JP2010279803A - Multi-piece solid golf ball - Google Patents

Abstract

A rubber base comprising a polybutadiene synthesized using a rare earth element catalyst, a small amount of an organic peroxide, an unsaturated carboxylic acid and / or a metal salt thereof, an organic sulfur compound, and an inorganic filler. A multi-piece solid, wherein the intermediate layer comprising at least one layer is formed from a thermoplastic resin composition, and the cover is formed mainly from a thermoplastic polyurethane material. Golf ball.
[Effects] According to the present invention, a multi-piece solid golf ball having excellent flight performance, softness of hitting, and excellent abrasion resistance of a cover and coating film as compared with a conventional golf ball. Obtainable.
[Selection] Figure 1

Description

  The present invention relates to a golf ball having excellent flight performance, soft feel, and excellent scuff resistance of a cover and excellent wear resistance of a coating film.

  Conventionally, golf balls having various structures have been proposed. Particularly, a solid golf ball, particularly a multi-piece solid golf ball in which a solid core is covered with a plurality of layers in terms of flight distance, controllability (spin amount), and feeling. Many proposals have been made, and the applicant has previously proposed many excellent golf balls.

For example, in Japanese Patent Laid-Open No. 9-215775, by optimizing the moment of inertia of the ball according to the outermost layer cover hardness and by optimizing the dimple mode, the flight distance, controllability, straightness on the green, and A multi-piece solid golf ball having a superior durability and a cover having excellent durability, Japanese Patent Application Laid-Open No. 10-151225 discloses that the specific gravity of the solid core is smaller than that of any of the intermediate layer and the cover, and the intermediate layer By making the Shore D hardness of the cover higher than the Shore D hardness of the cover and making the moment of inertia of the entire three-layer ball 83 gcm ² or more, a soft feel without reducing the flight distance and durability. Depending on the type of club, it can exhibit good spin performance, flight distance, durability, feel and spin control. Japanese Patent Application Laid-Open No. 10-151226, a high-performance golf ball with excellent rollability, prepares a solid core so that the deformation amount when loaded with 100 kgf is 2.5 mm or more, and the Shore D hardness of the intermediate layer By making the moment of inertia of the entire ball consisting of these three layers 83 gcm ² or more with a soft feel without reducing the flying distance and durability, A high-performance golf ball that can exhibit good spin performance depending on the type of club and has excellent flight distance, durability, feel, and spin control. Japanese Patent Application Laid-Open No. 11-104273 discloses a solid core with a 100 kgf load. The deformation amount under load is 2.4 mm or more, and the inner cover layer has an ionomer resin as a main material and has a Shore D hardness of 28 to 58. The outer cover layer is made of thermoplastic polyurethane elastomer as a main material and has a Shore D hardness of 30 to 55, so that the flight distance is large and the controllability in the iron shot is high, and the wood, iron, and putter A golf ball that has a good feeling when shot with any of the clubs, and has excellent resistance to tearing and excellent durability when controlled shots with an iron. Japanese Patent Application Laid-Open No. 2001-54588 discloses a solid The deformation amount of the core when loaded with 30 kgf is 1.1 mm or more, the Shore D hardness of the inner layer cover is 45 to 61, the Shore D hardness of the outer layer cover is 35 to 55, and the dimple diameter is in the dimple volume. Of the dimple ballistic volume obtained by multiplying the square root of By setting the sum to 530 to 750, it has a relatively low trajectory and a flying performance with a long trajectory, a large flight distance, and high controllability in iron shots, and shots in any club of wood, iron, and putter In the case of golf balls that have a good feeling even when controlled, and have excellent resistance to tearing when controlled by an iron, and excellent durability, Japanese Patent Application Laid-Open Nos. 2002-85587 to 2002-85589 Excellent flying performance, good spin characteristics, good feeling even when shot with wood, iron, or putter clubs, and excellent resistance to crushing and durability when shot with iron Each golf ball has excellent properties.

  However, these golf balls all have excellent hit feeling and flight distance performance, and can respond suitably to various requests such as the skill and use of the player, but the player's request is still high, There is a need for golf balls having excellent performance.

JP-A-9-215775 Japanese Patent Laid-Open No. 10-151225 Japanese Patent Laid-Open No. 10-151226 Japanese Patent Laid-Open No. 11-104273 JP 2001-54588 A JP 2002-85588 A JP 2002-85589 A JP 2002-85587 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a multi-piece solid golf ball having excellent flight performance, soft feel, and excellent abrasion resistance of a cover and coating film. To do.

  As a result of intensive studies to achieve the above object, the present inventor, in a multi-piece solid golf ball comprising a solid core, at least one intermediate layer and a cover, is formed from a specific rubber composition. And a solid core having a specific flexibility and diameter, at least one intermediate layer formed from a specific thermoplastic resin composition and having a specific thickness and hardness, and a specific resin composition In addition, the multi-piece solid golf ball is combined with a cover having a specific thickness and hardness, and the flexibility of the multi-piece solid golf ball as a whole is within a specific range, so that it can be compared with a conventional golf ball. Multi-piece solid rubber with very good flying performance, high abrasion resistance of the cover, abrasion resistance of the coating film, and soft feel It was found that Fuboru obtained, leading to completion of the present invention.

That is, the present invention provides the following multi-piece solid golf ball.
Claim 1:
In a multi-piece solid golf ball comprising a solid core, an intermediate layer, and a cover,
The solid core contains 60% or more of (A) a cis-1,4-bond and contains 100 to 100 parts by weight of a polybutadiene synthesized using a rare earth element catalyst. (B) Two or more organic peroxides having different half-lives, the organic peroxide having the shortest half-life at 155 ° C. (a) The organic peroxide having the longest half-life at 155 ° C. was a (b), half-life a _t of (a), when the half-life of (b) and b _t, a _t is 5 seconds to 120 seconds or less, b _t is 800 seconds or less than 300 seconds, the an organic peroxide ratio b _t / a _t half-life of 7 to 20 or less, the (a) additive amount of component (a) 0.05 part by mass or more with respect to 100 parts by weight of component 0. 5 parts by mass or less, and the amount of component (b) added is 0.05 parts by mass or more with respect to 100 parts by mass of component (A). 0.7 parts by mass or less, and the total amount of components (a) and (b) is 0.1 to 0.8 parts by weight, (C) unsaturated carboxylic acid and / or metal salt thereof, (D) organic sulfur Compound, (E) formed from a rubber composition containing an inorganic filler, the deformation of the solid core when loaded with 980N (100 kgf) is 3.0 to 6.0 mm, and the diameter of the solid core is 30 ~ 40mm and
The intermediate layer comprises (P) an olefin-unsaturated carboxylic acid binary random copolymer and / or a metal ion neutralized product of an olefin-unsaturated carboxylic acid binary random copolymer, and (Q) an olefin-unsaturated product. 100: 0 to mass ratio of carboxylic acid-unsaturated carboxylic acid ternary random copolymer and / or metal ion neutralized product of olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ternary random copolymer. With respect to 100 parts by mass of a resin component formulated such that the base resin blended so as to be 25:75 and the (T) non-ionomer thermoplastic elastomer are blended so that the mass ratio is 100: 0 to 50:50, R) Fatty acid having a molecular weight of 280 to 1500 and / or 5 to 80 parts by mass of a derivative thereof, and (S) a base capable of neutralizing an unneutralized acid group in the base resin and (R) component A thermoplastic resin composition containing 0.1 to 10 parts by mass of an inorganic metal compound as an essential component is formed as a main material, and the intermediate layer has a thickness of 0.5 to 2.0 mm, and the intermediate layer The Shore D hardness of the layer is 20-60,
The cover is formed of (F) a thermoplastic polyurethane material as a main component, and the (F) thermoplastic polyurethane material comprises (M) a thermoplastic polyurethane and (N) an isocyanate mixture, and (N) an isocyanate. (N-1) An isocyanate compound having two or more isocyanate groups as functional groups in one molecule, and (N-2) an isocyanate dispersed in a thermoplastic resin that does not substantially react with the isocyanate group. The cover has a thickness of 0.5 to 2.5 mm, and the cover has a Shore D hardness of 50 to 70, and the above (intermediate layer Shore D hardness) ≦ (cover Shore D hardness) There,
Moreover, the multi-piece solid golf ball comprising the solid core, the intermediate layer, and the cover has a deformation amount of 3.0 to 5.0 mm when loaded with a load of 980 N (100 kgf). Peace solid golf ball.
Claim 2:
The rubber composition contains 60% or more of the (A) cis-1,4-bond and contains 100 to 100 parts by weight of a polybutadiene synthesized using a rare earth element-based catalyst. 10-60 parts by weight of the (C) unsaturated carboxylic acid and / or metal salt thereof, (D) 0.1-5 parts by weight of the organic sulfur compound, and (E) 5-80 parts by weight of the inorganic filler. The multi-piece solid golf ball according to claim 1, comprising:
Claim 3:
The cover has a coating film on the surface, the coating film contains a hydroxyl group-containing polyester obtained by reacting a polyhydric alcohol component and a polybasic acid component, and a non-yellowing polyisocyanate, The multi-piece solid golf ball according to claim 1, wherein at least a part of the alcohol component is formed of a golf ball coating composition having an alicyclic structure in the molecule.
Claim 4:
The ratio of the total volume of the dimple space below the plane surrounded by the edge of each dimple to the volume of the phantom sphere assuming that the cover has a large number of dimples on the surface and there is no dimple on the cover surface (occupying the dimple volume) Ratio) VR is 0.70 to 1.00%, and the ratio of the total area of the phantom spherical surface surrounded by the edge of each dimple to the surface area of the phantom sphere (dimple surface occupancy ratio) SR is 70 to 85%. The multi-piece solid golf ball according to claim 1, 2 or 3.
Claim 5:
5. The multi-piece solid golf ball according to claim 1, wherein the (A) polybutadiene has a Mooney viscosity (ML _{1 + 4} (100 ° C.)) of 50 or more and 120 or less.
Claim 6:
In a multi-piece solid golf ball comprising a solid core, an intermediate layer, and a cover,
The solid core contains (A) 60% or more of cis-1,4-bonds, has a Mooney viscosity (ML _{1 + 4} (100 ° C.)) of 52 or more and 120 or less, and is synthesized using a rare earth element-based catalyst. (B) 0.1 to 0.8 part by weight of an organic peroxide, (C) an unsaturated carboxylic acid and / or its metal with respect to 100 parts by weight of a rubber base material containing 60 to 100% by weight of the polybutadiene prepared Formed from a rubber composition containing a salt, (D) an organic sulfur compound, and (E) an inorganic filler, and the deformation amount of the solid core when loaded with 980 N (100 kgf) is 3.0 to 6.0 mm, and The solid core has a diameter of 30 to 40 mm,
The intermediate layer comprises (P) an olefin-unsaturated carboxylic acid binary random copolymer and / or a metal ion neutralized product of an olefin-unsaturated carboxylic acid binary random copolymer, and (Q) an olefin-unsaturated product. 100: 0 to mass ratio of carboxylic acid-unsaturated carboxylic acid ternary random copolymer and / or metal ion neutralized product of olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ternary random copolymer. With respect to 100 parts by mass of a resin component formulated such that the base resin blended so as to be 25:75 and the (T) non-ionomer thermoplastic elastomer are blended so that the mass ratio is 100: 0 to 50:50, R) Fatty acid having a molecular weight of 280 to 1500 and / or 5 to 80 parts by mass of a derivative thereof, and (S) a base capable of neutralizing an unneutralized acid group in the base resin and (R) component A thermoplastic resin composition containing 0.1 to 10 parts by mass of an inorganic metal compound as an essential component is formed as a main material, and the intermediate layer has a thickness of 0.5 to 2.0 mm, and the intermediate layer The Shore D hardness of the layer is 20-60,
The cover is formed of (F) a thermoplastic polyurethane material as a main component, and the (F) thermoplastic polyurethane material comprises (M) a thermoplastic polyurethane and (N) an isocyanate mixture, and (N) an isocyanate. (N-1) An isocyanate compound having two or more isocyanate groups as functional groups in one molecule, and (N-2) an isocyanate dispersed in a thermoplastic resin that does not substantially react with the isocyanate group. The cover has a thickness of 0.5 to 2.5 mm, and the cover has a Shore D hardness of 50 to 70, and the above (intermediate layer Shore D hardness) ≦ (cover Shore D hardness) There,
Moreover, the multi-piece solid golf ball comprising the solid core, the intermediate layer, and the cover has a deformation amount of 3.0 to 5.0 mm when loaded with a load of 980 N (100 kgf). Peace solid golf ball.
Claim 7:
The rubber composition contains 60% or more of the (A) cis-1,4-bond and contains 100 to 100 parts by weight of a polybutadiene synthesized using a rare earth element-based catalyst. 10-60 parts by weight of the (C) unsaturated carboxylic acid and / or metal salt thereof, (D) 0.1-5 parts by weight of the organic sulfur compound, and (E) 5-80 parts by weight of the inorganic filler. The multi-piece solid golf ball according to claim 6, further comprising two or more organic peroxides (B).
Claim 8:
The cover has a coating film on the surface, the coating film contains a hydroxyl group-containing polyester obtained by reacting a polyhydric alcohol component and a polybasic acid component, and a non-yellowing polyisocyanate, The multi-piece solid golf ball according to claim 6 or 7, wherein at least a part of the alcohol component is formed of a golf ball coating composition having an alicyclic structure in the molecule.
Claim 9:
The ratio of the total volume of the dimple space below the plane surrounded by the edge of each dimple to the volume of the phantom sphere assuming that the cover has a large number of dimples on the surface and there is no dimple on the cover surface (dimple volume occupation Ratio) VR is 0.70 to 1.00%, and the ratio of the total area of the phantom spherical surface surrounded by the edge of each dimple to the surface area of the phantom sphere (dimple surface occupancy) SR is 70 to 85%. The multi-piece solid golf ball according to claim 6, 7 or 8.

  According to the present invention, it is possible to obtain a multi-piece solid golf ball that is extremely superior in flight performance as compared with conventional golf balls, has a soft feel, and has excellent abrasion resistance of the cover and abrasion resistance of the coating film. it can.

FIG. 5 is a schematic diagram illustrating an example of arrangement of dimple species A or C in Table 4. FIG. 5 is a schematic diagram illustrating an arrangement example of dimple species B in Table 4.

Hereinafter, the present invention will be described in more detail.
The solid core in the present invention has the following components,
(A) a rubber base material containing 60% or more of cis-1,4-bond and containing 60 to 100% by weight of polybutadiene synthesized using a rare earth element-based catalyst;
(B) an organic peroxide,
(C) an unsaturated carboxylic acid and / or a metal salt thereof,
(D) an organic sulfur compound,
(E) It is formed from a rubber composition containing an inorganic filler.

  In the rubber substrate containing 60 to 100% by weight of polybutadiene synthesized by using a rare earth element-based catalyst containing 60% or more of the above-mentioned (A) cis-1,4-bond in the present invention, the cis- The 1,4-bond content is 60% or more, preferably 80% or more, more preferably 90% or more, and most preferably 95% or more. When the content of cis-1,4-bonds contained in the polybutadiene is less than 60%, suitable resilience cannot be obtained.

  The polybutadiene in the present invention is synthesized with a rare earth element-based catalyst. As the rare earth element-based catalyst, known catalysts can be used. Examples thereof include a lanthanum series rare earth element compound, an organoaluminum compound, an alumoxane, a halogen-containing compound, and a catalyst comprising a combination of Lewis bases if necessary. be able to.

  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.

Also, when butadiene is polymerized in the presence of a rare earth element-based catalyst using a lanthanum series rare earth element compound, in order to make the cis content and Mw / Mn within the above ranges, the butadiene / lanthanum series rare earth element compound has a molar ratio. It is preferably 1,000 to 2,000,000, particularly 5,000 to 1,000,000, and the AlR ¹ R ² R ³ / lanthanum series rare earth element compound has a molar ratio of 1 to 1,000, particularly 3 to 3. 500 is preferable. Furthermore, the molar ratio of the halogen compound / lanthanum series rare earth element compound is preferably 0.1 to 30, and particularly preferably 0.2 to 15. The Lewis base / lanthanum series rare earth element compound is preferably in a molar ratio of 0 to 30, particularly 1 to 10. In the polymerization, a solvent may be used, or bulk polymerization or gas phase polymerization may be performed without using a solvent. The polymerization temperature is usually −30 to 150 ° C., preferably 10 to 100 ° C.

  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 to 150 ° C., preferably It can be 10-100 degreeC.

The Mooney viscosity (ML _{1 + 4} (100 ° C.)) of the polybutadiene is usually 40 or more, preferably 50 or more, more preferably 52 or more, most preferably 54 or more, and the upper limit is usually 140 or less, preferably 120 or less. More preferably, it is 100 or less, and most preferably 80 or less. When the Mooney viscosity is out of the above range, workability may be deteriorated or resilience may be reduced.

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. Further, M is Mooney viscosity, L is a large rotor (L type), 1 + 4 is a preheating time of 1 minute, and a rotor rotation time is 4 minutes, which is measured at 100 ° C.

  The polybutadiene in the present invention 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, a well-known thing can be used for a terminal modifier, and the terminal modifier described in following <1>-<7> can be used.
<1> First, a compound having an alkoxysilyl group is exemplified. 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.

（式中、Ｙは、酸素原子、チッ素原子又はイオウ原子を示す。）
〈５〉ハロゲン化イソシアノ化合物、
〈６〉Ｒ⁸−（ＣＯＯＨ）_m 、Ｒ⁹（ＣＯＸ）_m 、Ｒ¹⁰−（ＣＯＯ−Ｒ¹¹）_m 、Ｒ¹²−ＯＣＯＯ−Ｒ¹³、Ｒ¹⁴−（ＣＯＯＣＯ−Ｒ¹⁵）_m 、又は下記式で示されるカルボン酸、酸ハロゲン化物、エステル化合物、炭酸エステル化合物又は酸無水物、

（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。）
〈７〉Ｒ¹⁷ _l Ｍ″（ＯＣＯＲ¹⁸）_4-l 、Ｒ¹⁹ _lＭ″（ＯＣＯ−Ｒ²⁰−ＣＯＯＲ²¹）_4-l、又は下記式で示されるカルボン酸の金属塩

（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。）等を挙げることができる。 _{^{<2> 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,
<3> A heterocumulene containing a 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,
<4> Hetero 3-membered ring compound containing the following bond in the molecule;

(In the formula, Y represents an oxygen atom, a nitrogen atom or a sulfur atom.)
<5> halogenated isocyano compound,
^{<6> R 8 - (COOH} ) m, R 9 (COX) m, R 10 - (COO-R 11) m, R 12 -OCOO-R 13, R 14 - (COOCO-R 15) m, or the following Carboxylic acid, acid halide, ester compound, carbonate compound or acid anhydride represented by the formula:

(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.)
<7> 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

(Wherein R ^{17 to} R ²³ may be the same or different, a hydrocarbon group containing a carbon atom having 1 to 20 carbon atoms, M ″ is a tin atom, a silicon atom or a germanium atom, and l is 0 to 3) And the like.) And the like.

Specific examples of the terminal modifiers shown above and the reaction method include those described in JP-A-11-35633, JP-A-7-268132, JP-A-2002-293996, and the like. Can be mentioned.
Among the above-mentioned catalysts, rare earth element-based catalysts, particularly Nd-based catalysts are preferable.

  In the present invention, the polybutadiene has a molecular weight distribution Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) of 2.0 or more, preferably 2.2 or more, more preferably 2.4 or more, most preferably Preferably, it is 2.6 or more, and the upper limit is 8.0 or less, preferably 7.5 or less, more preferably 4.0 or less, and most preferably 3.4 or less, and Mw / Mn is small. If it is too large, the workability may be lowered, and if it is too large, the resilience may be lowered.

  The component (A) in the present invention is a rubber base material mainly composed of the above polybutadiene, and the content of polybutadiene in the main material is 60% by weight or more, preferably 70% by weight in the rubber base material. % Or more, more preferably 80% by weight or more, and most preferably 85% by weight or more. Further, 100% by weight of the rubber base material may be the polybutadiene, and the content may be 95% by weight or less, and in some cases 90% by weight or less. When the polybutadiene content is less than 60% by weight, the resilience is poor.

  Components other than polybutadiene contained in the component (A) include polybutadienes other than the above polybutadiene, such as polybutadiene obtained using a Group VIII metal compound catalyst, other diene rubbers such as styrene butadiene rubber, natural rubber, isoprene. Examples thereof include rubber and ethylene propylene diene rubber.

In this case, among the rubber components other than the above polybutadiene, it is synthesized using a Group VIII catalyst, and the Mooney viscosity (ML _{1 + 4} (100 ° C.)) is less than 50, and the viscosity of a 5 wt% toluene solution at 25 ° C. It is preferable to use the second polybutadiene having η of 200 mPa · s or more and 400 mPa · s or less because high resilience and good workability can be obtained.

Specific examples of the Group VIII catalyst include the following nickel-based catalysts and cobalt-based catalysts.
Here, examples of the nickel-based catalyst include a one-component system such as nickel diatomaceous earth, a two-component system such as Raney nickel / titanium tetrachloride, and a three-component system such as nickel compound / organometallic / boron trifluoride etherate. Can be mentioned. As the nickel compound, reduced nickel with support, Raney nickel, nickel oxide, nickel carboxylate, organic nickel complex salt, or the like is used. Examples of the organic metal include trialkylaluminum such as triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, and tri-n-hexylaluminum, n-butyllithium, sec-butyllithium, tert-butyllithium, 1, Examples include alkyl lithium such as 4-dilithium butane, and dialkyl zinc such as diethyl zinc and dibutyl zinc.

  In addition, as cobalt-based catalysts, cobalt and its compounds include Raney cobalt, cobalt chloride, cobalt bromide, cobalt iodide, cobalt oxide, cobalt sulfate, cobalt carbonate, cobalt phosphate, cobalt phthalate, cobalt carbonyl, cobalt acetyl. Examples thereof include acetonate, cobalt diethyldithiocarbamate, cobalt anilinium nitrite, cobalt dinitrosilkyl chloride and the like. -Trialkylaluminum such as n-propylaluminum, triisobutylaluminum, tri-n-hexylaluminum, ethylaluminum sesquik Aluminum alkyl sesquichloride of chloride etc., can be preferably exemplified a combination of aluminum chloride and the like.

  When the polymerization is performed using the above group VIII-based catalyst, particularly a nickel-based catalyst or a cobalt-based catalyst, usually, the reactor is continuously charged together with a solvent and a butadiene monomer, for example, the reaction temperature is 5 to 60 ° C, A method of operating the reaction pressure so as to obtain the Mooney viscosity can be exemplified by appropriately selecting the reaction pressure within the range of atmospheric pressure to 70 atm.

The Mooney viscosity of the second polybutadiene is less than 50, preferably 48 or less, more preferably 45 or less. In this case, the lower limit of Mooney viscosity is preferably 10 or more, more preferably 20 or more, still more preferably 25 or more, and most preferably 30 or more.
Further, the viscosity η of a 5 wt% toluene solution of the second polybutadiene at 25 ° C. is 200 mPa · s or more, more preferably 210 mPa · s or more, further preferably 230 mPa · s or more, particularly preferably 250 mPa · s or more, and 400 mPa · s. It is preferably s or less, more preferably 370 mPa · s or less, further preferably 340 mPa · s or less, particularly preferably 300 mPa · s or less.

  The viscosity η (mPa · s) of a 5% toluene solution at 25 ° C. referred to in the present invention is obtained by dissolving 2.28 g of polybutadiene to be measured in 50 ml of toluene, and then using a standard solution for constituting a viscometer (JIS) as a standard solution. Z8809) is a value measured under the condition of 25 ° C. with a predetermined viscometer.

  The blending amount of the second polybutadiene is 0% or more, preferably 5% or more, more preferably 10% or more, 40% or less, more preferably 30% or less, still more preferably 20% or less in the rubber substrate. The most preferable content is 15% or less.

Next, as the organic peroxide (B) in the present invention, it is preferable to use two or more kinds together. In this case, the organic peroxide having the shortest half-life at 155 ° C. is (a) 155 ° C. half-life is longest organic peroxide and (b) in the half-life of (a) a _t, the half-life of (b) when the b _t, as the ratio b _t / a _t half-life Is 7 or more, preferably 8 or more, more preferably 9 or more, still more preferably 10 or more, 20 or less, more preferably 18 or less, still more preferably 16 or less. Even when two or more organic peroxides are used, if they deviate from the above range, the resilience, compression, and durability may be inferior.

In this case, the as half-life a _t at 155 ° C. of (a) is 5 seconds or more, more preferably 10 seconds or more, more preferably 15 seconds or more, 120 seconds or less, more preferably 90 seconds or less, more preferably preferably is less than 60 seconds, the as half-life b _t at 155 ° C. of (b) is 300 seconds or more, more preferably 360 seconds or more, more preferably at least 420 seconds, 800 seconds or less, more preferably Is preferably 700 seconds or shorter, more preferably 600 seconds or shorter.

  Specific examples of the organic peroxide include dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, α, α′-bis (t-butylperoxy). ) Diisopropylbenzene. Commercially available products can be used as these organic peroxides, and examples include Park Mill D (manufactured by NOF Corporation), Perhexa 3M (manufactured by NOF Corporation), Luperco 231XL (manufactured by Atchem Corporation) and the like. In this case, the organic peroxide as the component (a) is preferably 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, and the organic peroxide as the component (b) Is preferably dicumyl peroxide.

The total amount of the organic peroxide containing the components (a) and (b) is 100 parts by weight of the component (A) (hereinafter, parts by weight may be abbreviated as “parts”). 0.1 parts or more, preferably 0.2 parts or more, more preferably 0.3 parts or more, still more preferably 0.4 parts or more, and the upper limit is 0.8 parts or less, preferably 0.7 parts or less, More preferably, it is 0.6 part or less, More preferably, it is 0.5 part or less. If the blending amount is too small, the time required for crosslinking becomes long, the productivity is greatly reduced, and the compression is also greatly reduced. If the amount is too large, the resilience and durability will decrease.
In the present invention, by using polybutadiene synthesized with a rare earth element-based catalyst, particularly preferably an Nd-based catalyst for the core, and adding the organic peroxide in the above range, the golf according to the present invention is used. The resilience of the ball is very good. Since the resilience is improved, the solid core or the entire golf ball can be softened, the initial conditions in a full shot such as a driver are low spin and high launch, and the flight distance is improved. A soft feel can also be obtained.

  In addition, as addition amount of (a) component, with respect to 100 parts of (A) component, 0.05 parts or more, more preferably 0.08 parts or more, still more preferably 0.1 parts or more, 0.5 parts Or less, more preferably 0.4 parts or less, still more preferably 0.3 parts or less, and the addition amount of component (b) is 0.05 parts or more, more preferably 0.15 parts or more, and further It is preferably 0.2 parts or more, 0.7 parts or less, more preferably 0.6 parts or less, and still more preferably 0.5 parts or less.

  Next, in (C) unsaturated carboxylic acid and / or its metal salt, as unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, etc. are mentioned, Acrylic acid and methacrylic acid are especially preferable. Examples of the metal salt of the unsaturated carboxylic acid include a zinc salt and a magnesium salt. Among them, zinc acrylate is preferably used.

  The amount of the component (C) is usually 10 parts or more, more preferably 15 parts or more, still more preferably 20 parts or more, and the upper limit is usually 60 parts or less, relative to 100 parts of the component (A). Preferably it is 50 parts or less, more preferably 45 parts or less, and most preferably 40 parts or less. When the blending amount of the component (C) is out of the above range, the resilience and feel may be reduced (inferior).

  Examples of the organic sulfur compound of the component (D) in the present invention include thiophenol, thiofitol, halogenated thiophenol, or metal salts thereof. More specifically, pentachlorothiophenol, pentafluorothiophenol, pentabromothiophenol, parachlorothiophenol or zinc salts thereof, diphenyl polysulfide having 2 to 4 sulfur atoms, dibenzyl polysulfide, dibenzoyl polysulfide, dibenzo Examples include thiazoyl polysulfide, dithiobenzoyl polysulfide, alkylphenyl disulfides, sulfur compounds having a furan ring, and sulfur compounds having a thiophene ring. In particular, zinc salts of pentachlorothiophenol and diphenyl disulfide are preferably used. Can do.

  The blending amount of the component (D) is 0.1 parts or more, more preferably 0.2 parts or more, still more preferably 0.4 parts or more, and most preferably 0.7 parts with respect to 100 parts of the component (A). Part or more, 5 parts or less, more preferably 4 parts or less, still more preferably 3 parts or less, most preferably 2 parts or less, and particularly preferably 1.5 parts or less. If the blending amount is too small, the effect of improving the resilience may be lost, and if it is too much, the hardness becomes too soft and sufficient resilience may not be obtained.

  Examples of the inorganic filler of the component (E) in the present invention include zinc oxide, barium sulfate, calcium carbonate and the like, and the blending amount thereof is usually 5 parts or more, more preferably 7 parts per 100 parts of the component (A). Part or more, more preferably 10 parts or more, most preferably 13 parts or more, and the upper limit is usually 80 parts or less, more preferably 65 parts or less, still more preferably 50 parts or less, and most preferably 40 parts or less. If the amount is too large or too small, the proper weight and suitable resilience may not be obtained.

Moreover, an anti-aging agent can be further added to the rubber composition comprising the components (A) to (E) as necessary. The amount of the anti-aging agent added is 0.05 parts or more, more preferably 0.1 parts or more, still more preferably 0.2 parts or more and 3 parts or less, more preferably 100 parts by weight of component (A). 2 parts or less, more preferably 1 part or less, and most preferably 0.5 parts or less can be blended.
Commercially available products can be used as the anti-aging agent, and examples thereof include NOCRACK NS-6 and NS-30 (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., Yoshinox 425 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.)).

  The solid core in the present invention is formed from a rubber composition containing the above components (A) to (E). As a forming method, a method of vulcanizing and curing the rubber composition is suitable. is there. As vulcanization conditions, for example, a vulcanization temperature of 100 to 200 ° C. and a vulcanization time of 10 to 40 minutes can be carried out.

  The local hardness of the solid core formed as described above can be appropriately adjusted, and is not particularly limited. The local hardness distribution is equivalent from the center to the surface of the molded product. Even in the case of hardness, there may be a difference in hardness between the center and the surface of the molded product.

  The diameter of the solid core is 30 mm or more, preferably 32 mm or more, more preferably 34 mm or more, and the upper limit is 40 mm or less, preferably 39 mm or less, and more preferably 38 mm or less. When the diameter of the solid core is less than 30 mm, the feel and resilience deteriorate, and when it exceeds 40 mm, the crack durability deteriorates.

  The amount of deflection of the solid core under a load of 980 N (100 kgf) is 3.0 mm or more, preferably 3.5 mm or more, more preferably 4.0 mm or more, most preferably 4.2 mm or more, and the upper limit is 6. It is 0 mm or less, preferably 5.8 mm or less, more preferably 5.5 mm or less, and most preferably 5.3 mm or less. When the amount of deformation is less than 3.0 mm, the feeling of hitting becomes worse, and in particular, when a long shot in which large deformation occurs in the ball of a driver or the like, the spin increases excessively and does not fly. As the feeling becomes dull, the rebound is not sufficient and it will not fly, and the durability to cracking by repeated hitting will deteriorate.

The specific gravity (g / cm ³ ) 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. It is recommended that it is preferably 1.2 or less.

  The thermoplastic resin composition forming the intermediate layer in the present invention contains (P) a metal ion of an olefin-unsaturated carboxylic acid binary random copolymer and / or an olefin-unsaturated carboxylic acid binary random copolymer. In a metal ion of a hydrate, (Q) olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ternary random copolymer and / or olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ternary random copolymer A base resin blended with a Japanese product in a mass ratio of 100: 0 to 25:75 and a (T) non-ionomer thermoplastic elastomer blended in a mass ratio of 100: 0 to 50:50 (R) 5 to 80 parts by mass of a fatty acid having a molecular weight of 280 to 1500 and / or a derivative thereof, and (S) the base resin and R) is formed from a thermoplastic resin composition and unneutralized acid groups capable of neutralizing basic inorganic metal compound from 0.1 to 10 parts by weight by blending as essential component in the component.

  Here, the olefin in the base resin preferably has a carbon number of usually 2 or more and an upper limit of 8 or less, particularly 6 or less, regardless of whether it is a component (P) or a component (Q). Examples thereof include ethylene, propylene, butene, pentene, hexene, heptene, octene and the like, and ethylene is particularly preferable.

  Moreover, as unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid etc. can be mentioned, for example, It is especially preferable that they are acrylic acid and methacrylic acid.

  Further, as the unsaturated carboxylic acid ester, the lower alkyl ester of the unsaturated carboxylic acid described above is preferable. Specifically, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, acrylic Examples include ethyl acrylate, propyl acrylate, and butyl acrylate, and butyl acrylate (n-butyl acrylate and i-butyl acrylate) is particularly preferable.

  In the present invention, the (P) component olefin-unsaturated carboxylic acid binary random copolymer and the (Q) component olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester ternary random copolymer (hereinafter referred to as (P)). The component and the copolymer in the component (Q) are collectively referred to as a random copolymer) can be obtained by adjusting the materials described above and randomly copolymerizing them by a known method.

  It is recommended that the random copolymer has an adjusted unsaturated carboxylic acid content (acid content). Here, the content of the unsaturated carboxylic acid contained in the random copolymer of the component (P) is usually 4% by mass (synonymous with% by weight, the same shall apply hereinafter) or more, preferably 6% by mass or more, more preferably 8% by mass. % Or more, more preferably 10% by mass or more, and the upper limit is 30% by mass or less, preferably 20% by mass or less, more preferably 18% by mass or less, and further preferably 15% by mass or less.

  Similarly, the content of unsaturated carboxylic acid contained in the random copolymer of component (Q) is usually 4% by mass or more, preferably 6% by mass or more, more preferably 8% by mass or more, and the upper limit is 15% by mass or less. It is recommended that the amount be 12% by mass or less, more preferably 10% by mass or less. If the acid content of the random copolymer is too low, the resilience may be reduced, and if it is too high, the processability may be reduced.

  Metal ion neutralized product of olefin-unsaturated carboxylic acid binary random copolymer of component (P) and metal of olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester ternary random copolymer of component (Q) The ion neutralized product (hereinafter, the metal ion neutralized product of the copolymer in the component (P) and the component (Q) is generically referred to as a metal ion neutralized product of a random copolymer) is the random copolymer. It can be obtained by partially neutralizing the acid groups therein with metal ions.

Here, examples of metal ions that neutralize acid groups include Na ⁺ , K ⁺ , Li ⁺ , Zn ⁺⁺ , Cu ⁺⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Co ⁺⁺ , Ni ⁺⁺ , and Pb. ^++, etc. can be mentioned, preferably Na ^+, Li ^+, Zn ^++, can be preferably used Mg ⁺⁺ or the like, it is recommended that further preferably Zn ^++.

  In order to obtain a metal ion neutralized product of a random copolymer in the present invention, the random copolymer may be neutralized with the metal ion, for example, formate, acetate, nitrate of the metal ion. A method of neutralizing using a compound such as carbonate, hydrogen carbonate, oxide, hydroxide and alkoxide can be employed. The neutralization degree with respect to the random copolymer of these metal ions is not specifically limited.

  In the present invention, zinc ion neutralized ionomer resin can be suitably used as the metal ion neutralized product of the random copolymer, increasing the melt flow rate of the material and adjusting it to the optimum melt flow rate described later. Is easy and the moldability can be improved.

  Commercially available products may be used as the base resin for the component (P) and the component (Q). For example, as the random copolymer of the component (P), Nucrel 1560, 1214, and 1035 (all are Mitsui DuPont Polychemical Co., Ltd.), ESCOR 5200, 5100, 5000 (both manufactured by EXXONMOBIL CHEMICAL), etc. are used as random copolymers of the (Q) component, for example, Nukurel AN4311, AN43318 (both Mitsui, DuPont Poly). Chemical Co., Ltd.), ESCOR ATX325, ATX320, ATX310 (all manufactured by EXXONMOBIL CHEMICAL).

  Moreover, as the metal ion neutralized product of the random copolymer of the component (P), for example, Himilan 1554, 1557, 1601, 1605, 1706, AM7311 (all manufactured by Mitsui DuPont Polychemical Co., Ltd.), Surlyn 7930 (manufactured by DuPont, USA), Iotech 3110, 4200 (manufactured by EXXONMOBIL CHEMICAL), etc. are used as the metal ion neutralized product of the random copolymer of component (Q), for example, Himiran 1855, 1856, AM7316. (All are made by Mitsui DuPont Polychemical Co., Ltd.), Surlyn 6320, 8320, 9320, 8120 (all manufactured by DuPont, USA), Iotech 7510, 7520 (all manufactured by EXXONMOBIL CHEMICAL), etc. Can do. Examples of zinc-neutralized ionomer resins suitable as the metal ion neutralized product of the random copolymer include Himiran 1706, 1557, and AM7316.

  In the preparation of the base resin, the blending of the component (P) and the component (Q) is 100: 0 to 25:75, preferably 100: 0 to 50:50, more preferably 100: 0 to 75 by mass ratio. : 25, more preferably 100: 0. When the blending amount of the component (P) is too small, the resilience of the molded material is lowered.

  Further, in the present invention, the base resin of the component (P) and the component (Q) is adjusted by adjusting the blending ratio of the random copolymer and the neutralized metal ion of the random copolymer in addition to the above preparation. The moldability can be further improved, and the random copolymer: neutralized metal ion of random copolymer is usually 0: 100 to 60:40, preferably 0: 100 to 40:60, more preferably. Is recommended to be 0: 100 to 20:80, more preferably 0: 100. If the amount of the random copolymer is too large, the moldability during mixing may decrease.

  The (T) component is an optional component for further improving the feeling and resilience upon impact. In the present invention, the base resin and the (T) component are collectively referred to as a resin component. The component (T) is a non-ionomer thermoplastic elastomer other than an ionomer resin, and specific examples include olefin elastomers, styrene elastomers, polyester elastomers, urethane elastomers, polyamide elastomers, and the like. In particular, olefin-based elastomers and polyester-based elastomers can be preferably used from the viewpoint of further improving the resistance.

  Commercially available products may be used as the component (T). Examples of the olefin-based elastomer include Dynalon (manufactured by JSR), and examples of the polyester-based elastomer include Hytrel (manufactured by Toray DuPont).

  The blending amount of the component (T) is usually 0 parts by mass or more, particularly 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, further preferably 100 parts by mass of the base resin of the present invention. Is 4 parts by mass or more and the upper limit is 100 parts by mass or less, preferably 60 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 20 parts by mass or less. If the blending amount is too large, the compatibility of the mixture is lowered, and the durability of the golf ball may be significantly lowered.

  Next, the component (R) is a fatty acid having a molecular weight of 280 or more and 1500 or less, or a derivative thereof. The molecular weight is extremely small compared to the base resin, and the melt viscosity of the mixture is appropriately adjusted. It is a component that contributes to The (R) component of the present invention contains a relatively high content of acid groups (derivatives) and can suppress excessive rebound loss.

  The molecular weight of the (R) component fatty acid or derivative thereof is 280 or more, preferably 300 or more, more preferably 330 or more, still more preferably 360 or more, and the upper limit is 1500 or less, preferably 1000 or less, more preferably 600 or less. More preferably, it is necessary to be 500 or less. If the molecular weight is too low, the heat resistance cannot be improved, and if it is too high, the fluidity cannot be improved.

  Examples of the fatty acid of the component (R) or a fatty acid derivative thereof include, for example, an unsaturated fatty acid (derivative) containing a double bond or a triple bond in the alkyl group, or a saturated fatty acid in which the bond in the alkyl group is composed of only a single bond. (Derivatives) can be suitably used as well, but in any case, the number of carbon atoms in one molecule is usually 18 or more, preferably 20 or more, more preferably 22 or more, still more preferably 24 or more, and the upper limit is 80 or less. It is recommended that it is preferably 60 or less, more preferably 40 or less, and still more preferably 30 or less. If the number of carbon atoms is too small, improvement in heat resistance cannot be achieved, and there is too much content of acid groups, resulting in less fluidity improvement due to interaction with acid groups contained in the base resin. There is. On the other hand, when the number of carbon atoms is too large, the molecular weight increases, and thus the effect of fluidity modification may not be noticeable.

  Here, as the fatty acid of the component (R), specifically, stearic acid, 12-hydroxystearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, lignoceric acid, and the like are preferably used. , Stearic acid, arachidic acid, behenic acid, lignoceric acid, more preferably behenic acid.

In addition, the fatty acid derivative of the component (R) can be exemplified by metal soap in which protons contained in the acid group of the fatty acid described above are substituted with metal ions. In this case, as the metal ion, for ^{example, Na +, Li +, Ca} ++, Mg ++, Zn ++, Mn ++, Al +++, Ni ++, Fe ++, Fe +++, Examples thereof include Cu ⁺⁺ , Sn ⁺⁺ , Pb ⁺⁺ , and Co ⁺⁺ , and Ca ⁺⁺ , Mg ⁺⁺ , and Zn ⁺⁺ are particularly preferable.

  Specific examples of the fatty acid derivative (R) include magnesium stearate, calcium stearate, zinc stearate, 12-hydroxy magnesium stearate, 12-hydroxy calcium stearate, zinc 12-hydroxy stearate, magnesium arachidate, and arachidin. Calcium acid, Zinc arachidate, Magnesium behenate, Calcium behenate, Zinc behenate, Magnesium lignocerate, Calcium lignocerate, Zinc lignocerate, etc. Especially magnesium stearate, calcium stearate, zinc stearate , Magnesium arachidate, calcium arachidate, zinc arachidate, magnesium behenate, calcium behenate, zinc behenate, lignoserine Magnesium, calcium lignoceric acid, can be preferably used lignoceric acid zinc.

  In the present invention, a known metal soap-modified ionomer (USP 5312857, USP 5306760, WO 98/46671, etc.) is used as a combination of the base resin composed of the component (P) and the component (Q) and the component (R). ) Etc. can also be used.

  In the present invention, the component (S) is a basic inorganic metal compound capable of neutralizing the acid groups in the base resin and the component (R), and is an indispensable component in the present invention. When the component (S) is not blended, a metal soap-modified ionomer resin (for example, only a metal soap-modified ionomer resin described in the above patent publication) is used alone, and is included in the metal soap and ionomer resin during heating and mixing. Unneutralized acid groups exchange to generate a large amount of fatty acid, and the generated fatty acid has low thermal stability and easily vaporizes during molding, causing molding defects and sticking to the surface of the molded product. As a result, the problem of significantly reducing the adhesion of the coating film is caused.

  In the present invention, in order to solve such a problem, as the component (S), a basic inorganic metal compound that neutralizes the acid group contained in the base resin and the component (R) is blended as an essential component, It is intended to improve the resilience of the molded product.

  That is, the (S) component is blended as an essential component in the material, whereby the base resin and the acid group in the (R) component are not only neutralized appropriately, but also by optimization of each component. With a synergistic effect, the thermal stability of the mixture can be increased, and good moldability can be imparted and resilience can be improved.

  Here, the basic inorganic metal compound of the component (S) has high reactivity with the base resin and does not contain an organic acid in the reaction by-product, so that the neutralization degree of the mixture is not impaired without impairing the thermal stability. It is recommended that

The metal ions in the basic inorganic metal compound (S) are, for example, Li ⁺ , Na ⁺ , K ⁺ , Ca ⁺⁺ , Mg ⁺⁺ , Zn ⁺⁺ , Al ⁺⁺⁺ , Ni ⁺⁺ , Fe ⁺⁺ , Fe ⁺⁺⁺ , Cu ⁺⁺ , Mn ⁺⁺ , Sn ⁺⁺ , Pb ⁺⁺ , Co ^{++ and the} like. As the basic inorganic metal compound, known basic inorganic fillers containing these metal ions can be used. Specifically, magnesium oxide, magnesium hydroxide, magnesium carbonate, zinc oxide, sodium hydroxide, carbonate Sodium, calcium oxide, calcium hydroxide, lithium hydroxide, lithium carbonate and the like can be mentioned, but hydroxides or monoxides are particularly recommended, and more preferably high reactivity with the base resin. It is recommended to use calcium hydroxide, magnesium oxide, more preferably calcium hydroxide.

  In the golf ball of the present invention, the thermoplastic resin composition that forms an intermediate layer composed of at least one layer includes, as described above, a base resin containing a predetermined amount of the (P) component and the (Q) component, and an optional resin. By blending a predetermined amount of the (R) component and the (S) component to the resin component blended with the (T) component, the thermal stability, fluidity, and moldability are excellent, and the rebound is dramatically improved. An improvement can be imparted to the molding.

  The blending amount of the (R) component and the (S) component is such that the blending amount of the (R) component is based on 100 parts by mass of the resin component appropriately blending the above (P), (Q), and (T) components. 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 18 parts by mass or more, and the upper limit is 80 parts by mass or less, preferably 40 parts by mass or less, more preferably 25 parts by mass or less, More preferably, it is 22 parts by mass or less, and the blending amount of the component (S) is 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and the upper limit. Is 10 parts by mass or less, preferably 8 parts by mass or less, more preferably 6 parts by mass or less, and still more preferably 5 parts by mass or less. When the blending amount of the component (R) is too small, the melt viscosity is lowered and the processability is lowered, and when it is too much, the durability is lowered. If the blending amount of the component (S) is too small, heat stability and resilience are not improved, and if it is too large, the heat resistance of the golf ball material decreases due to an excessive basic inorganic metal compound.

  In the golf ball of the present invention, the thermoplastic resin composition forming the intermediate layer is formed by blending predetermined amounts of the above-described resin component, (R) component, and (S) component, respectively. It is recommended that 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more of the acid group is neutralized. By such high neutralization, it is possible to more reliably suppress the exchange reaction that becomes a problem when only the above-mentioned base resin and fatty acid (derivative) are used, and to prevent the generation of fatty acids, Stability is remarkably improved, moldability is good, and a molded product having very excellent resilience compared to conventional ionomer resins can be obtained.

  Here, the degree of neutralization is the degree of neutralization of acid groups contained in the mixture of the base resin and the fatty acid (derivative) of the component (R), and the metal ion neutralization of the random copolymer in the base resin. When the ionomer resin is used as a product, it is different from the neutralization degree of the ionomer resin itself. When comparing the mixture of the present invention having the same degree of neutralization with only the ionomer resin having the same degree of neutralization, the mixture of the present invention contains a large amount of metal ions, so that ion crosslinking that contributes to improvement in resilience is present. Density can be increased and excellent resilience can be imparted to the molded product.

  In the present invention, the acid group of the mixture is neutralized with a transition metal ion and an alkali metal and / or alkaline earth metal ion in order to more reliably achieve both high neutralization and excellent fluidity. It is recommended. Neutralization with transition metal ions is weaker in ion agglomeration than alkali (earth) metal ions, but by using these different types of ions in combination, neutralization of acid groups in the mixture can The improvement of the property can be aimed at.

  In the present invention, the molar ratio of the transition metal ion to the alkali metal and / or alkaline earth metal ion is usually 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30: It is recommended that it be 70-70: 30, more preferably 40: 60-60: 40. If the molar ratio of transition metal ions is too small, the effect of improving fluidity may not be sufficiently imparted, and if the molar ratio of transition metal ions is too large, the resilience may be lowered.

  Examples of the metal ions include zinc ions as transition metal ions, and at least one selected from sodium ions, lithium ions, magnesium ions, and the like as alkali metal ions or alkaline earth metal ions. Although an ion can be mentioned, these are not specifically limited.

  In the present invention, in order to obtain a mixture in which the desired amount of acid groups is neutralized with a transition metal ion and an alkali metal ion or an alkaline earth metal ion, a known method can be employed. The method of neutralizing by ion) is a method of using zinc soap in the fatty acid derivative, and a zinc ion neutralized product (for example, zinc ion neutralized type) when blending (P) component and (Q) component as the base resin Examples thereof include a method using an ionomer resin) and a method using a zinc compound such as zinc oxide as the basic inorganic metal compound of component (S).

  In the golf ball of the present invention, the thermoplastic resin composition forming the intermediate layer can further contain various additives as required, and can be prepared according to the use of the material. For example, when a cover material is used, a pigment, a dispersant, an anti-aging agent, an ultraviolet absorber, a light stabilizer and the like can be added in addition to the above essential components. When these additives are blended, the blending amount is preferably 0.1 parts by weight with respect to 100 parts by weight of the total blending amount of the essential components of the present invention (resin component, (R) component, (S) component). Above, more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, the upper limit is 10 parts by mass or less, more preferably 6 parts by mass or less, and further preferably 4 parts by mass or less. it can.

  In order to obtain the thermoplastic resin composition, it suffices to obtain a mixture in which the above-described essential components and optional components are blended as necessary. As a heating and mixing condition, for example, a heating temperature of 150 to 250 ° C., as a mixer, for example, The kneading can be carried out using an internal mixer such as a kneading type twin screw extruder, Banbury or kneader. In this case, there is no particular limitation on the blending method, a method of blending together with the essential components of the present invention and heating and mixing at the same time, a method of heating and mixing the essential components in advance, and then adding an optional additive and further heating and mixing Etc. can be adopted.

  The thermoplastic resin composition preferably has a flow rate particularly suitable for injection molding and is preferably adjusted for a melt flow rate in order to improve moldability. In this case, the test temperature is 190 ° C. according to JIS-K7210. The melt flow rate (MFR) when measured according to a load of 21.18 N (2.16 kgf) is usually 0.5 dg / min or more, preferably 1 dg / min or more, more preferably 1.5 dg / min or more, and further preferably The upper limit is 20 dg / min or less, preferably 10 dg / min or less, more preferably 5 dg / min or less, and further preferably 3 dg / min or less. If the melt flow rate is too large or too small, the workability may be significantly reduced.

Further, the thermoplastic resin composition belongs to a carboxylate anion stretching vibration of 1530 to 1630 cm ⁻¹ with respect to absorbance of an absorption peak attributed to a carbonyl stretching vibration of 1690 to 1710 cm ⁻¹ that is usually detected in infrared absorption measurement. It is preferable to optimize the relative absorbance at the absorption peak (absorbance at the absorption peak attributed to the carboxylate anion stretching vibration / absorbance at the absorption peak attributed to the carbonyl stretching vibration).

  Here, the carboxylate anion stretching vibration means a carboxyl group (a carboxyl group neutralized by a metal ion) having dissociated protons, and the carbonyl stretching vibration means a vibration of an undissociated carboxyl group. The intensity ratio of each peak depends on the degree of neutralization. In the case of an ionomer resin having a neutralization degree of about 50 mol% that is generally used, the absorbance ratio of each peak is about 1: 1.

  In the present invention, in order to improve the thermal stability, fluidity, moldability, and resilience of the golf ball material, the peak absorbance attributed to the carboxylate anion stretching vibration of the material is changed to the peak absorbance due to the carbonyl stretching vibration. Of at least 1.3 times, preferably 1.5 times or more, more preferably 2 times or more, and still more preferably no peak attributed to carbonyl stretching vibration.

  The thermoplastic resin composition can be measured for thermostability by thermogravimetry, but in thermogravimetry, the weight loss rate at 250 ° C based on the mass at 25 ° C is usually 2% by mass or less. It is recommended that the amount be 1.5% by mass or less, more preferably 1% by mass or less.

In the present invention, a known method can be used as a method for forming the intermediate layer using the thermoplastic resin composition. Although not particularly limited, for example, a method in which a core prepared in advance is placed in a mold, the thermoplastic resin composition is heated and mixed and melted, and injection molding can be employed. In this case, the production of the golf ball can be performed in a state where excellent fluidity and moldability are ensured, and the obtained golf ball is preferable because of its high resilience.
In addition, a method of forming a pair of hemispherical half cups in advance with the intermediate layer material of the thermoplastic resin composition, wrapping the core with the half cups, and press-molding at 120 to 170 ° C. for 1 to 5 minutes is used. May be.

  The thickness of the intermediate layer is 0.5 mm or more, preferably 0.7 mm or more, and the upper limit is 2.0 mm or less, preferably 1.8 mm or less. If the thickness of each layer of the intermediate layer is less than 0.5 mm, the effect of adding the intermediate layer cannot be obtained, while if it exceeds 2.0 mm, the feel and resilience are reduced.

The Shore D hardness of the intermediate layer is 20 or more, preferably 25 or more, and the upper limit is 60 or less, preferably 58 or less. When the Shore D hardness of the intermediate layer is less than 20, the resilience is lowered. On the other hand, when it exceeds 60, the feeling at the time of hitting the formed golf ball is remarkably lowered.
In the present invention, it is necessary that the Shore D hardness of the intermediate layer is not more than the Shore D hardness of the cover described later. By making the Shore D hardness of the intermediate layer and the Shore D hardness of the cover in such a relationship, it is possible to achieve low spin and high launch of the obtained golf ball, and for the intermediate layer. Since a highly neutralized ionomer resin is used as a material, the resilience is high, and a good flight distance is realized due to the combined effects of both.

  The cover used in the present invention is formed with (F) a thermoplastic polyurethane material as a main component (hereinafter sometimes abbreviated as a cover material), and (F) the thermoplastic polyurethane material includes (M) thermoplasticity. Polyurethane and (N) isocyanate mixture, wherein (N) isocyanate mixture is (N-1) an isocyanate compound having two or more isocyanate groups as functional groups in one molecule; An isocyanate mixture dispersed in a thermoplastic resin that does not substantially react with isocyanate groups is used.

  The (M) thermoplastic polyurethane used in the present invention is not particularly limited as long as it is a thermoplastic resin mainly composed of polyurethane, but it comprises a high-molecular polyol compound constituting a soft segment and a hard segment. The diisocyanate and the monomolecular chain extender are suitable.

Although it does not restrict | limit especially as a high molecular polyol compound, For example, a polyester-type polyol, a polyether-type polyol etc. are mentioned, From a viewpoint of impact resilience or a low-temperature characteristic, a polyether type is used preferably.
Examples of the polyether-based polyol include polytetramethylene glycol and polypropylene glycol, and polytetramethylene glycol is particularly preferably used. Moreover, these number average molecular weights become like this. Preferably it is 1000-5000, More preferably, it is 1500-3000.

  The diisocyanate is not particularly limited. For example, aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate, and aliphatics such as hexamethylene diisocyanate. Diisocyanate is mentioned. In the present invention, 4,4'-diphenylmethane diisocyanate is preferably used from the viewpoint of reaction stability with the isocyanate mixture when an isocyanate mixture described later is blended.

  Although it does not restrict | limit especially as a monomolecular chain extender, A normal polyhydric alcohol and amines can be used, for example, 1, 4- butylene glycol, 1, 2- ethylene glycol, 1, 3- propylene glycol, 1 , 3-butanediol, 1,6-hexylene glycol, 2,2-dimethyl-1,3-propanediol, 1,3-butylene glycol, dicyclohexylmethylmethanediamine (hydrogenated MDA), isophoronediamine (IPDA), etc. Is mentioned. These chain extenders preferably have an average molecular weight of 20 to 15000.

  Commercially available products can be used as such polyurethane elastomers, for example, Pandex T7298, TR3080, T8290, T8295, T8260 (DCI Bayer Polymer Co., Ltd.), Resamine 2593, 2597 (Daiichi Seika) (Made by an industrial company) etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  For the cover in the present invention, a cover obtained by further blending the above-described (F) thermoplastic polyurethane with a specific isocyanate mixture described later is preferably used. By blending the specific isocyanate mixture, feeling, controllability, cut resistance, scratch resistance, and handling are improved as compared with a golf ball using an outer layer cover formed mainly of a normal polyurethane elastomer alone. It is possible to obtain a golf ball that is further excellent in durability to cracking upon return hitting.

  The (N) isocyanate mixture used in the present invention includes (N-1) an isocyanate compound having two or more isocyanate groups as functional groups in one molecule, and (N-2) a substantial reaction with the isocyanate group. Preferably, the isocyanate mixture is dispersed in a thermoplastic resin that does not.

  Here, as the isocyanate compound (N-1), an isocyanate compound used in the conventional technology relating to polyurethane can be used, for example, an aromatic isocyanate compound, a hydrogenated aromatic isocyanate compound, an aliphatic diisocyanate, an oil. Although cyclic diisocyanate etc. are mentioned, it is not limited to these.

Examples of the aromatic isocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and a mixture of both, 4,4′-diphenylmethane diisocyanate, m-phenylene diisocyanate, 4,4′-biphenyl diisocyanate, and the like. It is done.
Examples of the hydrogenated product of the aromatic isocyanate compound include dicyclohexylmethane diisocyanate.
Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and octamethylene diisocyanate.
Examples of the alicyclic diisocyanate include xylene diisocyanate.

  The thermoplastic resin (N-2) is preferably a resin having low water absorption and excellent compatibility with the thermoplastic polyurethane material. Examples of such resins include, but are not limited to, polystyrene resins, polyvinyl chloride resins, ABS resins, polycarbonate resins, polyester elastomers (polyether / ester block copolymers, polyester / ester block copolymers, etc.). Is not to be done. From the viewpoint of impact resilience and strength, a polyether / ester block copolymer is particularly preferred.

  The blending ratio of the component (N-2) and the component (N-1) in producing the isocyanate mixture is 100: 5 to 100: 100 (weight ratio), particularly 100: 10 to 100: 40 (weight ratio). ) Is preferable. If the blending amount of the (N-1) component relative to the (N-2) component is too small, more isocyanate mixture must be added in order to obtain a sufficient amount for the crosslinking reaction with the polyurethane elastomer. However, the physical properties of the polyurethane elastomer after crosslinking may become insufficient due to the great influence of the component (N-2), and if the amount is too large, the component (N-1) slips during kneading. May be difficult to synthesize the mixture.

For the isocyanate mixture, for example, the (N-1) component is blended with the (N-2) component, and these are sufficiently kneaded with a mixing roll or Banbury mixer at a temperature of 130 to 250 ° C., pelletized or cooled and then pulverized. Can be obtained.
As the isocyanate mixture, a commercially available product can be used. For example, Clonate EM30 manufactured by Dainichi Seika Kogyo Co., Ltd. is preferably used, but is not limited thereto.

  The amount of the isocyanate mixture is usually 1 part by weight or more, preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and the upper limit is usually 100 parts by weight or less with respect to 100 parts by weight of the thermoplastic polyurethane (M). The amount is preferably 50 parts by weight or less, more preferably 30 parts by weight or less. If the blending amount is too small, sufficient crosslinking reaction may not be obtained and physical properties may not be improved.If the blending amount is too large, discoloration due to aging, heat, and ultraviolet rays may increase, and rebound may decrease. Problems may arise.

  As described above, the outer cover layer of the golf ball of the present invention is particularly preferably formed of (M) a thermoplastic polyurethane as a main material, but other components such as pigments, dispersants, antioxidants, ultraviolet rays are optionally used. Absorbers, ultraviolet stabilizers, plasticizers and the like and inorganic fillers (zinc oxide, barium sulfate, titanium dioxide, etc.) can also be blended.

  As a compounding quantity of the said additive, it is 0.1-50 weight part normally with respect to 100 weight part of said (F) thermoplastic polyurethane materials, Preferably it is 0.5-30 weight part, More preferably, it is 1-6 weight part It is. When the compounding amount of the additive is too large, the durability may be lowered, and when the compounding ratio of the additive is too small, the effect of the additive may not be obtained.

  In the present invention, the cover material has a hardness (Shore D) of 50 or more, preferably 53 or more, and an upper limit of 70 or less, preferably 64 or less. If the Shore D hardness is too low, the rebound is inferior. If the Shore D hardness is too high, improvement in feel and controllability is not observed. In the present invention, the Shore D hardness is a hardness measured with a D-type durometer according to ASTM D2240.

The method for producing the cover material in the present invention is not particularly limited. For example, at a heating temperature of 150 to 250 ° C., an internal mixer such as a kneading type twin-screw extruder, Banbury, kneader or the like is used as a mixer, and each of the components described above is used. It can be obtained by kneading.
When various additives are blended with the cover material in addition to the components (F) and (G), the blending method is not particularly limited, and is blended with the components (F) and (G). The components (F) and (G) may be heated and mixed in advance, and then an arbitrary additive or the like may be added and further heated and mixed.

The cover material shown above exhibits very good scuff resistance and adheres very well to the paint described below.
By combining the soft core and the cover described above, the golf ball hardness can be softened without sacrificing the flight distance, and a soft feel can be realized, and the hardness is soft. For this reason, the contact area between the club and the golf ball at the time of hitting is increased, so that the impact force at the time of hitting is dispersed, and the scratch resistance and cracking durability are further improved.

In the multi-piece solid golf ball of the present invention, the core is covered with an intermediate layer composed of at least one layer formed of the thermoplastic resin composition, and the intermediate layer is formed of the cover material. A multi-piece solid golf ball formed by covering a cover.
As a method for forming the cover, a known method can be used as in the case of forming the intermediate layer, and is not particularly limited. For example, a previously prepared core is disposed in a mold, and the cover material is formed. A method of heating, mixing, melting, and injection molding can be employed. In this case, the production of the golf ball can be performed in a state where excellent fluidity and moldability are ensured, and the obtained golf ball is preferable because of its high resilience.
Moreover, you may use the method of shape | molding a pair of hemispherical half cup previously with the cover material of this invention, wrapping a core with this half cup, and press-molding at 120-170 degreeC for 1 to 5 minutes.

  The cover material in the present invention preferably has a melt flow rate adjusted to ensure fluidity particularly suitable for injection molding and to improve moldability. In this case, the test temperature is 190 ° C. according to JIS-K6760. The melt flow rate (MFR) when measured according to a load of 21.18 N (2.16 kgf) is usually 0.5 dg / min or more, preferably 1 dg / min or more, more preferably 1.5 dg / min or more, and further preferably The upper limit is usually 20 dg / min or less, preferably 10 dg / min or less, more preferably 5 dg / min or less, and further preferably 3 dg / min or less. If the melt flow rate is too large or too small, the workability may be significantly reduced.

  The cover thickness formed by the cover material is 0.5 mm or more, preferably 0.9 mm or more, more preferably 1.1 mm or more, and the upper limit is 2.5 mm or less, more preferably 2.0 mm or less. When the cover thickness is too large, the resilience is lowered, and when the cover thickness is too small, the durability is lowered.

  In the multi-piece golf ball of the present invention, it is preferable to form a large number of dimples on the surface of the cover, and to perform various treatments such as base treatment, stamping, painting, etc. on the cover. When arranging the dimples, it is preferable to arrange the dimples so that there is no single great circular line that does not intersect the dimples. If there is a great circle line that does not intersect the dimples, there may be variations in flight.

  It is preferable that the number of dimples and the total number of dimples are optimized, and the trajectory is more stable due to the synergistic effect of optimization of the number and total number of dimples, and the flight distance performance is excellent. Golf balls can be obtained.

  Here, the number of types of dimples refers to the number of types of dimples having different dimple diameters and / or depths, and it is usually recommended that the number of types is two or more, preferably three or more. In addition, it is recommended that the upper limit is 8 or less, particularly 6 or less.

  The total number of dimples is usually 300 or more, preferably 320 or more, and the upper limit is 480 or less, preferably 455 or less. Even if the total number of dimples is too small or the total number of dimples is too large, the optimal lift may not be obtained and it may not fly.

  As the dimple, it is recommended that the dimple volume occupancy VR (%) and the dimple surface occupancy SR (%) are optimized. The synergistic effect of the optimization of SR in combination with these VRs allows the trajectory to be optimized, the flight distance can be improved, the balance of appropriate lift and drag can be obtained, and the better flight distance performance can be achieved. Can be granted.

The ratio (volume occupancy) of the volume of the golf ball surface dimples to the virtual golf ball volume assumed to have no dimples is defined as VR (unit:%). The VR value (%) of the multi-piece golf ball of the present invention is usually 0.70 or more, preferably 0.75 or more, and the upper limit is usually 1.00 or less, preferably 0.82 or less, more preferably 0.79. It is as follows.
Further, the ratio (dimple surface occupancy) SR value (%) occupied by the total area of the phantom spherical surface surrounded by the edge of each dimple is usually 70% or more, preferably 72% or more, and the upper limit is usually 85% or less. , Preferably 83% or less.
If these VR value and SR value are out of the above ranges, an appropriate trajectory may not be obtained and the flight distance may be reduced.
By combining the solid core and the cover with the relatively high trajectory dimples, it is possible to prevent a drop and extend the flight distance with a higher and flat trajectory.

  The calculation of the volume occupancy rate VR and the dimple surface occupancy rate SR of the dimple is a value obtained by measuring the dimple of the product golf ball. When a stamp finishing process or the like is performed, the calculation is performed based on the shape of the dimple of the product ball in which all the processes are completed.

In the present invention, when performing the above-mentioned coating, a coating composition disclosed in JP-A-10-234848, that is, a hydroxyl group-containing polyester obtained by reacting a polyhydric alcohol component and a polybasic acid component, It is particularly preferred to use a golf ball coating composition containing non-yellowing polyisocyanate and at least a part of the polyhydric alcohol component having an alicyclic structure in the molecule. The coating composition is excellent in cohesive fracture strength, impact resistance that can withstand repeated hits by golf clubs, sand wear resistance that can withstand bunker shots, excellent herbaceous soil resistance, weather resistance, and water resistance. However, it has been found that it can be satisfactorily adhered to the cover layer in the present invention.

  The multi-piece golf ball of the present invention may conform to the golf regulations for competition purposes, and may be formed to have a diameter of 42.67 mm or more, preferably 45.0 to 45.93 g.

  The multi-piece golf ball according to the present invention includes the core and the cover, and preferably includes a large number of dimples on the cover surface. The amount of deflection of the entire ball when a load of 980 N (100 kgf) is applied, 3.0 mm or more, preferably 3.2 mm or more, more preferably 3.4 mm or more, most preferably 3.6 mm or more, and the upper limit is 5.0 mm or less, preferably 4.8 mm or less, more preferably 4.6 mm or less. Most preferably, it is 4.4 mm or less. If the amount of deformation is less than 3.0 mm, the feeling of hitting will be worse, and especially when a long shot in which a ball such as a driver undergoes large deformation, the spin will increase and will not fly. As the feeling becomes dull, the rebound becomes insufficient and does not fly, and the durability against cracking due to repeated impacts deteriorates.

  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 1-3, Comparative Examples 1-3]
Using the rubber composition shown in Table 1, a solid core was prepared by vulcanization at 155 ° C. for 17 minutes.
The intermediate layer material having the composition shown in Table 2 was mixed at 200 ° C. with a kneading type twin screw extruder to obtain a pellet-shaped intermediate layer material, and then injected into the mold provided with the solid core. A solid core coated with the material was produced.
Furthermore, after mixing the cover material of the composition shown in Table 3 with a kneading type twin screw extruder at 200 ° C. to obtain a pellet-shaped cover material, a mold provided with a solid core covered with the intermediate layer material A multi-piece solid golf ball was produced by injecting the product into the interior. Table 4 shows the dimple types arranged on the cover surface. Examples of arrangement of the dimple species A to C described in Table 4 are shown in FIGS.
Table 5 shows properties of the obtained golf balls.

ＨＣＢＮ−１３
ＪＳＲ社製、Ｃｉｓ１，４量９６％、ムーニー粘度（ＭＬ₁₊₄（１００℃））５３、分子量分布Ｍｗ／Ｍｎ３．２、触媒Ｎｄ。
ＢＲ０１
ＪＳＲ社製、Ｃｉｓ１，４量９６％、ムーニー粘度（ＭＬ₁₊₄（１００℃））４４、分子量分布Ｍｗ／Ｍｎ４．２、触媒Ｎｉ、溶液の粘度１５０ｍＰａ・ｓ。
ＢＲ１１
ＪＳＲ社製、Ｃｉｓ１，４量９６％、ムーニー粘度（ＭＬ₁₊₄（１００℃））４４、分子量分布Ｍｗ／Ｍｎ４．１、触媒Ｎｉ、溶液の粘度２７０ｍＰａ・ｓ。
パーヘキサ３Ｍ−４０
日本油脂社製。パーヘキサ３Ｍ−４０は４０％希釈品であり、添加量は１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサンの実質添加量で示した。
パークミルＤ
日本油脂社製、ジクミルパーオキサイド。
アクリル酸亜鉛
日本蒸留工業（株）製。
ペンタクロロチオフェノール亜鉛塩
東京化成工業（株）製。
酸化亜鉛
堺化学工業（株）製。
ノクラックＮＳ−６
大内新興化学社製、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）

HCBN-13
JSR, Cis 1,4 amount 96%, Mooney viscosity (ML _{1 + 4} (100 ° C.)) 53, molecular weight distribution Mw / Mn 3.2, catalyst Nd.
BR01
JSR, Cis 1,4 amount 96%, Mooney viscosity (ML _{1 + 4} (100 ° C.)) 44, molecular weight distribution Mw / Mn 4.2, catalyst Ni, solution viscosity 150 mPa · s.
BR11
JSR, Cis 1,4 amount 96%, Mooney viscosity (ML _{1 + 4} (100 ° C.)) 44, molecular weight distribution Mw / Mn 4.1, catalyst Ni, solution viscosity 270 mPa · s.
Perhexa 3M-40
Made by Nippon Oil & Fats. Perhexa 3M-40 is a 40% diluted product, and the addition amount is shown as the substantial addition amount of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane.
Park Mill D
Dicumyl peroxide manufactured by NOF Corporation.
Zinc acrylate manufactured by Nippon Distillation Co., Ltd.
Pentachlorothiophenol zinc salt manufactured by Tokyo Chemical Industry Co., Ltd.
Made by Zinc Oxide Chemical Industries.
NOCRACK NS-6
2,2'-methylenebis (4-methyl-6-t-butylphenol) manufactured by Ouchi Shinsei Chemical Co., Ltd.

ハイミラン１６０５
三井・デュポンポリケミカル社製。
ハイミラン１６０１
三井・デュポンポリケミカル社製。
ダイナロン６１００Ｐ
ＪＳＲ（株）製オレフィン結晶ブロックを有するブロックコポリマー。
ベヘニン酸
日本油脂社製。

High Milan 1605
Made by Mitsui DuPont Polychemicals.
High Milan 1601
Made by Mitsui DuPont Polychemicals.
Dynalon 6100P
A block copolymer having an olefin crystal block manufactured by JSR Corporation.
Behenic acid manufactured by Nippon Oil & Fats.

パンデックスＴ８２６０
ＤＩＣバイエルポリマー（株）製、熱可塑性ポリウレタンエラストマー。
パンデックスＴ８２９５
ＤＩＣバイエルポリマー（株）製、熱可塑性ポリウレタンエラストマー。
クロスネートＥＭ３０
大日精化工業（株）製
サーリン７９３０
米国デュポン社製。アイオノマー樹脂。
サーリン６３２０
米国デュポン社製。アイオノマー樹脂。
ニュクレル９−１
米国デュポン社製 三元酸共重合体。

Pandex T8260
A thermoplastic polyurethane elastomer manufactured by DIC Bayer Polymer Co., Ltd.
Pandex T8295
A thermoplastic polyurethane elastomer manufactured by DIC Bayer Polymer Co., Ltd.
Crossnate EM30
Dainichi Seika Kogyo Co., Ltd.
Surlyn 7930
Made by US DuPont. Ionomer resin.
Surlyn 6320
Made by US DuPont. Ionomer resin.
Nukurel 9-1
A ternary acid copolymer manufactured by DuPont, USA.

ＶＲ（％）
各ディンプルの縁部によって囲まれる平面下のディンプル空間体積の全ディンプルの総和の、ゴルフボール表面にディンプルがないと仮定した仮想球の全体積に対する割合（％）。
ＳＲ（％）
ゴルフボールをディンプルのない球状とみなした仮想球面とした際、個々のディンプルの縁部によって囲まれる仮想球面の表面積の合計が上記仮想球面の全面積を占める割合（％）。

VR (%)
The ratio (%) of the sum of all dimples in the dimple space volume below the plane surrounded by the edge of each dimple to the total volume of the phantom sphere assuming no dimples on the golf ball surface.
SR (%)
When a golf ball is a virtual sphere that is regarded as a spherical shape without dimples, the ratio (%) that the total surface area of the virtual sphere surrounded by the edge of each dimple occupies the total area of the phantom sphere.

コア外径（ｍｍ）
表面を５点測定した平均値。
コア硬度（ｍｍ）
９８０Ｎ（１００ｋｇｆ）荷重負荷時の変形量（ｍｍ）を計測した。
中間層厚み（ｍｍ）
（中間層被覆コア外径−コア外径）÷２として算出した。
中間層硬度
ＡＳＴＭ Ｄ−２２４０に準じて測定したショアＤ硬度。
カバー厚み（ｍｍ）
（ボール外径−中間層被覆コア外径）÷２により算出した
カバー硬度
ＡＳＴＭ Ｄ−２２４０に準じて測定したショアＤ硬度。
ボール外径（ｍｍ）
ディンプルのない部分を５点測定した平均値。
ボール硬度（ｍｍ）
得られたゴルフボールに対し、９８０Ｎ（１００ｋｇｆ）荷重負荷時の変形量（ｍｍ）を計測した。
飛び
打撃マシン（（株）ミヤマエ社製）を用い、ドライバー（Ｗ＃１）でヘッドスピード４０ｍ／ｓで打撃し、初速度、スピン量、キャリー飛距離、トータル飛距離をそれぞれ測定した。
打感
各ボールについて、アマチュア上級者５名によるドライバー（Ｗ＃１）及びパター打撃したときの打感を下記基準で評価し、最も多かった評価をボールに対する評価とした
○：軟らかい
△：普通
×：硬い
耐擦過傷性
ボールを２３℃に保温し、ピッチングウェッジをスイングロボットマシンに取り付け、ヘッドスピード３３ｍ／ｓにて打撃し、打撃傷を目視で判断した。次の評価基準で評価した。
○：傷がない、もしくは使用上、全く気にならない程度の傷。
×：表面が毛羽立つ、ディンプルが欠ける、などのひどい傷。
塗膜耐久性
内容量８Ｌの磁性のボールミルに、ボールとバンカー用の砂３Ｌを入れ、２時間ミキシングし、砂磨耗による表面の傷つき度合い、光沢減少の度合い、砂の付着度合いを目視により確認した。比較球（ブリヂストンスポーツ株式会社製「ＡＬＴＵＳ ＮＥＷＩＮＧ」）と同時に評価を行い、次の評価基準で評価した。
○：比較球よりも良好な塗膜耐久性。
△：比較球と同等の塗膜耐久性。
×：比較球よりも悪い塗膜耐久性。

Core outer diameter (mm)
Average value obtained by measuring 5 points on the surface.
Core hardness (mm)
The amount of deformation (mm) when a load of 980 N (100 kgf) was applied was measured.
Intermediate layer thickness (mm)
It was calculated as (intermediate layer coated core outer diameter−core outer diameter) ÷ 2.
Intermediate layer hardness Shore D hardness measured according to ASTM D-2240.
Cover thickness (mm)
Calculated by (ball outer diameter−intermediate layer coated core outer diameter) ÷ 2.
Cover hardness Shore D hardness measured according to ASTM D-2240.
Ball outer diameter (mm)
Average value of 5 points measured without dimples.
Ball hardness (mm)
The amount of deformation (mm) when a load of 980 N (100 kgf) was applied to the obtained golf ball was measured.
Using a flying hitting machine (manufactured by Miyamae Co., Ltd.), the driver (W # 1) was hit at a head speed of 40 m / s, and the initial speed, spin rate, carry flight distance, and total flight distance were measured.
For feel each ball, the feel of when the driver (W # 1) and putter hit by amateur senior's five and evaluated according to the following criteria, and the evaluation of the evaluation was the highest for the ball ○: soft △: Normal × :hard
The scratch-resistant ball was kept warm at 23 ° C., a pitching wedge was attached to the swing robot machine, and the ball was hit at a head speed of 33 m / s. Evaluation was performed according to the following evaluation criteria.
○: Scratches that are not scratched or are not of any concern during use.
X: Severe scratches such as fuzzy surfaces and lack of dimples.
Put 3L of ball and bunker sand into a magnetic ball mill with a coating film durability internal capacity of 8L, mix for 2 hours, and visually check the degree of surface scratching, gloss reduction, and sand adhesion due to sand abrasion. . The evaluation was performed at the same time as the comparative ball (“ALTUS NEWING” manufactured by Bridgestone Sports Co., Ltd.), and the following evaluation criteria were used.
○: Coating film durability better than that of the comparative sphere.
(Triangle | delta): The coating-film durability equivalent to a comparison ball | bowl.
X: Coating film durability worse than that of the comparative sphere.

Claims (9)

In a multi-piece solid golf ball comprising a solid core, an intermediate layer, and a cover,
The solid core contains 60% or more of (A) a cis-1,4-bond and contains 100 to 100 parts by weight of a polybutadiene synthesized using a rare earth element catalyst. (B) Two or more organic peroxides having different half-lives, the organic peroxide having the shortest half-life at 155 ° C. (a) The organic peroxide having the longest half-life at 155 ° C. was a (b), half-life a _t of (a), when the half-life of (b) and b _t, a _t is 5 seconds to 120 seconds or less, b _t is 800 seconds or less than 300 seconds, the an organic peroxide ratio b _t / a _t half-life of 7 to 20 or less, the (a) additive amount of component (a) 0.05 part by mass or more with respect to 100 parts by weight of component 0. 5 parts by mass or less, and the amount of component (b) added is 0.05 parts by mass or more with respect to 100 parts by mass of component (A). 0.7 parts by mass or less, and the total amount of components (a) and (b) is 0.1 to 0.8 parts by weight, (C) unsaturated carboxylic acid and / or metal salt thereof, (D) organic sulfur Compound, (E) formed from a rubber composition containing an inorganic filler, the deformation of the solid core when loaded with 980N (100 kgf) is 3.0 to 6.0 mm, and the diameter of the solid core is 30 ~ 40mm and
The intermediate layer comprises (P) an olefin-unsaturated carboxylic acid binary random copolymer and / or a metal ion neutralized product of an olefin-unsaturated carboxylic acid binary random copolymer, and (Q) an olefin-unsaturated product. 100: 0 to mass ratio of carboxylic acid-unsaturated carboxylic acid ternary random copolymer and / or metal ion neutralized product of olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ternary random copolymer. With respect to 100 parts by mass of a resin component formulated such that the base resin blended so as to be 25:75 and the (T) non-ionomer thermoplastic elastomer are blended so that the mass ratio is 100: 0 to 50:50, R) Fatty acid having a molecular weight of 280 to 1500 and / or 5 to 80 parts by mass of a derivative thereof, and (S) a base capable of neutralizing an unneutralized acid group in the base resin and (R) component A thermoplastic resin composition containing 0.1 to 10 parts by mass of an inorganic metal compound as an essential component is formed as a main material, and the intermediate layer has a thickness of 0.5 to 2.0 mm, and the intermediate layer The Shore D hardness of the layer is 20-60,
The cover is formed of (F) a thermoplastic polyurethane material as a main component, and the (F) thermoplastic polyurethane material comprises (M) a thermoplastic polyurethane and (N) an isocyanate mixture, and (N) an isocyanate. (N-1) An isocyanate compound having two or more isocyanate groups as functional groups in one molecule, and (N-2) an isocyanate dispersed in a thermoplastic resin that does not substantially react with the isocyanate group. The cover has a thickness of 0.5 to 2.5 mm, and the cover has a Shore D hardness of 50 to 70, and the above (intermediate layer Shore D hardness) ≦ (cover Shore D hardness) There,
Moreover, the multi-piece solid golf ball comprising the solid core, the intermediate layer, and the cover has a deformation amount of 3.0 to 5.0 mm when loaded with a load of 980 N (100 kgf). Peace solid golf ball.   The rubber composition contains 60% or more of the (A) cis-1,4-bond and contains 100 to 100 parts by weight of a polybutadiene synthesized using a rare earth element-based catalyst. 10-60 parts by weight of the (C) unsaturated carboxylic acid and / or metal salt thereof, (D) 0.1-5 parts by weight of the organic sulfur compound, and (E) 5-80 parts by weight of the inorganic filler. The multi-piece solid golf ball according to claim 1, comprising:   The cover has a coating film on the surface, the coating film contains a hydroxyl group-containing polyester obtained by reacting a polyhydric alcohol component and a polybasic acid component, and a non-yellowing polyisocyanate, The multi-piece solid golf ball according to claim 1, wherein at least a part of the alcohol component is formed of a golf ball coating composition having an alicyclic structure in the molecule.   The ratio of the total volume of the dimple space below the plane surrounded by the edge of each dimple to the volume of the phantom sphere assuming that the cover has a large number of dimples on the surface and there is no dimple on the cover surface Ratio) VR is 0.70 to 1.00%, and the ratio of the total area of the phantom spherical surface surrounded by the edge of each dimple to the surface area of the phantom sphere (dimple surface occupancy ratio) SR is 70 to 85%. The multi-piece solid golf ball according to claim 1, 2 or 3. 5. The multi-piece solid golf ball according to claim 1, wherein the (A) polybutadiene has a Mooney viscosity (ML _{1 + 4} (100 ° C.)) of 50 or more and 120 or less. In a multi-piece solid golf ball comprising a solid core, an intermediate layer, and a cover,
The solid core contains (A) 60% or more of cis-1,4-bonds, has a Mooney viscosity (ML _{1 + 4} (100 ° C.)) of 52 or more and 120 or less, and is synthesized using a rare earth element-based catalyst. (B) 0.1 to 0.8 part by weight of an organic peroxide, (C) an unsaturated carboxylic acid and / or its metal with respect to 100 parts by weight of a rubber base material containing 60 to 100% by weight of the polybutadiene prepared Formed from a rubber composition containing a salt, (D) an organic sulfur compound, and (E) an inorganic filler, and the deformation amount of the solid core when loaded with 980 N (100 kgf) is 3.0 to 6.0 mm, and The solid core has a diameter of 30 to 40 mm,
The intermediate layer comprises (P) an olefin-unsaturated carboxylic acid binary random copolymer and / or a metal ion neutralized product of an olefin-unsaturated carboxylic acid binary random copolymer, and (Q) an olefin-unsaturated product. 100: 0 to mass ratio of carboxylic acid-unsaturated carboxylic acid ternary random copolymer and / or metal ion neutralized product of olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ternary random copolymer. With respect to 100 parts by mass of a resin component formulated such that the base resin blended so as to be 25:75 and the (T) non-ionomer thermoplastic elastomer are blended so that the mass ratio is 100: 0 to 50:50, R) Fatty acid having a molecular weight of 280 to 1500 and / or 5 to 80 parts by mass of a derivative thereof, and (S) a base capable of neutralizing an unneutralized acid group in the base resin and (R) component A thermoplastic resin composition containing 0.1 to 10 parts by mass of an inorganic metal compound as an essential component is formed as a main material, and the intermediate layer has a thickness of 0.5 to 2.0 mm, and the intermediate layer The Shore D hardness of the layer is 20-60,
The cover is formed of (F) a thermoplastic polyurethane material as a main component, and the (F) thermoplastic polyurethane material comprises (M) a thermoplastic polyurethane and (N) an isocyanate mixture, and (N) an isocyanate. (N-1) An isocyanate compound having two or more isocyanate groups as functional groups in one molecule, and (N-2) an isocyanate dispersed in a thermoplastic resin that does not substantially react with the isocyanate group. The cover has a thickness of 0.5 to 2.5 mm, and the cover has a Shore D hardness of 50 to 70, and the above (intermediate layer Shore D hardness) ≦ (cover Shore D hardness) There,
Moreover, the multi-piece solid golf ball comprising the solid core, the intermediate layer, and the cover has a deformation amount of 3.0 to 5.0 mm when loaded with a load of 980 N (100 kgf). Peace solid golf ball.   The rubber composition contains 60% or more of the (A) cis-1,4-bond and contains 100 to 100 parts by weight of a polybutadiene synthesized using a rare earth element-based catalyst. 10-60 parts by weight of the (C) unsaturated carboxylic acid and / or metal salt thereof, (D) 0.1-5 parts by weight of the organic sulfur compound, and (E) 5-80 parts by weight of the inorganic filler. The multi-piece solid golf ball according to claim 6, further comprising two or more organic peroxides (B).   The cover has a coating film on the surface, the coating film contains a hydroxyl group-containing polyester obtained by reacting a polyhydric alcohol component and a polybasic acid component, and a non-yellowing polyisocyanate, The multi-piece solid golf ball according to claim 6 or 7, wherein at least a part of the alcohol component is formed of a golf ball coating composition having an alicyclic structure in the molecule.   The ratio of the total volume of the dimple space below the plane surrounded by the edge of each dimple to the volume of the phantom sphere assuming that the cover has a large number of dimples on the surface and there is no dimple on the cover surface Ratio) VR is 0.70 to 1.00%, and the ratio of the total area of the phantom spherical surface surrounded by the edge of each dimple to the surface area of the phantom sphere (dimple surface occupancy ratio) SR is 70 to 85%. The multi-piece solid golf ball according to claim 6, 7 or 8.

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