JP5212603B2 - Solid golf balls - Google Patents

Description

  The present invention relates to a solid golf ball having a solid core and a cover layer covering the core. More specifically, the present invention provides high resilience at the time of a full shot with a driver to increase the flight distance and approach shot. The present invention relates to a solid golf ball that has good performance and feel and is further excellent in scratch resistance.

2. Description of the Related Art Conventionally, various golf balls that satisfy the required characteristics of golf balls such as flying, hit feeling, approach controllability, etc. have been improved. For example, golf balls proposed in Japanese Patent Laid-Open No. 6-98949 Is mentioned.
However, this golf ball has a problem in spin performance because the cover is hard.

  As another proposal, JP-A-9-308708, JP-A-2003-70936, JP-A-2003-180879, etc. have cover thickness, flexural rigidity, and Shore D hardness within a specific range. Thus, a solid golf ball with improved feeling and controllability has been proposed without reducing resilience and cut resistance.

  However, this golf ball lacks the resilience of the core, the core hardness distribution is not optimized, and problems remain in the flight distance, spin performance, and the like.

  Further, Japanese Patent Laid-Open Nos. 9-215778 and 9-271538 propose solid golf balls using a polyurethane material as a cover material. However, this golf ball has room for improvement in terms of flight distance and cover scratch resistance because the resilience of the core is not sufficient and the scratch resistance of the resin forming the cover is insufficient. Met.

  In addition, the golf balls described in Japanese Patent Application Laid-Open Nos. 2002-355338 and 2004-180793 have good core resilience, but the golf balls have high deflection hardness and are soft. However, the problem still remains in the flight distance.

Japanese Patent Laid-Open No. 6-98949 JP-A-9-308708 JP 2003-70936 A JP 2003-180879 A JP-A-9-215778 Japanese Patent Laid-Open No. 9-271538 JP 2002-355338 A JP 2004-180793 A

  The present invention has been made in view of the above circumstances, and imparts high resilience at the time of a full shot with a driver to increase the flight distance, and the spin performance and feel of the approach are good, and the scratch resistance is further improved. An object of the present invention is to provide a solid golf ball having excellent performance.

  As a result of intensive studies in order to achieve the above object, the present inventors have mainly improved the spin performance of the approach by optimizing the solid core hardness distribution and optimizing the relationship between the cover surface and the core surface hardness. The present inventors have found a solid golf ball that is excellent and has a low spin in a full shot and thus has an improved flight distance and a good hit feeling, and has led to the present invention. In addition, this solid golf ball has a low bending rigidity compared to a normal cover layer made of an ionomer resin or the like, although the cover layer is hard, so that the spin performance and its stability are extremely low. It is expensive. Furthermore, this solid golf ball is excellent in abrasion resistance and cracking durability when repeatedly hit. Based on such knowledge, the solid golf ball of the present invention includes the following solid core I and cover layer II.

I. Organic sulfur with respect to 100 parts by mass of a rubber base material containing 60 to 100 parts by mass of polybutadiene rubber containing 60% or more of solid core (i) cis-1,4-bond and synthesized using a rare earth element-based catalyst A solid core is formed with a rubber composition containing 0.1 to 5 parts by mass of a compound, an unsaturated carboxylic acid or a metal salt thereof, an organic peroxide, and an inorganic filler.
(Ii) The deformation when the solid core is loaded from an initial load of 10 kgf to a final load of 130 kgf is 2.0 to 3.5 mm.
(Iii) The hardness distribution of the solid core satisfies the following table.

II. Cover layer (i) The cover layer is obtained by kneading the raw materials of (A) thermoplastic polyurethane and (B) polyisocyanate compound in an inert gas atmosphere or in a vacuum state, and mainly (A) and (B) . It is formed by injection molding one type of resin pellet made of a resin compound as a component, and at least a portion of one molecule is contained in the resin pellet that is put into an injection molding machine immediately before injection molding. (Ii) the cover layer has a thickness of 0.5 to 2.5 mm and a surface hardness of Shore D hardness of 50 to 70. The core surface hardness is smaller within the range of Shore D hardness 1 to 15 than the cover surface hardness.

Accordingly, the present invention provides the following solid golf ball.
[1] A solid golf ball comprising a solid core and a cover layer covering the solid core, wherein a plurality of dimples are formed on the outer surface of the outermost layer of the cover layer. 0.1 to 5 parts by mass of an organic sulfur compound with respect to 100 parts by mass of a rubber substrate containing 60 to 100 parts by mass of polybutadiene rubber containing 60% or more of 4-bonds and synthesized using a rare earth element-based catalyst, It is formed from a rubber composition containing an unsaturated carboxylic acid or a metal salt thereof, an organic peroxide, an inorganic filler, and has a deformation amount of 2.0 to 2.0 when the solid core is loaded from an initial load of 10 kgf to a final load of 130 kgf. 3.5 mm, and the solid core has the hardness distribution of [Table 1] described above, and the cover layer comprises (A) thermoplastic polyurethane and (B) polyisocyanate. Kneaded each raw material of an object in an inert gas atmosphere or vacuum, the (A) and (B) one kind of resin pellets made of a resin blend consisting mainly those formed by injection molding In the resin pellets that are put into the injection molding machine immediately before the injection molding, at least a part thereof contains a polyisocyanate compound in which all isocyanate groups in one molecule remain in an unreacted state. The cover layer has a thickness of 0.5 to 2.5 mm, its surface hardness is Shore D hardness 50 to 70, and the core surface hardness is within the range of Shore D hardness 1 to 15 than the cover surface hardness. A solid golf ball characterized by having a deformation amount of 2.0 to 2.9 mm when loaded from an initial load of 10 kgf to a final load of 130 kgf.
[2] The solid golf ball according to [1], wherein the solid core has a diameter of 37.6 to 43.0 mm, and the golf ball has a diameter of 42.67 to 44.0 mm.
[3] In the solid core, the amount of the unsaturated carboxylic acid or metal salt thereof is 30 to 45 parts by mass, the amount of the organic peroxide is 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the rubber base material, The solid golf ball according to [1] or [2], wherein the blending amount of the inorganic filler is 5 to 80 parts by mass and the antiaging agent is blended in an amount of 0 to 0.2 parts by mass.
[4] The solid golf ball according to [1], [2] or [3], wherein the hardness difference at any two locations in a portion of 5 mm to 10 mm from the center of the solid core is within ± 2 in Shore D hardness .
[5] In the above dimples, the total number is 250 to 450, the average depth of all the dimples is 0.125 to 0.170 mm, the average diameter is 3.5 to 5.0 mm, and the types are four or more types The solid golf ball according to any one of [1] to [4].
[6] The solid golf ball according to any one of [1] to [5], wherein (C) a thermoplastic elastomer other than the thermoplastic polyurethane is further blended with the resin blend.
[7] In the resin blend, a part of the isocyanate group of the component (B) forms a bond with active hydrogen in the component (A) and / or (C), and the other isocyanate groups are in an unreacted state. The solid golf ball according to [6], which remains in the resin compound.
[8] The solid golf ball according to [6] or [7], wherein the composition ratio of each component is (A) :( B) :( C) = 100: 2 to 50: 0 to 50 by mass ratio.
[9] The solid golf ball according to [6] or [7], wherein the composition ratio of each component is (A) :( B) :( C) = 100: 2-30: 8-50 in terms of mass ratio.
[10] The solid golf ball according to any one of [1] to [9], wherein the total mass of the component (A) and the component (B) is 90% by mass or less of the total mass of the cover layer.
[11] The solid golf ball according to any one of [1] to [10], wherein the resin composition has a melt mass flow rate (MFR) value at 210 ° C. of 5 g / 10 min or more.
[12] Component (B) is 4,4′-diphenylmethane diisocyanate, 2,4- (or) 2,6-toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthylene 1,5-diisocyanate, tetramethylxylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, trimethylhexamethylene diisocyanate, one or more kinds on whether we selected from the group consisting of dimer acid diisocyanate The solid golf ball according to any one of [1] to [11], which is a polyisocyanate compound.
[13] The component (B) is one or more polyisocyanate compounds selected from the group consisting of 4,4′-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate. The solid golf ball according to claim 1.
[14] Component (C) is polyester elastomer, polyamide elastomer, ionomer resin, styrene block elastomer, hydrogenated styrene butadiene rubber, styrene-ethylene / butylene-ethylene block copolymer or a modified product thereof, ethylene-ethylene / butylene- One or more heat selected from the group consisting of an ethylene block copolymer or a modified product thereof, a styrene-ethylene butylene-styrene block copolymer or a modified product thereof, ABS resin, polyacetal, polyethylene and nylon resin the solid golf ball according to any one of a thermoplastic elastomer [6] to [13].
[15] The solid golf ball of [14], wherein the component (C) is one or more thermoplastic elastomers selected from the group consisting of polyester elastomers, polyamide elastomers, and polyacetals.
[16] The solid golf ball according to any one of [1] to [15], wherein the resin composition has a melt mass flow rate (MFR) value at 210 ° C. of 5 g / 10 min or more.
[17] The solid golf ball of any one of repulsion elasticity conforming to JIS K7311 of the cover layer is 47% or more [1] to [16].

  According to the solid golf ball of the present invention, the resilience is improved by the solid core hardness distribution, the selection of the cover material, and the solid core and cover hardness, the deflection amount of the entire ball, etc. The ball spin rate is reduced during shots to increase the flight distance of the ball, and compared to a normal ionomer cover, the bending rigidity is lower for a harder cover, resulting in superior approach spin performance. , Its stability is very high. Furthermore, the golf ball of the present invention has excellent scratch resistance and resistance to cracking when repeatedly hit, and is a very advantageous ball in terms of the game overall.

Hereinafter, the present invention will be described in more detail.
The solid golf ball of the present invention comprises a solid core and one or more cover layers covering the solid core.

  The solid core is a heat-molded product of a rubber composition using polybutadiene as a base rubber.

  Here, the polybutadiene has cis 1,4 bonds of 60% or more, preferably 80% or more, more preferably 90% or more, most preferably 95% or more, and 1,2 vinyl bonds of 2%. % Or less, preferably 1.7% or less, more preferably 1.5% or less, and most preferably 1.3% or less. When deviating from the above range, the resilience decreases.

The polybutadiene has a Mooney viscosity (ML _{1 + 4} (100 ° C.)) of 30 or more, preferably 35 or more, more preferably 40 or more, still more preferably 50 or more, and most preferably 52 or more. It is recommended that it be 100 or less, preferably 80 or less, more preferably 70 or less, and most preferably 60 or less.

The Mooney viscosity referred to in the present invention is an industrial viscosity index (JIS-K6300) measured with a Mooney viscometer, which is a kind of rotational plasticity meter, and ML _{1 + 4} as a unit symbol. (100 ° C.) is used. M represents Mooney viscosity, L represents a large rotor (L-type), 1 + 4 represents a preheating time of 1 minute, and a rotor rotation time of 4 minutes, and the measurement was performed at 100 ° C.

  Furthermore, the molecular weight distribution Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) of the polybutadiene is 2.0 or more, preferably 2.2 or more, more preferably 2.4 or more, and still more preferably 2. The upper limit is 6.0 or less, preferably 5.0 or less, preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.4 or less. When Mw / Mn is too small, workability may be reduced, and when Mw / Mn is too large, resilience may be reduced.

  The polybutadiene is preferably synthesized with a rare earth element-based catalyst, and a known one can be used as the rare earth element-based catalyst.

  For example, a catalyst comprising a combination of a lanthanum series rare earth element compound, an organoaluminum compound, an alumoxane, a halogen-containing compound and, if necessary, a Lewis base can be used.

  Examples of the lanthanum series rare earth element compounds include metal halides having an atomic number of 57 to 71, carboxylates, alcoholates, thioalcolates, and amides.

Examples of the organoaluminum compound include AlR ¹ R ² R ³ (wherein R ¹ , R ² and R ³ may be the same or different, and each represents hydrogen or a hydrocarbon residue having 1 to 8 carbon atoms. Can be used.

  Preferred examples of the alumoxane include compounds having a structure represented by the following formula (I) or the following formula (II). In this case, Fine Chemicals, 23, (9), 5 (1994), J. Am. Am. Chem. Soc. 115, 4971 (1993); Am. Chem. Soc. 117, 6465 (1995).

（式中、Ｒ⁴は、炭素数１〜２０の炭素原子を含む炭化水素基、ｎは２以上の整数である。）

(In the formula, R ⁴ is a hydrocarbon group containing a carbon atom having 1 to 20 carbon atoms, and n is an integer of 2 or more.)

Examples of the halogen-containing compound include AlX _n R _3-n (where X represents halogen, R is a hydrocarbon residue having 1 to 20 carbon atoms, such as an alkyl group, an aryl group, and an aralkyl group. And n represents 1, 1.5, 2 or 3), strontium halides such as Me ₃ SrCl, Me ₂ SrCl ₂ , MeSrHCl ₂ and MeSrCl ₃ , and others, silicon tetrachloride, tetrachloride Metal halides such as tin and titanium tetrachloride are used.

  The Lewis base can be used to complex a lanthanum series rare earth element compound, and examples thereof include acetylacetone and ketone alcohol.

  In the present invention, in particular, the use of a neodymium-based catalyst using a neodymium compound as a lanthanum series rare earth element compound is superior in polybutadiene rubber having a high content of 1,4-cis bonds and a low content of 1,2-vinyl bonds. Since it is obtained by polymerization activity, it is preferable, and specific examples of these rare earth element-based catalysts include those described in JP-A No. 11-35633.

  When butadiene is polymerized in the presence of a rare earth element-based catalyst, a solvent may be used, bulk polymerization or gas phase polymerization may be performed without using a solvent, and the polymerization temperature is usually −30 ° C. to 150 ° C., preferably Can be 10-100 degreeC.

  The polybutadiene may be obtained by reacting a terminal modifier with the active terminal of the polymer subsequent to the polymerization using the rare earth element-based catalyst.

  Here, the terminal modifier can use a well-known thing, for example, can mention the compound described in following (i)-(vii).

(I) It can be obtained by reacting a compound having an alkoxysilyl group at the active terminal of the polymer. As the compound having an alkoxysilyl group, an alkoxysilane compound having at least one epoxy group or isocyanate group in the molecule is preferably used. Specific examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, (3-glycidyloxypropyl) methyldimethoxysilane, (3-glycidyloxypropyl) methyldiethoxysilane, β- (3 , 4-epoxycyclohexyl) trimethoxysilane, β- (3,4-epoxycyclohexyl) triethoxysilane, β- (3,4-epoxycyclohexyl) methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethoxy Epoxy group-containing alkoxysilanes such as silane, 3-glycidyloxypropyltrimethoxysilane condensate, (3-glycidyloxypropyl) methyldimethoxysilane condensate; 3-isocyanatopropyltrimethoxysilane, 3 Isocyanatopropyltriethoxysilane, (3-isocyanatopropyl) methyldimethoxysilane, (3-isocyanatopropyl) methyldiethoxysilane, condensate of 3-isocyanatopropyltrimethoxysilane, (3-isocyanatopropyl) methyl Examples include isocyanate group-containing alkoxysilane compounds such as dimethoxysilane condensates.

  In addition, when the compound having an alkoxysilyl group is reacted with the active terminal, a Lewis acid can be added to accelerate the reaction. The Lewis acid acts as a catalyst to promote the coupling reaction, improving the cold flow of the modified polymer and improving the storage stability. Specific examples of the Lewis acid include dialkyl tin dialkyl malate, dialkyl tin dicarboxylate, aluminum trialkoxide and the like.

^{_{(Ii) R 5 n M'X 4}} -n, M'X 4, M'X 3, R 5 n M '(- R 6 -COOR 7) 4-n or _{^{R 5 n M' (- R}} 6 - COR ⁷ ) _4-n (wherein R ⁵ and R ⁶ may be the same or different and each represents a hydrocarbon group containing 1 to 20 carbon atoms, R ⁷ is a carbon atom having 1 to 20 carbon atoms) Which may contain a carbonyl group or an ester group in the side chain, M ′ is a tin atom, silicon atom, germanium atom or phosphorus atom, X is a halogen atom, and n is an integer of 0 to 3 A halogenated organometallic compound, a halogenated metal compound or an organometallic compound

(Iii) heterocumulene containing Y = C = Z bond in the molecule (wherein Y represents a carbon atom, oxygen atom, nitrogen atom or sulfur atom, and Z represents an oxygen atom, nitrogen atom or sulfur atom) Compound

(Iv) Hetero 3-membered ring compound containing the following bond in the molecule

（式中、Ｙは、酸素原子、チッ素原子又はイオウ原子を示す）

(In the formula, Y represents an oxygen atom, a nitrogen atom or a sulfur atom)

(V) Halogenated isocyano compound

^{(Vi) R 8 - (COOH} ) m, R 9 (COX) m, R 10 - (COO-R 11), R 12 -OCOO-R 13, R 14 - (COOCO-R 15) m, or the following formula Carboxylic acid, acid halide, ester compound, carbonate compound or acid anhydride represented by

（式中、Ｒ⁸〜Ｒ¹⁶は、同一でも異なっていてもよく、炭素数１〜５０の炭素原子を含む炭化水素基、Ｘはハロゲン原子、ｍは１〜５の整数を示す）

(In formula, R < ⁸ > -R < ¹⁶ > may be same or different, The hydrocarbon group containing a C1-C50 carbon atom, X is a halogen atom, m shows the integer of 1-5.)

(Vii) R ¹⁷ _l M ″ (OCOR ¹⁸ ) _4-l , R ¹⁹ _l M ″ (OCO-R ²⁰ —COOR ²¹ ) _4-l , or a metal salt of a carboxylic acid represented by the following formula

（式中、Ｒ¹⁷〜Ｒ²³は、同一でも異なっていてもよく、炭素数１〜２０の炭素原子を含む炭化水素基、Ｍ”はスズ原子、ケイ素原子又はゲルマニウム原子、ｌは０〜３の整数を示す。）

(In formula, R < ¹⁷ > -R < ²³ > may be same or different, A hydrocarbon group containing a C1-C20 carbon atom, M "is a tin atom, a silicon atom, or a germanium atom, l is 0-3. Indicates an integer.)

  Specific examples of the terminal modifiers shown in the above (i) to (vii) and the reaction method are, for example, JP-A-11-35633, JP-A-7-268132, JP-A-2002-293996, and the like. And the methods and methods described in.

  In the rubber base material, the polybutadiene is 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, most preferably 90% by mass or more, and the upper limit is 100% by mass or less, preferably 98% by mass. In the following, it is necessary that 95% by mass or less is blended. If the blending amount is insufficient, it becomes difficult to obtain a golf ball with good resilience.

  In addition, rubbers other than the above polybutadiene can be used and blended together as long as the object of the present invention is not impaired. Specific examples include polybutadiene rubber (BR), styrene butadiene rubber (SBR), natural rubber, polyisoprene rubber, ethylene propylene diene rubber (EPDM), and the like. These can be used individually by 1 type or in combination of 2 or more types.

  The thermoformed product that is the solid core is provided with an unsaturated carboxylic acid and / or a metal salt thereof, an organic sulfur compound, an inorganic filler, and an organic peroxide as essential components with respect to 100 parts by mass of the rubber base material. It is formed of a rubber composition mixed in a fixed amount.

  Here, specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, and fumaric acid, and acrylic acid and methacrylic acid are particularly preferable.

  Moreover, as a metal salt of unsaturated carboxylic acid, zinc salts of unsaturated fatty acids such as zinc methacrylate and zinc acrylate, magnesium salts and the like can be blended, and zinc acrylate can be particularly preferably used.

  The unsaturated carboxylic acid and / or metal salt thereof is 30 parts by mass or more, preferably 31 parts by mass or more, more preferably 32 parts by mass or more, with an upper limit of 45 parts by mass or less, relative to 100 parts by mass of the base rubber. Preferably it is 43 mass parts or less, More preferably, it is 41 mass parts or less, Most preferably, it is 39 mass parts or less. If the amount is too large, it will be too hard, resulting in an unbearable feel, and if it is too small, the resilience will be reduced.

  An organic sulfur compound is an essential component for imparting excellent resilience. Specifically, it is recommended that thiophenols, thionaphthols, halogenated thiophenols, or metal salts thereof be blended. Specifically, zinc salts such as pentachlorothiophenol, pentafluorothiophenol, pentabromothiophenol, parachlorothiophenol, pentachlorothiophenol, diphenyl polysulfide having 2 to 4 sulfur atoms, dibenzyl polysulfide, dibenzoyl Polysulfide, dibenzothiazoyl polysulfide, dithiobenzoyl polysulfide and the like can be mentioned, and in particular, zinc salt of pentachlorothiophenol and diphenyl disulfide can be preferably used.

  The organic sulfur compound is 0.1 parts by mass or more, preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and most preferably 0.4 parts by mass or more with respect to 100 parts by mass of the base rubber. The upper limit is 5 parts by mass or less, preferably 4 parts by mass or less, more preferably 3 parts by mass or less, and most preferably 2 parts by mass or less. If the amount is too large, the hardness becomes too soft, and if it is too small, improvement in resilience cannot be expected.

  As an inorganic filler, zinc oxide, barium sulfate, calcium carbonate etc. can be mentioned, for example, The compounding quantity is 5 mass parts or more with respect to 100 mass parts of the above-mentioned base rubber, preferably 6 mass parts or more, More preferably, it is 7 parts by mass or more, most preferably 8 parts by mass or more, and the upper limit is 80 parts by mass or less, preferably 60 parts by mass or less, more preferably 40 parts by mass or less, and most preferably 20 parts by mass or less. If the blending amount is too large or too small, an appropriate mass and suitable resilience cannot be obtained.

  Examples of the organic peroxide include commercially available products, such as Park Mill D (manufactured by NOF Corporation), Perhexa 3M (manufactured by NOF Corporation), Perhexa C (manufactured by NOF Corporation), Luperco 231XL (manufactured by Atchem Corporation). ) And the like. If necessary, two or more different organic peroxides may be mixed and used.

  The organic peroxide is 0.1 parts by mass or more, preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and most preferably 0.4 parts by mass with respect to 100 parts by mass of the base rubber. The upper limit is 0.5 parts by mass or less, preferably 0.45 parts by mass or less, and more preferably 0.42 parts by mass or less. If the blending amount is too large or too small, a suitable hardness distribution, that is, hit feeling, durability and resilience cannot be obtained.

  Moreover, an anti-aging agent can be mix | blended as needed, for example, as a commercial item, NOCRACK NS-6, NS-30 (made by Ouchi Shinsei Chemical Co., Ltd.), Yoshinox 425 (made by Yoshitomi Pharmaceutical Co., Ltd.), etc. Can be mentioned. 0 parts by mass or more, preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, and 0.2 parts by mass or less as an upper limit, preferably 0.1 parts by mass with respect to 100 parts by mass of the base rubber. Part or less, more preferably 0.08 parts by mass or less is recommended from the viewpoint of obtaining suitable resilience and durability.

  In addition, it is preferable to perform primer treatment on the surface of the solid core from the viewpoint of ensuring adhesion between the cover layer and the solid core and durability. Specifically, an adhesive layer can be provided between the solid core and the cover layer for the purpose of improving durability during impact. In this case, examples of the adhesive may include an epoxy resin adhesive, a vinyl resin adhesive, a rubber adhesive, and the like. In particular, a urethane resin adhesive and a chlorinated polyolefin adhesive may be used. preferable.

  In this case, the adhesive layer can be formed by dispersion coating, but the type of emulsion used for the dispersion coating is not limited. As the resin powder for preparing the emulsion, thermoplastic resin powder or thermosetting resin powder can be used. For example, vinyl acetate resin, vinyl acetate copolymer resin, EVA (ethylene-vinyl acetate copolymer resin), acrylate ester (Co) polymer resin, epoxy resin, thermosetting urethane resin, thermoplastic urethane resin, and the like can be used. Among these, an epoxy resin, a thermosetting urethane resin, a thermoplastic urethane resin, and an acrylate (co) polymer resin are particularly preferable, and a thermoplastic urethane resin is particularly preferable.

  The thickness of the adhesive layer is preferably 0.1 to 30 μm, particularly preferably 0.2 to 25 μm, and particularly preferably 0.3 to 20 μm.

  The solid core (thermoformed product) can be obtained by vulcanizing and curing the above-described rubber composition in the same manner as a known golf ball rubber composition. The vulcanization conditions can be carried out, for example, at a vulcanization temperature of 100 to 200 ° C. and a vulcanization time of 10 to 40 minutes.

  The deformation amount of the solid core when the initial load is 10 kgf to the final load 130 kgf is 2.0 mm or more, preferably 2.3 mm or more, more preferably 2.7 mm or more, and most preferably 2.8 mm or more. . As an upper limit, it is 3.5 mm or less, Preferably it is 3.4 mm or less, More preferably, it is 3.3 mm or less, Most preferably, it is 3.2 mm or less. If the amount of deformation of this solid core is too small, the hit feeling will be worse, especially when a long shot in which a ball such as a driver is greatly deformed, the spin will increase and will not fly, and if it is too soft, the hit feeling will be dull. In some cases, the repulsion is not sufficient and does not fly, and the durability to cracking due to repeated impacts may deteriorate.

  In the present invention, the solid core has the hardness distribution shown in the following table.

  The solid core has a Shore D hardness of 35 or more, preferably 37 or more, more preferably 39 or more, and most preferably 40 or more. The upper limit is 55 or less, preferably 52 or less, more preferably 49 or less. Most preferably, it is 45 or less. If the Shore D hardness is too low, the resilience is lowered, and if it is too high, the hit feeling is too hard, the spin amount of the driver is increased, and the flight distance is reduced. There is a fear.

  The hardness of the region of 5 mm to 10 mm from the center of the solid core is Shore D hardness of 39 or more, preferably 41 or more, more preferably 43 or more, most preferably 44 or more, and the upper limit is 58 or less, preferably 55 or less. More preferably, it is 52 or less, most preferably 49 or less. If the Shore D hardness is too low, the resilience is lowered, and if it is too high, the hit feeling is too hard, and the spin amount of the driver is increased. The flight distance may be reduced.

  Note that the hardness difference between any two locations in the region of 5 to 10 mm from the center of the solid core is Shore D hardness of 0 or more, preferably ± 0.2 or more, more preferably ± 0.5 or more. , Preferably within ± 2, more preferably within ± 1.7, even more preferably within ± 1.5, and most preferably within ± 1.2.

  The hardness of the portion 15 mm from the center of the solid core is Shore D hardness of 48 or more, preferably 50 or more, more preferably 51 or more, most preferably 52 or more, and the upper limit is 66 or less, preferably 63 or less, Preferably, it is 60 or less, and most preferably 57 or less. If the Shore D hardness is too low, the resilience is lowered, and if it is too high, the hit feeling is too hard, the spin amount of the driver is increased, and the flight distance is increased. May decrease.

  The hardness of the surface of the solid core is not less than 50, preferably not less than 52, more preferably not less than 53, most preferably not less than 54 in Shore D hardness, and the upper limit is 68 or less, preferably 65 or less, more preferably 62 or less. However, if the Shore D hardness is too low, the resilience is lowered, and if it is too high, the hit feeling is too hard, the spin amount of the driver is increased, and the flight distance is reduced. There is a risk that.

  The hardness difference between the surface and the center of the solid core is 5 or more, preferably 8 or more, more preferably 11 or more, most preferably 14 or more in Shore D hardness, and the upper limit is 20 or less, preferably 19 or less. Most preferably, it is 18 or less. If the difference in hardness is smaller than the above, the spin amount of the driver increases and the flight distance may decrease. Conversely, if the hardness difference is larger than the above, the resilience and durability may be reduced.

  The diameter of the solid core is 37.6 mm or more, preferably 38.2 mm or more, more preferably 38.8 mm or more, most preferably 39.6 mm or more, and the upper limit is 43.0 mm or less, preferably 42.0 mm or less, more preferably Is recommended to be 41.5 mm or less, and most preferably 41.0 mm or less.

  The specific gravity of the solid core is usually 0.9 or more, preferably 1.0 or more, more preferably 1.1 or more, and the upper limit is 1.4 or less, preferably 1.3 or less, more preferably 1.2 or less. It is recommended that there be.

  In the present invention, the cover layer is formed mainly of a polyurethane material. When a cover layer is formed using such a polyurethane material as the main material, excellent feeling, controllability, cut resistance, scratch resistance, and durability against cracking when repeatedly struck are obtained without impairing resilience. It is. Although the cover layer may have a multilayer structure of not only one layer but also two or more layers, the outermost layer cover needs to be mainly made of the polyurethane material described here.

  In this case, the cover layer can be formed of a molded product of a resin blend mainly composed of (A) thermoplastic polyurethane and (B) polyisocyanate compound. A golf ball made of such a thermoplastic polyurethane has excellent resilience, spin performance, and scratch resistance.

  The cover layer is mainly composed of thermoplastic polyurethane, and is formed from a resin blend mainly composed of (A) thermoplastic polyurethane and (B) polyisocyanate compound.

  In order to exhibit the effect of the present invention sufficiently effectively, a necessary and sufficient amount of unreacted isocyanate groups may be present in the cover resin material. Specifically, the above components (A) and (B) Is recommended to be 60% or more of the total mass of the cover layer, and more preferably 70% or more. The components (A) and (B) will be described in detail below.

  When the thermoplastic polyurethane (A) is described, the structure of the thermoplastic polyurethane comprises a soft segment composed of a high-molecular polyol (polymeric glycol) which is a long-chain polyol, and a hard segment composed of a chain extender and a polyisocyanate compound. Including. Here, as the long-chain polyol as a raw material, any of those conventionally used in the technology relating to thermoplastic polyurethane can be used, and is not particularly limited. For example, polyester polyol, polyether polyol, polycarbonate polyol , Polyester polycarbonate polyol, polyolefin polyol, conjugated diene polymer polyol, castor oil polyol, silicone polyol, vinyl polymer polyol and the like. One kind of these long-chain polyols may be used, or two or more kinds may be used in combination. Of these, polyether polyols are preferred because they can synthesize thermoplastic polyurethanes having high impact resilience and excellent low-temperature properties.

  Examples of the polyether polyol include poly (ethylene glycol), poly (propylene glycol), poly (tetramethylene glycol), poly (methyltetramethylene glycol) and the like obtained by ring-opening polymerization of a cyclic ether. Can do. As the polyether polyol, one type may be used, or two or more types may be used in combination. Of these, poly (tetramethylene glycol) and / or poly (methyltetramethylene glycol) are preferred.

  The number average molecular weight of these long-chain polyols is preferably in the range of 1,500 to 5,000. By using a long-chain polyol having such a number average molecular weight, a golf ball made of a thermoplastic polyurethane composition excellent in various properties such as the resilience and productivity described above can be obtained with certainty. The number average molecular weight of the long-chain polyol is more preferably in the range of 1,700 to 4,000, and further preferably in the range of 1,900 to 3,000.

  In addition, the number average molecular weight of said long chain polyol is the number average molecular weight computed based on the hydroxyl value measured based on JISK-1557.

  As the chain extender, those used in the conventional technology relating to thermoplastic polyurethane can be suitably used. For example, a low molecular weight of 400 or less having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule. It is preferably a molecular compound. Examples of the chain extender include 1,4-butylene glycol, 1,2-ethylene glycol, 1,3-butanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, and the like. However, it is not limited to these. Of these, the chain extender is preferably an aliphatic diol having 2 to 12 carbon atoms, and more preferably 1,4-butylene glycol.

  As a polyisocyanate compound, what is used in the technique regarding the conventional thermoplastic polyurethane can be used suitably, and there is no restriction | limiting in particular. Specifically, 4,4′-diphenylmethane diisocyanate, 2,4- (or) 2,6-toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthylene 1,5-diisocyanate, tetramethylxylene diisocyanate, hydrogenated One type or two or more types selected from the group consisting of xylylene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate can be used. However, some isocyanate species make it difficult to control the crosslinking reaction during injection molding. In the present invention, 4,4'-diphenylmethane diisocyanate, which is an aromatic diisocyanate, is most preferable from the viewpoint of the balance between the stability during production and the physical properties to be expressed.

  The most preferable thermoplastic polyurethane as the component (A) is a thermoplastic polyurethane synthesized using a polyether polyol as a long-chain polyol, an aliphatic diol as a chain extender, and an aromatic diisocyanate as a polyisocyanate compound. The polyether polyol is a polytetramethylene glycol having a number average molecular weight of 1,900 or more, the chain extender is 1,4-butylene glycol, and the aromatic diisocyanate is 4,4′-diphenylmethane diisocyanate, However, it is not limited to these.

  In addition, the active hydrogen atom: isocyanate group mixing ratio in the polyurethane forming reaction described above is a golf ball made of a thermoplastic polyurethane composition having various properties such as resilience, spin performance, scratch resistance and productivity as described above. Can be adjusted within a preferable range. Specifically, in producing a thermoplastic polyurethane by reacting the long-chain polyol, the polyisocyanate compound and the chain extender, with respect to 1 mol of active hydrogen atoms of the long-chain polyol and the chain extender, It is preferable to use each component in such a ratio that the isocyanate group contained in the polyisocyanate compound is 0.95 to 1.05 mol.

  The method for producing the thermoplastic polyurethane as the component (A) is not particularly limited, and a prepolymer method, a one-shot, using a long-chain polyol, a chain extender, and a polyisocyanate compound and utilizing a known urethanization reaction. It may be produced by any of the methods. Among them, it is preferable to perform melt polymerization in the substantial absence of a solvent, and it is particularly preferable to produce by continuous melt polymerization using a multi-screw extruder.

  As the specific component (A) thermoplastic polyurethane, commercially available products may be used, such as Pandex T8295, T8290, T8260, T8295, and T8290 (all manufactured by DCI Bayer Polymer Co., Ltd.). Can be mentioned.

Next, with respect to the polyisocyanate compound used as the component (B), at least a part of the resin blend of one kind of resin pellets used remains all the isocyanate groups in one molecule unreacted. It is necessary to do. That is, it suffices if there is a polyisocyanate compound in which all the isocyanate groups in one molecule are completely free in a single resin compound. A polyisocyanate compound in a free state may coexist.

  Although there is no restriction | limiting in particular as this polyisocyanate compound, Various isocyanate can be employ | adopted, Specifically, 4,4'- diphenylmethane diisocyanate, 2, 4- (or) 2, 6-toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthylene 1,5-diisocyanate, tetramethylxylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, trimethylhexamethylene diisocyanate, 1 type (s) or 2 or more types selected from the group which consists of dimer acid diisocyanate can be used. Adoption of 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate among the above isocyanate groups affects the moldability due to an increase in viscosity associated with the reaction of the component (A) with the thermoplastic polyurethane. And a balance with the physical properties of the obtained golf ball cover material.

  In the present invention, although not an essential component, a thermoplastic elastomer other than the thermoplastic polyurethane can be blended as the component (C) in the components (A) and (B). By blending the component (C) with the resin blend, various physical properties required for a golf ball cover material such as further improvement in fluidity, resilience, and abrasion resistance of the resin blend can be enhanced. .

  Specific examples of the thermoplastic elastomer other than the thermoplastic polyurethane as the component (C) include polyester elastomer, polyamide elastomer, ionomer resin, styrene block elastomer, hydrogenated styrene butadiene rubber, styrene-ethylene / butylene-ethylene block. Copolymer or modified product thereof, ethylene-ethylene / butylene-ethylene block copolymer or modified product thereof, styrene-ethylene / butylene-styrene block copolymer or modified product thereof, ABS resin, polyacetal, polyethylene and nylon resin It is chosen and the 1 type (s) or 2 or more types can be used. In particular, it is preferable to employ a polyester elastomer, a polyamide elastomer and a polyacetal for reasons such as improving the resilience and scratch resistance by reaction with an isocyanate group while maintaining good productivity.

  The composition ratio of the components (A), (B) and (C) is not particularly limited, but in order to exhibit the effects of the present invention sufficiently effectively, (A) :( B) in mass ratio. : (C) = 100: 2 to 50: 0 to 50, preferably (A) :( B) :( C) = 100: 2 to 30: 8 to 50 (mass ratio) It is to be.

  In this invention, (A) component and (B) component, and also (C) component are mixed, and a resin compound is created, In that case, all the isocyanate is included in at least one part among polyisocyanate compounds. It is necessary to select conditions such that there is a polyisocyanate compound in which groups remain in an unreacted state. For example, it is necessary to take measures such as mixing in an inert gas such as nitrogen gas or in a vacuum state. This resin compound is then injection-molded around the core arranged in the mold, but for reasons of smooth and easy handling, it has a length of 1 to 10 mm and a diameter of 0.5 to 5 mm. It is preferable to form in a pellet form. In the resin pellets, unreacted isocyanate groups remain, and the unreacted isocyanate groups are converted into components (A) and (C) by post-treatment such as during the injection molding on the core and subsequent annealing. Reacts with ingredients to form a cross-linked product.

  Furthermore, various additives other than the components constituting the thermoplastic polyurethane can be blended with the resin blend as necessary. For example, pigments, dispersants, antioxidants, light stabilizers. , Ultraviolet absorbers, release agents and the like can be appropriately blended.

  The melt mass flow rate (MFR) value at 210 ° C. of the resin blend is not particularly limited, but is preferably 5 g / 10 min or more, more preferably 6 g / 10 min or more from the viewpoint of improving fluidity and productivity. . When the melt mass flow rate of the resin compound is small, the fluidity is lowered, which not only causes eccentricity at the time of injection molding, but also may reduce the degree of freedom of the cover thickness that can be molded. In addition, the measured value of said melt mass flow rate is a measured value based on JIS-K7210 (1999 edition).

  As a method of forming the cover layer, for example, the cover layer can be formed by supplying the above-mentioned resin compound to an injection molding machine and injecting the molten resin compound around the core. In this case, although it changes with kinds, such as thermoplastic polyurethane, as a molding temperature, it is the range of 150-250 degreeC normally.

  In addition, when performing injection molding, purging or vacuuming with an inert gas such as nitrogen or a low temperature gas such as low dew point dry air at a part or all of the resin path from the resin supply part into the mold. Although it is desirable to perform molding in a low humidity environment, the present invention is not limited to this. Moreover, as a pressure feeding medium at the time of resin conveyance, low-humidity gas such as low dew point dry air or nitrogen gas is preferable, but is not limited thereto. By molding in the above-mentioned low humidity environment, the progress of the reaction of isocyanate groups before the resin is filled inside the mold is suppressed, and a polyisocyanate in a form in which the isocyanate groups are unreacted to some extent is formed into a resin molded product. By including in, it can reduce the fluctuation factors such as an unnecessary increase in viscosity, and can improve the substantial crosslinking efficiency.

  In addition, as a method for confirming the presence of the unreacted polyisocyanate compound in the resin compound before injection molding around the core, it is confirmed by extracting with an appropriate solvent that selectively dissolves only the polyisocyanate compound. However, as a simple method, a method of confirming by simultaneous differential thermothermal gravimetric measurement (TG-DTA measurement) in an inert atmosphere can be mentioned. For example, when the resin compound (cover material) used in the present invention is heated at a heating rate of 10 ° C./min in a nitrogen atmosphere, a moderate weight reduction of diphenylmethane diisocyanate is confirmed from about 150 ° C. Can do. On the other hand, in the resin sample in which the reaction between the thermoplastic polyurethane material and the isocyanate mixture is completely performed, the weight reduction from about 150 ° C. is not confirmed, and the weight reduction from about 230 to 240 ° C. can be confirmed.

  After the resin composition is molded as described above, annealing is performed to further advance the crosslinking reaction, and the characteristics as a golf ball cover can be further improved. Annealing means aging for a certain period in a certain environment.

  One or more cover layers constituting the golf ball of the present invention are formed of the thermoplastic polyurethane composition, but at least one of the cover layers is formed of the thermoplastic polyurethane composition. The surface hardness is generally 30 to 90, preferably 35 to 85, more preferably 40 to 80, and still more preferably 45 to 75 in terms of durometer D-type hardness. If the surface hardness of the cover layer is too low, the spin rate at the time of driver hitting may increase and the flight distance may decrease. Further, if the surface hardness of the cover layer is too high, the feeling may be deteriorated and the resilience performance and durability performance of the urethane material may be inferior.

  In the present invention, the durometer D-type hardness means a hardness measured by a type D durometer in accordance with JIS K7215.

  The rebound resilience of the cover layer is usually 35% or more, preferably 40% or more, more preferably 45% or more, and still more preferably 47% or more. Since thermoplastic polyurethane is not so excellent in resilience from the beginning, it is preferable to strictly select the resilience modulus. If the rebound resilience of the cover layer is too low, the flight distance of the golf ball may be significantly reduced. Also, if the rebound resilience of the cover layer is too high, the initial speed may become too high for shots and puttings that require control within 100 yards, which may not match the golfer's feeling. In the present invention, the rebound resilience refers to a rebound resilience based on JIS K7311.

  The Shore D hardness on the surface of the cover layer is 50 or more, preferably 53 or more, more preferably 56 or more, still more preferably 58 or more, and most preferably 60 or more, and the upper limit is 70 or less, preferably 68 or less, More preferably, it is 66 or less, and the most preferable is 65 or less. If the cover hardness is too soft, the spin may be applied too much, the rebound will be insufficient and the flight distance may be reduced, and the scratch resistance may be deteriorated. On the other hand, if it is too hard, durability against cracking due to repeated hitting may deteriorate, and the hit feeling of short games and putters may deteriorate. The Shore D of the cover is a value measured by a Type D durometer based on ASTM D2240.

  The bending rigidity of the cover material is 50 MPa or more, preferably 60 Mpa or more, more preferably 70 MPa or more, and the upper limit is 300 MPa or less, preferably 280 MPa or less, more preferably 260 MPa or less, and most preferably 240 MPa or less. With this, a cover material suitable for approach spin performance and controllability can be provided by lowering the bending rigidity for a hard cover.

  From the viewpoint of spin characteristics by the driver, the core surface hardness is preferably smaller than the cover surface hardness. Specifically, the difference in surface hardness between the two is 1 or more, preferably 2 or more, in Shore D hardness. Is adjusted within the range of 5 or more and 15 or less as an upper limit, preferably 13 or less, more preferably 11 or less.

  Regarding the thickness of the cover, the lower limit is 0.5 mm, preferably 0.8 mm, more preferably 1.1 mm, still more preferably 1.4 mm, and most preferably 1.7 mm. The upper limit of the cover thickness is 2.5 mm or less, preferably 2.3 mm or less, more preferably 2.1 mm or less, and most preferably 2.0 mm or less. If the cover is too thin, the durability against cracking due to repeated impacts may deteriorate, or the resin may not easily turn to the apex portion due to injection molding, resulting in poor sphericity. On the other hand, if the cover is too thick, when hit with W # 1, the spin increases and the flight distance may not be obtained, or the hit feeling may become hard.

  The cover layer in the present invention may be a single layer or a plurality of layers of two or more layers. When the cover is formed in a plurality of layers, it is necessary to set the hardness of the outer cover and the total thickness of the cover within the above ranges. Moreover, the formation method is a known method such as a method of directly injection-molding the core, or a method of forming two half cups in a hemispherical shell in advance, covering the core with these cups, and pressurizing and heating. The method can be adopted.

  A large number of dimples are formed on the surface of the golf ball of the present invention (the surface of the cover layer). In this case, the number of dimples is 250 or more, preferably 270 or more, more preferably 290 or more, and most preferably. Is 310, and the upper limit is 450 or less, preferably 440 or less, more preferably 420 or less, and most preferably 400 or less. In the present invention, this range is easily subjected to lift, and in particular, the flight distance with a driver can be increased. The dimple is preferably formed in a planar circular shape from the viewpoint of obtaining an appropriate trajectory, and the average diameter is 3.5 mm or more, preferably 3.6 mm or more, more preferably 3.8 mm or more, and the upper limit is 5. 0 mm or less, preferably 4.7 mm or less, more preferably 4.5 mm or less, and most preferably 4.3 mm or less, and the average depth is 0.125 mm or more, preferably 0.130 mm or more, more preferably 0. 133 mm or more, most preferably 0.135 mm or more, and the upper limit is 0.170 mm or less, preferably 0.160 mm or less, more preferably 0.150 mm or less, and most preferably 0.148 mm or less. Further, the dimples are 4 types or more, preferably 5 types or more, more preferably 6 types or more, having different diameters and / or depths, and the upper limit is not particularly limited, but is preferably 20 types or less, more preferably 15 types. In the following, it is recommended that the number is 12 or less, and most preferably 9 or less.

  The average depth is an average value of the depths of all the dimples. The measurement of the diameter of the dimple is a position where the dimple portion is in contact with the land portion (a portion where no dimple is formed), that is, the diameter (passage) between the highest points of the dimple portion. In many cases, a golf ball is painted, but in such a ball, the dimple diameter is in a paint-coated state. The measurement of the dimple depth is a vertical distance from the center position to the bottom (deepest position) of the dimple when the imaginary plane is drawn by connecting the land joint positions of the dimple.

  The surface of the solid golf ball of the present invention can be subjected to marking, painting, and surface treatment as necessary.

  The deformation amount when the solid golf ball of the present invention is loaded from an initial load of 10 kgf to a final load of 130 kgf is 2.0 mm or more, preferably 2.2 mm or more, more preferably 2.4 mm or more, and further preferably 2.5 mm. The upper limit is 2.9 mm or less, preferably 2.8 mm or less.

  The solid golf ball of the present invention may be in compliance with golf rules for competition purposes, and may be formed with a diameter of 42.67 mm or more and a weight of 45.93 g or less. The upper limit of the diameter is usually 44.0 mm or less, preferably 43.8 mm or less, more preferably 43.5 mm or less, and most preferably 43.0 mm or less. Further, the lower limit of the weight is usually 44.5 g or more, preferably 45.0 g or more, more preferably 45.1 g or more, and further preferably 45.2 g or more.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Examples 1-9, Comparative Examples 1-8]
No. shown in Table 3 1-No. After adjusting the core composition by blending any one of 11, the solid core was prepared by vulcanization molding under the vulcanization conditions shown in Table 3. For this core, a single-layer cover layer was formed by injection molding using one of the a , b , c , and d types shown in Table 4, and a cover was formed around the solid core. . Then, a two-piece solid golf ball in which dimple types I (330 pieces), II (432 pieces), and III (500 pieces) were formed by combining various types of dimples was created.

In Examples and Comparative Examples using a and b type cover formulations, each raw material (unit: part by mass) shown in Table 4 was kneaded in a nitrogen gas atmosphere by a twin screw extruder, and a cover resin formulation was prepared. I got a thing. This resin blend was in the form of a pellet having a length of 3 mm and a diameter of 1 to 2 mm.

  Then, the solid core was placed in an injection mold, and the cover material was injection molded around the core to obtain a two-piece golf ball having a cover. Regarding the cover physical properties, the sheet having a predetermined thickness obtained by injection molding was subjected to an annealing treatment at 100 ° C. for 8 hours, and further left to stand at room temperature for 1 week, and then the cover physical properties were measured.

On the other hand, in Comparative Example 7 using the c type, the solid core was placed in an injection mold, and a thermoplastic polyurethane pellet and an isocyanate mixture pellet were dry blended around the core. The two-piece golf ball having a cover was obtained by injection molding. Subsequent processing was performed in the same manner as described above. In Comparative Example 8 using the d type, pellets made solely of thermoplastic polyurethane were injection molded alone and were not annealed.

＊表中のコア配合の数字は「質量部」を示す。

* The number of the core composition in the table indicates “part by mass”.

  In addition, the brand name of the main material described in the table | surface is as follows.

BR11
Polybutadiene rubber: Ni-based catalyst, cis-1,4 bond content 96%, 1,2 vinyl content 2.0%, Mooney viscosity 43, Mw / Mn = 4.1; manufactured by JSR

BR730
Polybutadiene rubber: Nd-based catalyst, cis-1,4 bond content 96%, 1,2 vinyl content 1.3%, Mooney viscosity 55, Mw / Mn = 3; manufactured by JSR

Perhexa C-40
1,1-bis (t-butylperoxy) cyclohexane 40% diluted; manufactured by NOF Corporation “Perhexa C-40” is a 40% diluted product, so the actual addition amount is shown in the above table.

Park Mill D
Dicumyl peroxide: manufactured by NOF Corporation

・ Zinc oxide: manufactured by Sakai Chemical Co., Ltd. ・ Anti-aging agent: 2,2′-methylene-bis (4-methyl-6-tert-butylphenol) “NOCRAK NS-6”; manufactured by Ouchi Shinsei Chemical Co., Ltd./acrylic acid Zinc: manufactured by Nippon Distillation Co., Ltd. Zinc stearate: manufactured by Nippon Oil & Fats Co., Ltd.

＊表中の数字は「質量部」を示す。

* The numbers in the table indicate “parts by mass”.

  In addition, the brand name of the main material described in the table | surface is as follows.

"Pandex T8260"
MDI-PTMG type thermoplastic polyurethane material, durometer D type resin hardness “56”, rebound resilience 45%
"Pandex T8295"
MDI-PTMG type thermoplastic polyurethane material, resin hardness JIS-A "97", rebound resilience 44%

Isocyanate compound 4,4'-diphenylmethane diisocyanate

Isocyanate mixture crossnate EM-30 (isocyanate masterbatch manufactured by Dainichi Seika Kogyo Co., Ltd., containing 30% 4,4'-diphenylmethane diisocyanate. The masterbatch base resin is a polyester elastomer)

Thermoplastic elastomer Thermoplastic polyetherester elastomer ("Hytrel 4001" manufactured by Toray DuPont) is used.

Polyethylene wax “Sun Wax 161P” (manufactured by Sanyo Chemical Co., Ltd.)
Montan wax "Lico wax E" (manufactured by Clariant Japan)

Melt mass flow rate (MFR)
Melt flow rate (or melt index) of the material measured according to JIS-K7210 (test temperature 210 ° C., test load 21 N (2.16 kgf)).

  Further, for each of the obtained golf balls of Examples 1 to 9 and Comparative Examples 1 to 8, the amount of deflection of the ball and the physical properties of the ball, the flying performance, the approach spin, the scratch resistance, the hit feeling, and the productivity of the ball are shown. evaluated. The results are shown in Tables 5 and 6.

Solid core hardness distribution (Shore D hardness)
After adjusting the temperature to 23 ° C., both hardnesses were measured by Shore D hardness (ASTM-2240 standard durometer type D).
-Surface hardness shows the average value of the value which measured each arbitrary 2 points | pieces of five core surfaces at random.
-Center hardness shows the average value of the hardness of the center part of the cross section of two hemispheres of each of five cores, when a core is cut in half with a fine cutter.
-Each cross-sectional hardness shows the average value of the hardness of the applicable part of the cross section of two hemispheres of each of five cores, when a core is cut in half.

After controlling the temperature of the cover layer to a surface hardness of 23 ° C., the bank portion without dimples on the surface of five products was randomly measured at two points on each surface. It was measured by a durometer “type D” of ASTM-2240 standard.

Rebound resilience of the cover material The impact resilience according to JIS-K7311 was measured.

Deflection amount of solid core and product Using Instron Corporation model 4204, compress the solid core and product at a speed of 10 mm / min, and measure the difference between the deformation amount at 10 kg and the deformation amount at 130 kg did.

The initial speed and initial speed were measured using an initial speed measuring device of the same type as the USGA drum rotation type initial speed meter approved by R & A. The balls were conditioned at a temperature of 23 ± 1 ° C. for more than 3 hours and tested in a room at room temperature 23 ± 2 ° C. The ball was hit at a hitting speed of 143.8 ft / s (43.83 m / s) using a 250 pound (113.4 kg) head (striking mass). One dozen balls were hit four times, and the time required to pass between 6.28 ft (1.91 m) was measured, and the initial speed was calculated. This cycle was performed in about 15 minutes.

Total distance when a flying driver (Bridgestone Sports, Tour Stage X-DRIVE TYPE350 PROSPEC, loft angle 8 °) is mounted on a swing robot (Miyamae) and hit at a head speed (HS) of 45 m / s. Was measured. The spin amount is a value obtained by measuring a ball immediately after hitting with a high-speed camera.

Using an approach spin sand wedge (SW) (manufactured by Bridgestone Sports Co., Ltd., Tour Stage X-wedge, loft angle 58 °), the amount of spin when hit with HS 20 m / s was measured. The spin amount was measured by the same method as the above flight distance measurement.
It is.

Feel 10 amateur golfers to hit with a driver to tee up, also, was hit with a putter, it was evaluated as follows by the number of people who answered "soft" for the feel of that time. The driver used was Bridgestone Sports, X-DRIVE TYPE350 PROSPEC, with a loft angle of 10 °, and the putter was Tour Stage ViQ Model-III.
・ Evaluated as “bad” (×) when 1 to 3 people judged to be soft.
-The case where 4-6 persons judged that it was soft was evaluated as "normal" ((triangle | delta)).
-The case where 7-10 persons judged that it was soft was evaluated as "good" ((circle)).

Scratch resistance (crust resistance)
Using a swing robot machine, the club uses a pitching wedge (square groove specification), adjusts the temperature of each ball to 23 ° C, hits the ball at a head speed of 33 m / s, and the ball condition is determined by the following three standards. Visual evaluation was performed and the average value was quantified.
10 points No scratches at all.
8 points I don't really care.
5 points.
3 points Can be used somehow.
1 point Cannot be used at all.

In the ball productivity comparative examples 8 and 9, the molding conditions were unstable in mass production, and the occurrence frequency of resin burns was high. For other examples and comparative examples, the molding conditions were stable in mass production, and there was little occurrence of resin burns and the like.

  From the results of Tables 5 and 6, in Comparative Example 1, the ball product hardness was too hard, the hit feeling was hard, the spin was too much, and the flight distance was reduced. In Comparative Example 2, the ball product hardness was too soft, the resilience was low, the flight distance was reduced, and the approach performance was low. In Comparative Example 3, the hardness distribution of the core was small, the spin was increased, the flight distance was decreased, and the resilience was also decreased. In Comparative Example 4, the cover was too thick, the resilience was not obtained, and the flight distance was reduced. In Comparative Example 5, the cover was softer than the core surface, the spin was too much, and the flight distance was reduced. In Comparative Example 6, since nickel catalyst-based polybutadiene rubber was used as the core material, the resilience was low and the flight distance was deteriorated. In Comparative Example 7, the cover material was a material obtained by injection molding of each of the thermoplastic polyurethane pellets and the isocyanate mixture pellets which were dry blended, and the scratch resistance was poor. In Comparative Example 8, as a cover material, a pellet made of only thermoplastic polyurethane was used alone, and the abrasion resistance was very poor.

Claims (17)

A solid golf ball comprising a solid core and a cover layer covering the solid core, wherein a plurality of dimples are formed on the outer surface of the outermost layer of the cover layer, wherein the solid core is a cis-1,4-bond In an amount of 0.1 to 5 parts by weight of an organic sulfur compound and 100% by weight of an unsaturated carboxylic acid, based on 100 parts by weight of a rubber base material containing 60 to 100 parts by weight of a polybutadiene rubber synthesized using a rare earth element catalyst. It is formed from a rubber composition containing an acid or a metal salt thereof, an organic peroxide, and an inorganic filler, and the deformation amount when the solid core is loaded from an initial load of 10 kgf to a final load of 130 kgf is 2.0 to 3.5 mm. , and the and the solid core has a hardness distribution in the following table, the cover layer, the respective raw materials of (a) a thermoplastic polyurethane and (B) a polyisocyanate compound not Kneaded with sex gas atmosphere or vacuum, and the above (A) and that one kind of resin pellets of the (B) from the resin formulations as a main component is formed by injection molding, injection molding immediately before In the resin pellets put into the injection molding machine, at least a part of the polyisocyanate compound in which all isocyanate groups in one molecule remain unreacted exists, and the cover layer The thickness of the golf ball is 0.5 to 2.5 mm, the surface hardness is Shore D hardness 50 to 70, the core surface hardness is smaller than the cover surface hardness within the range of Shore D hardness 1 to 15, A solid golf ball having a deformation amount of 2.0 to 2.9 mm when an initial load of 10 kgf to a final load of 130 kgf is applied.

  The solid golf ball according to claim 1, wherein the solid core has a diameter of 37.6 to 43.0 mm, and the golf ball has a diameter of 42.67 to 44.0 mm.   In the solid core, the amount of unsaturated carboxylic acid or metal salt thereof is 30 to 45 parts by weight, the amount of organic peroxide is 0.1 to 0.5 parts by weight, and the inorganic filler is 100 parts by weight of rubber base material. The solid golf ball according to claim 1, wherein the blending amount is 5 to 80 parts by mass and 0 to 0.2 parts by mass of the antioxidant is blended.   4. The solid golf ball according to claim 1, wherein a hardness difference between any two portions in a portion of 5 mm to 10 mm from the center of the solid core is within ± 2 in Shore D hardness.   In the above dimples, the total number of the dimples is 250 to 450, the average depth of all the dimples is 0.125 to 0.170 mm, the average diameter is 3.5 to 5.0 mm, and the dimples are configured with four or more types. Item 5. The solid golf ball according to any one of Items 1 to 4.   The solid golf ball according to claim 1, wherein (C) a thermoplastic elastomer other than the thermoplastic polyurethane is further blended with the resin blend.   In the resin blend, a part of the isocyanate group of the component (B) forms a bond with active hydrogen in the component (A) and / or the component (C), and the other isocyanate groups remain in an unreacted state. The solid golf ball according to claim 6 remaining in the inside.   The solid golf ball according to claim 6 or 7, wherein the composition ratio of each component is (A) :( B) :( C) = 100: 2 to 50: 0 to 50 in terms of mass ratio.   The solid golf ball according to claim 6 or 7, wherein the composition ratio of each component is (A) :( B) :( C) = 100: 2 to 30: 8 to 50 in terms of mass ratio.   The solid golf ball according to claim 1, wherein the total mass of the component (A) and the component (B) is 90% by mass or less of the mass of the entire cover layer.   The solid golf ball according to claim 1, wherein the resin composition has a melt mass flow rate (MFR) value at 210 ° C. of 5 g / 10 min or more. The component (B) is 4,4′-diphenylmethane diisocyanate, 2,4- (or) 2,6-toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthylene 1,5-diisocyanate, tetramethylxylene diisocyanate, water Attachment xylylene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, trimethylhexamethylene diisocyanate, one or on two or more kinds or Ranaru polyisocyanate selected from the group consisting of dimer acid diisocyanate The solid golf ball according to claim 1, which is a compound.   The component (B) is one or two or more polyisocyanate compounds selected from the group consisting of 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate. Solid golf ball. Component (C) is polyester elastomer, polyamide elastomer, ionomer resin, styrene block elastomer, hydrogenated styrene butadiene rubber, styrene-ethylene / butylene-ethylene block copolymer or a modified product thereof, ethylene-ethylene / butylene-ethylene block One or more thermoplastic elastomers selected from the group consisting of a polymer or a modified product thereof, a styrene-ethylene butylene-styrene block copolymer or a modified product thereof, ABS resin, polyacetal, polyethylene and nylon resin solid golf ball according to any one of a certain claim 6 to 13.   The solid golf ball according to claim 14, wherein the component (C) is one or more thermoplastic elastomers selected from the group consisting of polyester elastomers, polyamide elastomers, and polyacetals. The solid golf ball of any one of claims 1 to 15 melt mass flow rate (MFR) of value at 210 ° C. of the resin formulation is 5 g / 10min or more. The solid golf ball of any one of claims 1 to 16 modulus of repulsion elasticity conforming to JIS K7311 of the cover layer is 47% or more.