ionomers of the present invention may also be more conventional ionomers, i.e., partially neutralized with metal cations. The acid moiety of the acid copolymer is from about 1 to about 100%, preferably from at least about 40, depending on the cations such as lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum or mixtures thereof. Approximately 100%, more preferably at least about 90 to about 100% neutralized to produce ionomers.

In a preferred embodiment, the single layer core of the invention is surrounded by two cover layers, the inner cover layer having a thickness of about 0.01 inches to about 0.06 inches, more preferably about 0.015 inches to about 0.040 inches, most preferably about. From 0.02 inch to about 0.035 inch, the inner cover layer is a partially or fully neutralized ionomer with a shore D hardness greater than about 55, more preferably greater than about 60, and most preferably greater than about 65. Manufactured from. In this example, the thickness of the outer cover layer is from about 0.015 inches to about 0.055 inches, more preferably from about 0.02 inches to about 0.04 inches, most preferably from about 0.025 inches to about 0.035 inches, yet its hardness is about. The shore D should be 60 or less, more preferably about 55 or less, and most preferably about 52 or less. The inner cover layer needs to be harder than the outer cover layer. In this example, the outer cover layer has a partially or fully neutralized ionomer, polyurethane, polyurea, or a blend thereof. The most preferred outer cover layer is castable or reactive injection molded polyurethane, polyurea, or a hybrid thereof, the shore D hardness of which is from about 40 to about 50. The most preferred inner cover layer material is a partially neutralized ionomer with zinc, sodium, or lithium neutralized ionomers, such as SURLYN 8940, 8945, 9910, 7930, 7940 or blends thereof. And the shore D hardness is about 63 to about 68.

In the other multilayer cover, single core embodiment, the material and thickness of the outer cover and inner cover layers are the same, but the hardness range is reversed. That is, the outer cover layer is harder than the inner cover layer.

In an alternative preferred embodiment, the golf ball is a one-piece golf ball that comprises a dimple surface and whose surface hardness is less than or equal to the center hardness (ie, negative hardness gradient). Preferably, the one-piece ball has a diameter of about 1.680 inches to about 1.690 inches, its weight is about 1.620 ounces, its Atti compression is about 40 to 120, and its COR is about 0.750 to about 0.825.

In a preferred two-piece ball embodiment, a single layer core with a negative hardness gradient has a shore D hardness of about 20 to about 80, more preferably about 40 to about 75, and most preferably about 45 to about 70. Encapsulated in cover material, thermoplastic or thermocurable polyurethane, polyurea, polyamide, polyester, polyester elastomer, polyether-amide or polyester-amide, partially or fully neutralized ionomer, polyolefin, eg polyethylene, polypropylene , Polyethylene copolymers such as ethylene-butyl acrylate or ethylene-methyl acrylate, poly (ethylene methacrylate) co- and terpolymers, metalrose-catalyzed polyolefins, polar group-functional polyolefins, and blends thereof. A preferred cover material in the two-piece embodiment is an ionomer (conventional or HNP) with a hardness of about 50 to about 70 Shore D. Another preferred cover material in the two-piece embodiment is a thermoplastic or thermosetting polyurethane or polyurea. Preferred ionomers are high acid ionomers that have a copolymer of ethylene with methacrylic acid or acrylic acid and have an acid content of at least 16 to about 25 weight percent. In this case, the decrease in spin caused by the relatively robust, high-acid ionomer is offset to some extent by the negatively gradient core that increases the spin. The diameter of the core may be from about 1.0 inch to about 1.64 inch, preferably from about 1.30 inch to about 1.620 inch, most preferably from about 1.40 inch to about 1.60 inch.

Other preferred cover materials include castable or reactive injection-moldable polyurethanes, polyureas, or polyurethane / polyurea copolymers or hybrids. Preferably, the cover is thermosetting, but may also be thermoplastic, with a shore D hardness of about 20 to about 70, more preferably about 30 to about 65, most preferably about 35 to about 60. is there. The water vapor barrier layer, eg, that disclosed in US Pat. Nos. 6,632,147, 6,932,720, 7,004,854, and 7,182,702, is adopted as an option between the cover layer and the core. These patent documents are incorporated herein by reference.

Although any of the examples presented herein may accompany any known dimple number and pattern, the preferred number of dimples is 252 to 456, more preferably 330 to 392. The dimples may be with any width, depth, and edge angle disclosed in the prior art, and the pattern may have multiple dimples of different width, depth, and edge writing. The parting line structure of such a pattern may be a straight line or a staggered wave parting line (SWPL). Most preferably the number of dimples is 330, 332, or 392 with 5 to 7 dimple dimensions. The dividing line is SWPL.

In any of these examples, the single layer core may be replaced with a core consisting of two or more layers. However. At least one core layer has a negative hardness gradient.

Other matters in the working example, or, unless stated otherwise, all numerical ranges, quantities, values, percentages, such as those regarding the quantity of material, and others in the specification, even if the value, quantity or Even if the term "about" is not displayed in relation to the range, it can be read as if "about" is placed before it. Therefore, unless indicated otherwise, the parameters of the numbers expressed in the specification and claims are approximate, depending on the desired properties intended to be obtained by the present invention. Change. At a minimum, of course, it does not constrain the application of the doctrine of equivalents, but the parameters of each number should be interpreted in the light of the number of significant figures recorded and the usual rounding process.

Although the numerical ranges and parameters that indicate the broad scope of the invention are approximate, the numbers shown in the embodiments were recorded as accurately as possible. Any number will nevertheless contain an error due to the standard deviation found in each test measurement. Further, it should be understood that any combination of values, including the illustrated values, can be used when numerical ranges of various scopes are indicated.

It is clear that the exemplary embodiments of the invention described herein satisfy the preferred embodiments of the invention, but it should be appreciated that those skilled in the art can conceive of various modifications and other embodiments. Examples of such changes include slight changes in the numbers mentioned above. Therefore, the above-mentioned numerical values and the numerical values in the claims include such numerical values, and also include values that are close to and very close to the values described in the above-mentioned and claims. Therefore, it should be understood that the claims are intended to cover all such modifications and other embodiments and fall within the spirit and scope of the invention.