JP2008161345A - Rubber composition for golf ball and golf ball - Google Patents

Abstract

Provided is a rubber composition for a golf ball, which is capable of producing a golf ball having good rebound resilience and has excellent manufacturing workability such as roll processability and extrusion processability.
The 1,2-vinyl bond content is less than 0.5%, the cis 1,4-bond content is 98.5% or more, and the weight average molecular weight (Mw) and number average measured by gel permeation chromatography. A rubber component containing 30 to 100% by mass of a conjugated diene polymer having a molecular weight (Mn) ratio (Mw / Mn) of 3.5 or less and an inorganic filler are contained in 100 parts by mass of the rubber component. In contrast, the rubber composition for golf balls contains 5 to 80 parts by mass of an inorganic filler.
[Selection figure] None

Description

  The present invention relates to a rubber composition for a golf ball and a golf ball. More specifically, a golf ball rubber composition excellent in manufacturing workability such as roll processability and extrusion processability, which can produce a golf ball having good rebound resilience, and manufactured using this golf ball rubber composition The present invention relates to a golf ball having good rebound resilience.

  Golf balls are roughly classified into solid golf balls and thread wound golf balls. For solid golf balls, a one-piece solid golf ball made of a cross-linked product obtained by integrally molding a rubber composition, and a two-piece or more multi-piece solid in which a cover is coated on a solid core having a layer structure made of a cross-linked product of a hard rubber composition There is a golf ball. Of these solid golf balls, multi-piece solid golf balls have a particularly great flight distance, and in recent years have dominate round golf balls. However, this multi-piece solid golf ball has a drawback that the shot feeling is harder than a wound golf ball. Thus, attempts have been made to improve the feel at impact of the multi-piece solid golf ball by increasing the collapse at the time of hitting by making the core softer and further softening the closer to the center. However, if the core is softened, the rebound resilience is reduced, and the flight distance is reduced. Therefore, development of a multi-piece solid golf ball having excellent rebound resilience even with the same core hardness is desired.

  Conventionally, the core of a multi-piece solid golf ball and the core (solid center) of a one-piece golf ball have a high repulsion property, so that they have been synthesized using a nickel-based catalyst or a cobalt-based catalyst. A rubber composition containing polybutadiene having a -1,4 bond content of 80 mol% or more is preferably used. In addition, it is known that polybutadiene synthesized using a rare earth element-based catalyst can be used for similar applications.

  For example, Patent Documents 1 to 7 disclose that a rubber composition using polybutadiene synthesized using a rare earth element-based catalyst is suitable for golf ball applications. However, sufficient performance is not obtained with respect to the rebound performance of the obtained golf ball. Further, sufficient performance is not obtained in terms of manufacturing workability.

  Patent Document 8 discloses the use of polybutadiene modified with a compound having an alkoxysilyl group as a rubber composition for a golf ball. However, manufacturing workability is not sufficient, and there is still room for further improvement with respect to rebound performance.

  Further, Patent Document 9 discloses a rubber composition containing polybutadiene produced using a metallocene type complex of a samarium (Sm) compound as a catalyst, and a golf ball using the rubber composition. However, the rebound performance of this golf ball is still not sufficient, and there remains room for further improvement.

Japanese Patent Publication No. 3-59931 Japanese Patent Publication No. 6-80123 Japanese Patent No. 2678240 JP-A-6-79018 JP 7-268132 A JP 11-319148 A JP 11-164912 A JP 2002-293996 A JP 2005-111049 A

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is to produce a golf ball with good rebound resilience, such as roll processability and extrusion processability. An object of the present invention is to provide a golf ball rubber composition excellent in manufacturing workability and a golf ball having good rebound resilience.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a rubber component containing a predetermined conjugated diene polymer having a high cis content and a relatively narrow molecular weight distribution, an inorganic filler, It has been found that the above-mentioned problems can be achieved by containing a predetermined ratio, and the present invention has been completed.

  That is, according to the present invention, the following golf ball rubber composition and golf ball are provided.

  [1] The 1,2-vinyl bond content is less than 0.5%, the cis 1,4-bond content is 98.5% or more, and the weight average molecular weight (Mw) and number average molecular weight measured by gel permeation chromatography A rubber component containing 30 to 100% by mass of a conjugated diene polymer having a ratio (Mw / Mn) to (Mn) of 3.5 or less, and an inorganic filler, and 100 parts by mass of the rubber component On the other hand, a golf ball rubber composition containing 5 to 80 parts by mass of the inorganic filler.

[2] Modification in which the conjugated diene polymer is modified from at least one compound selected from the group consisting of the following components (a) to (g) from an unmodified conjugated diene polymer having an active end. The rubber composition for a golf ball according to the above [1], which is a conjugated diene polymer.
Component (a): alkoxysilane compound containing at least one epoxy group and / or isocyanate group in the molecule (b) component: halogenated represented by any one of the following general formulas (1) to (5) Organometallic compound, halogenated metal compound, or organometallic compound R ¹ _n M′X _4-n (1)
M'X ₄ (2)
M'X ₃ (3)
R ¹ _n M ′ (R ² —COOR ³ ) _4-n (4)
R ¹ _n M ′ (R ² —COR ³ ) _4-n (5)
(In the general formulas (1), (4), and (5), R ¹ and R ² are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and n is an integer of 0 to 3. In the general formulas (4) and (5), R ³ is a hydrocarbon group having 1 to 20 carbon atoms which may contain a carbonyl group or an ester group in the side chain. In (5), M ′ is a tin atom, a silicon atom, a germanium atom, or a phosphorus atom, and in the general formulas (1) to (3), X is a halogen atom.
Component (c): Y = C = Z bond (where Y is a carbon atom, oxygen atom, nitrogen atom or sulfur atom, and Z is an oxygen atom, nitrogen atom or sulfur atom) in the molecule A heterocumulene compound (d) component; a hetero 3-membered ring compound containing a bond represented by the following general formula (6) in the molecule (excluding the component (a))

（前記一般式（６）中、Ｙは酸素原子、窒素原子又は硫黄原子である）

(In the general formula (6), Y is an oxygen atom, a nitrogen atom or a sulfur atom)

(E) Component: Halogenated isocyano compound (f) Component: Carboxylic acid, acid halide, ester compound, carbonate compound, or acid anhydride represented by any of the following general formulas (7) to (12) ⁴ (COOH) _m (7)
R ⁵ (COX) _m (8)
R ⁶ COO-R ⁷ (9)
^{R 8 -OCOO-R 9 (10} )
R ¹⁰ (COOCO-R ¹¹ ) _m (11)

（前記一般式（７）〜（１２）中、Ｒ^４〜Ｒ^１２は、同一又は異なる、炭素数１〜５０の炭化水素基である。前記一般式（８）中、Ｘはハロゲン原子である。また、前記一般式（７）、（８）、（１１）、及び（１２）中、ｍは１〜５の整数である）

(In the general formulas (7) to (12), R ^{4 to} R ¹² are the same or different hydrocarbon groups having 1 to 50 carbon atoms. In the general formula (8), X is a halogen atom. In the general formulas (7), (8), (11), and (12), m is an integer of 1 to 5.

Component (g); the following general formula (13) to either a carboxylic acid metal salt represented by R ¹³ _l M of _{^{(15) "(OCOR 14)}} 4-l (13)
_{^{R 15 l M "(OCO-}} R 16 -COOR 17) 4-l (14)

（前記一般式（１３）〜（１５）中、Ｒ^１３〜Ｒ^１９は、同一又は異なる、炭素数１〜２０の炭化水素基であり、Ｍ”はスズ原子、ケイ素原子、又はゲルマニウム原子であり、ｌは０〜３の整数である）

(In the general formulas (13) to (15), R ^{13 to} R ¹⁹ are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and M ″ is a tin atom, a silicon atom, or a germanium atom. , L is an integer from 0 to 3)

[3] The above-mentioned [2], wherein the unmodified conjugated diene polymer is obtained by polymerizing 1,3-butadiene using a catalyst mainly composed of the following components (h) to (j): ] The rubber composition for golf balls as described in any one of Claims 1-3.
(H) component; a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base (i) component; alumoxane and / or AlR ²⁰ R ²¹ R ²² (provided that R ²⁰ and R ²¹ are the same or different, a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, R ²² is a hydrocarbon group having 1 to 10 carbon atoms, and R ²² is the same as R ²⁰ or R ²¹ . An organoaluminum compound represented by the formula (j): an iodine-containing compound containing at least one iodine atom in its molecular structure

  [4] A structural unit in which the conjugated diene polymer is derived from at least one conjugated diene compound selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. The rubber composition for a golf ball according to any one of [1] to [3], which is contained.

  [5] The rubber composition for a golf ball according to any one of [1] to [4], wherein the inorganic filler is at least one selected from the group consisting of zinc oxide, barium sulfate, and silica.

  [6] Natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber, acrylonitrile-butadiene copolymer rubber, chloroprene rubber, and halogen The rubber composition for a golf ball according to any one of the above [1] to [5], wherein at least one selected from the group consisting of chlorinated butyl rubber is further included in the rubber component.

  [7] Said [1]-containing 10-50 mass parts of crosslinking agents, 5-80 mass parts of inorganic fillers, and 0.1-10 mass parts of organic peroxides with respect to 100 mass parts of said rubber components. [6] The rubber composition for golf balls according to any one of [6].

  [8] A golf ball obtained by crosslinking and molding the golf ball rubber composition according to any one of [1] to [7].

  The rubber composition for a golf ball of the present invention can produce a golf ball having good rebound resilience, and has an effect of being excellent in manufacturing workability such as roll processability and extrusion processability.

  The golf ball of the present invention has an effect of good rebound resilience and can be manufactured with good workability.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

1. Golf Ball Rubber Composition One embodiment of the golf ball rubber composition of the present invention has a 1,2-vinyl bond content of less than 0.5%, a cis 1,4-bond content of 98.5% or more, and Rubber component containing 30 to 100% by mass of a conjugated diene polymer having a ratio (Mw / Mn) of 3.5 or less of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography And an inorganic filler is contained, and 5-80 mass parts of inorganic fillers are contained with respect to 100 mass parts of rubber components. The details will be described below.

(Conjugated diene polymer)
The rubber component contained in the golf ball rubber composition of the present embodiment contains a conjugated diene polymer at a predetermined ratio. This conjugated diene polymer has a 1,2-vinyl bond content of less than 0.5%, a cis 1,4-bond content of 98.5% or more, and a weight average molecular weight (Mw) measured by gel permeation chromatography. ) And the number average molecular weight (Mn) (Mw / Mn) is 3.5 or less, there is no particular limitation. Specific examples of the conjugated diene polymer are selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and myrcene. And those containing a structural unit derived from at least one monomer. Among these, those containing a structural unit derived from at least one monomer selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene can be suitably used.

  The 1,2-vinyl bond content of the conjugated diene polymer is less than 0.5%, preferably 0.3% or less. When the 1,2-vinyl bond content of the conjugated diene polymer is 0.5% or more, the rebound resilience of the golf ball obtained using the rubber composition containing the conjugated diene polymer is lowered. The 1,2-vinyl bond content of the conjugated diene polymer can be easily adjusted by controlling the polymerization temperature.

  The cis 1,4-bond content of the conjugated diene polymer is 98.5% or more, preferably 99.0% or more. When the cis 1,4-bond content of the conjugated diene polymer is less than 98.5%, the rebound resilience of the golf ball obtained using the rubber composition containing the conjugated diene polymer is lowered. The cis 1,4-bond content of the conjugated diene polymer can be easily adjusted by controlling the polymerization temperature.

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the conjugated diene polymer measured by gel permeation chromatography is 3.5 or less, preferably 2.0 or less. is there. When the value of Mw / Mn is more than 3.5, the rebound resilience of a golf ball obtained using the rubber composition containing this conjugated diene polymer is lowered. The value of Mw / Mn of the conjugated diene polymer can be easily adjusted by controlling the molar ratio of the components (h) to (j) described later.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the conjugated diene polymer is preferably 5 to 50, more preferably 10 to 40. When the Mooney viscosity is less than 5, mechanical properties after vulcanization, wear resistance, and the like may deteriorate. On the other hand, if the Mooney viscosity is more than 50, the processability during kneading of the modified conjugated diene polymer after the modification reaction may be lowered. This Mooney viscosity can be easily adjusted by controlling the molar ratio of the components (h) to (j) described later.

  In order to produce a conjugated diene polymer, polymerization may be performed using a solvent, or polymerization may be performed in the absence of a solvent. As a polymerization solvent, an inert organic solvent can be mentioned as a suitable example. Examples of the inert organic solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons having 6 to 20 carbon atoms such as cyclopentane and cyclohexane; Monoolefins such as 1-butene and 2-butene; aromatic hydrocarbons such as benzene, toluene and xylene; methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene and bromobenzene And halogenated hydrocarbons such as chlorotoluene.

  The temperature of the polymerization reaction in producing the conjugated diene polymer is usually −30 ° C. to + 200 ° C., preferably 0 to + 150 ° C. Moreover, there is no restriction | limiting in particular about the form of a polymerization reaction, You may carry out using a batch type reactor, and you may carry out by a continuous type using apparatuses, such as a multistage continuous type reactor. In addition, when using a polymerization solvent, it is preferable to make the monomer concentration in this polymerization solvent into 5-50 mass%, and it is still more preferable to set it as 7-35 mass%. In addition, in order to produce a conjugated diene polymer and not to deactivate an unmodified conjugated diene polymer having an active terminal, which will be described later, a deactivation effect of oxygen, water, carbon dioxide gas, etc. in the polymerization system It is preferable to take care to minimize the mixing of certain compounds.

(Modified conjugated diene polymer)
From the viewpoint of storage stability, it is preferable to use a modified conjugated diene polymer as the conjugated diene polymer contained in the rubber component contained in the golf ball rubber composition of the present embodiment. This modified conjugated diene polymer is obtained by modifying an unmodified conjugated diene polymer having an active end with at least one compound (modifier) selected from the group consisting of the components (a) to (g). It is obtained by doing.

((A) component)
The component (a) is an alkoxysilane compound containing at least one epoxy group and / or isocyanate group in its molecular structure. Specific examples of the alkoxysilane compound containing at least one epoxy group among the components (a) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropyltriphenoxysilane. , (3-glycidyloxypropyl) methyldimethoxysilane, (3-glycidyloxypropyl) methyldiethoxysilane, (3-glycidyloxypropyl) methyldiphenoxysilane, (3-glycidyloxypropyl) methyldimethoxysilane condensate, (3-glycidyloxypropyl) methyldiethoxysilane condensate, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane condensate, 3-glyci And the like condensates of Le trimethoxy silane.

  Specific examples of the alkoxysilane compound containing at least one isocyanate group among the component (a) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropyl. Triphenoxysilane, (3-isocyanatopropyl) methyldimethoxysilane, (3-isocyanatopropyl) methyldiethoxysilane, (3-isocyanatopropyl) methyldiphenoxysilane, (3-isocyanatopropyl) methyldimethoxysilane Condensate, condensate of (3-isocyanatopropyl) methyldiethoxysilane, condensate of β- (isocyanatocyclohexyl) ethyltrimethoxysilane, (3-isocyanatopropyl) trimethoxysilane, (3-isocyanate Topuropiru) condensates of triethoxysilane and the like.

((B) component)
The component (b) is a halogenated organometallic compound, a halogenated metal compound, or an organometallic compound represented by any one of the general formulas (1) to (5). The compound represented by the general formula (1) is a halogenated organometallic compound, the compounds represented by the general formulas (2) and (3) are metal halide compounds, and the general formula The compounds represented by (4) and (5) are organometallic compounds.

Among the compounds represented by the general formulas (1) to (3), as M ¹ being a tin atom, for example, triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, tri Halogenated organometallic compounds such as octyltin chloride, diphenyltin dichloride, dibutyltin dichloride, dihexyltin dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride; halogenated metal compounds such as tin tetrachloride be able to.

Among the compounds represented by the general formulas (1) to (3), those in which M ¹ is a silicon atom include, for example, triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, trimethylchlorosilane, and diphenyl. Halogenated organometallic compounds such as dichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane, phenylchlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane; Mention may be made of metal halide compounds such as silicon chloride.

Among the compounds represented by the general formulas (1) to (3), those in which M ¹ is a germanium atom include, for example, triphenyl germanium chloride, dibutyl germanium dichloride, diphenyl germanium dichloride, and butyl germanium trichloride. And halogenated organic metal compounds such as germanium tetrachloride. Furthermore, as M ¹ is phosphorus atom, for example, a metal halide compound such as phosphorus trichloride.

  The compounds represented by the general formulas (4) and (5) are organometallic compounds containing an ester group or a carbonyl group in the molecular structure. As the component (b), the aforementioned halogenated organometallic compound, halogenated metal compound, and organometallic compound may be used in any proportion.

(Component (c))
The component (c) has a Y = C = Z bond (wherein Y is a carbon atom, oxygen atom, nitrogen atom or sulfur atom, and Z is an oxygen atom, nitrogen atom or sulfur atom) in its molecular structure. ) Containing heterocumulene compounds.

  Among the components (c), those in which Y is a carbon atom and Z is an oxygen atom are ketene compounds, those in which Y is a carbon atom and Z is a sulfur atom are thioketene compounds, Y is a nitrogen atom, and Z is an oxygen atom. Is an isocyanate compound, Y is a nitrogen atom, Z is a sulfur atom, a thioisocyanate compound, Y and Z are both nitrogen atoms, a carbodiimide compound, and both Y and Z are oxygen atoms. Is carbon dioxide, Y is an oxygen atom, Z is a sulfur atom, carbonyl sulfide is Y, and both Y and Z are sulfur atoms is carbon disulfide. In addition, (c) component is not limited to these combinations.

  Examples of the ketene compound include ethyl ketene, butyl ketene, phenyl ketene, and toluyl ketene. Examples of the thioketene compound include ethylene thioketene, butyl thioketene, phenyl thioketene, toluyl thioketene, and the like. Examples of the isocyanate compound include phenyl isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric type diphenylmethane diisocyanate, hexamethylene diisocyanate, and the like. Can be mentioned. Examples of the thioisocyanate compound include phenylthioisocyanate, 2,4-tolylene diisocyanate, hexamethylene dithioisocyanate, and the like. Examples of the carbodiimide compound include N, N′-diphenylcarbodiimide, N, N′-diethylcarbodiimide, and the like.

(Component (d))
The component (d) is a hetero 3-membered ring compound containing a bond represented by the general formula (6) in the molecular structure (excluding the component (a)). Specific examples of the component (d) include hetero three-membered ring compounds.

  Among the components (d), those having Y as an oxygen atom are epoxy compounds, those having a nitrogen atom are ethyleneimine derivatives, and those having a sulfur atom are thiirane compounds. Examples of the epoxy compound include ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, epoxidized natural rubber, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, and ethylene glycol diglycidyl. Ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycidyl methacrylate, glycidyl acrylate, N, N-diglycidyl Aniline, N, N-diglycidyl tolui Emissions, N, N-glycidyl-glycidyloxy aniline, can be mentioned tetraglycidyl diaminodiphenyl methane and the like. Examples of the ethyleneimine derivative include ethyleneimine, propyleneimine, N-phenylethyleneimine, N- (β-cyanoethyl) ethyleneimine and the like. Examples of the thiirane compound include thiirane, methylthiirane, phenylthiirane, and the like.

((E) component)
The component (e) is a halogenated isocyano compound. The halogenated isocyano compound refers to a compound having a structure represented by N═C—X (where X is a halogen atom). Examples of such halogenated isocyano compounds include 2-amino-6-chloropyridine, 2,5-dibromopyridine, 4-chloro-2-phenylquinazoline, 2,4,5-tribromoimidazole, 3,6 -Dichloro-4-methylpyridazine, 3,4,5-trichloropyridazine, 4-amino-6-chloro-2-mercaptopyrimidine, 2-amino-4-chloro-6-methylpyrimidine, 2-amino-4,6 -Dichloropyrimidine, 6-chloro-2,4-dimethoxypyrimidine, 2-chloropyrimidine, 2,4-dichloro-6-methylpyrimidine, 4,6-dichloro-2- (methylthio) pyrimidine, 2,4,5 6-tetrachloropyrimidine, 2,4,6-trichloropyrimidine, 2-amino-6-chloropyrazine, 2,6-dichloro Pyrazine, 2,4-bis (methylthio) -6-chloro-1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine, 2-bromo-5-nitrothiazole, 2- Examples thereof include chlorobenzothiazole and 2-chlorobenzoxazole.

((F) component)
The component (f) is a carboxylic acid, an acid halide, an ester compound, a carbonate compound, or an acid anhydride represented by any one of the general formulas (7) to (12). The compound represented by the general formula (7) is a carboxylic acid, the compound represented by the general formula (8) is an acid halide, and the compound represented by the general formula (9) is an ester. The compound represented by the general formula (10) is a carbonate compound, and the compounds represented by the general formulas (11) and (12) are acid anhydrides.

  Examples of the carboxylic acid represented by the general formula (7) include acetic acid, stearic acid, adipic acid, maleic acid, benzoic acid, acrylic acid, methacrylic acid, phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid. And hydrolysates or partial hydrolysates of pyromellitic acid, merit acid, polymethacrylic acid ester compound, polyacrylic acid compound and the like.

  Examples of the acid halide represented by the general formula (8) include acetic acid chloride, propionic acid chloride, butanoic acid chloride, isobutanoic acid chloride, octanoic acid chloride, acrylic acid chloride, benzoic acid chloride, stearic acid chloride, phthalate. Examples thereof include acid chloride, maleic acid chloride, oxalic acid chloride, acetyl iodide, benzoyl iodide, acetyl fluoride, and benzoyl fluoride.

  Examples of the ester compound represented by the general formula (9) include ethyl acetate, ethyl stearate, diethyl adipate, diethyl maleate, methyl benzoate, ethyl acrylate, ethyl methacrylate, diethyl phthalate, and terephthalate. Examples include dimethyl acid, tributyl trimellitic acid, tetraoctyl pyromellitic acid, hexaethyl merit acid, phenyl acetate, polymethyl methacrylate, polyethyl acrylate, polyisobutyl acrylate, and the like.

  Examples of the carbonate compound represented by the general formula (10) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dihexyl carbonate, diphenyl carbonate and the like.

  Examples of the acid anhydride represented by the general formula (11) include acetic anhydride, propionic anhydride, isobutyric anhydride, isovaleric anhydride, heptanoic anhydride, benzoic anhydride, and cinnamic anhydride. Can do. Examples of the acid anhydride represented by the general formula (12) include succinic anhydride, methyl succinic anhydride, maleic anhydride, glutaric anhydride, citraconic anhydride, phthalic anhydride, and styrene-maleic anhydride. A polymer etc. can be mentioned.

  In addition, the compound shown as a specific example of the component (f) contains an aprotic polar group such as an ether group or a tertiary amino group in the molecule within the range not impairing the object of the present invention. It does not matter. Moreover, (f) component may be used individually by 1 type, and may be used in combination of 2 or more type. Furthermore, this (f) component may contain the compound containing a free alcohol group and a phenol group as an impurity.

((G) component)
The component (g) is a carboxylic acid metal salt represented by any one of the general formulas (13) to (15). Examples of the compound represented by the general formula (13) include the compounds shown below.

  Triphenyltin laurate, triphenyltin-2-ethylhexarate, triphenyltin naphthate, triphenyltin acetate, triphenyltin acrylate, tri-n-butyltin laurate, tri-n-butyltin-2-ethylhexarate , Tri-n-butyltin naphthate, tri-n-butyltin acetate, tri-n-butyltin acrylate, tri-t-butyltin laurate, tri-t-butyltin-2-ethylhexarate, tri-t-butyltin naphthate , Tri-t-butyltin acetate, tri-t-butyltin acrylate, triisobutyltin laurate, triisobutyltin-2-ethylhexarate, triisobutyltin naphthate, triisobutyltin acetate, triisobutyltin acrylate , Triisopropyl tin laurate, triisopropyl tin-2-ethyl hexatate, triisopropyl tin naphthate, triisopropyl tin acetate, triisopropyl tin acrylate, trihexyl tin laurate, trihexyl tin-2-ethyl hexatate , Trihexyl tin acetate, trihexyl tin acrylate, trioctyl tin laurate, trioctyl tin-2-ethyl hexatate, trioctyl tin naphthate, trioctyl tin acetate, trioctyl tin acrylate, tri-2-ethylhexyl tin laur Rate, tri-2-ethylhexyltin-2-ethylhexarate, tri-2-ethylhexyltin naphthate, tri-2-ethylhexyltin acetate, tri-2-ethylhexyl 'S acrylate,

  Tristearyl tin laurate, Tristearyl tin-2-ethyl hexatate, Tristearyl tin naphthate, Tristearyl tin acetate, Tristearyl tin acrylate, Tribenzyl tin laurate, Tribenzyl tin-2-ethyl hexatate, Tribenge Rutin naphthate, tribenzyltin acetate, tribenzyltin acrylate, diphenyltin dilaurate, diphenyltin-di-2-ethylhexarate, diphenyltin distearate, diphenyltin dinaphthate, diphenyltin diacetate, diphenyltin diacrylate,

  Di-n-butyltin dilaurate, di-n-butyltin di-2-ethylhexarate, di-n-butyltin distearate, di-n-butyltin dinaphthate, di-n-butyltin diacetate, di-n-butyltin Diacrylate, di-t-butyltin dilaurate, di-t-butyltin di-2-ethylhexarate, di-t-butyltin distearate, di-t-butyltin dinaphthate, di-t-butyltin diacetate, di- t-Butyltin diacrylate, diisobutyltin dilaurate, diisobutyltin di-2-ethylhexarate, diisobutyltin distearate, diisobutyltin dinaphthate, diisobutyltin diacetate, diisobutyltin diacrylate, diisopropyltin dilaurate, diisopropyls -Di-2-ethylhexarate, diisopropyltin distearate, diisopropyltin dinaphthate, diisopropyltin diacetate, diisopropyltin diacrylate, dihexyltin dilaurate, dihexyltin di-2-ethylhexate, dihexyltin distearate Dihexyltin dinaphthate, dihexyltin diacetate, dihexyltin diacrylate, di-2-ethylhexyltin dilaurate, di-2-ethylhexyltin-di-2-ethylhexarate, di-2-ethylhexyltin distearate, Di-2-ethylhexyltin dinaphthate, di-2-ethylhexyltin diacetate, di-2-ethylhexyltin diacrylate, dioctyltin dilaurate, dioctyltin di-2-ethyl Kisateto, dioctyltin distearate, dioctyltin naphthoquinone Tate, dioctyltin diacetate, dioctyltin diacrylate,

  Distearyl tin dilaurate, distearyl tin di-2-ethylhexarate, distearyl tin distearate, distearyl tin dinaphthate, distearyl tin diacetate, distearyl tin diacrylate, dibenzyltin dilaurate, dibenzyltin di-2 -Ethyl hexatate, dibenzyl tin distearate, dibenzyl tin dinaphthate, dibenzyl tin diacetate, dibenzyl tin diacrylate, phenyl tin trilaurate, phenyl tin tri-2-ethyl hexatate, phenyl tin tri Naphthate, phenyltin triacetate, phenyltin triacrylate,

  n-butyltin trilaurate, n-butyltin tri-2-ethylhexarate, n-butyltin trinaphthate, n-butyltin triacetate, n-butyltin triacrylate, t-butyltin trilaurate, t-butyltin tri-2- Ethyl hexatate, t-butyl tin trinaphthate, t-butyl tin triacetate, t-butyl tin triacrylate, isobutyl tin trilaurate, isobutyl tin tri-2-ethyl hexatate, isobutyl tin trinaphthate, isobutyl tin triacetate, isobutyl tin Triacrylate, isopropyl tin trilaurate, isopropyl tin tri-2-ethyl hexatate, isopropyl tin trinaphthate, isopropyl tin triacetate, isopropyl tin triacrylate Hexyl tin trilaurate, hexyl tin tri-2-ethyl hexatate, hexyl tin trinaphthate, hexyl tin triacetate, hexyl tin triacrylate, octyl tin trilaurate, octyl tin tri-2-ethyl hexatate, Octyltin trinaphthate, octyltin triacetate, octyltin triacrylate, 2-ethylhexyltin trilaurate, 2-ethylhexyltin tri-2-ethylhexarate, 2-ethylhexyltin trinaphthate, 2-ethylhexyltin triacetate, 2 -Ethylhexyl tin triacrylate, stearyl tin trilaurate, stearyl tin tri-2-ethyl hexatate, stearyl tin trinaphthate, stearyl tin triacetate, stear Dibutyltin triacrylate, benzyl tin trilaurate, benzyl tin tri-2-ethyl hexa Tate, benzyl tin tri naphthoquinone Tate, benzyl tin triacetate, benzyl tin triacrylate.

  Examples of the compound represented by the general formula (14) include the compounds shown below.

  Diphenyltin bismethylmalate, diphenyltin bis-2-ethylhexylmalate, diphenyltin bisoctylmalate, diphenyltin bisbenzylmalate, di-n-butyltin bismethylmalate, di-n-butyltin bis-2-ethylhexylmalate, Di-n-butyltin bisoctylmalate, di-n-butyltin bisbenzylmalate, di-t-butyltin bismethylmalate, di-t-butyltin bis-2-ethylhexylmalate, di-t-butyltin bisoctylmalate Malate, di-t-butyltin bisbenzyl malate, diisobutyltin bismethyl malate, diisobutyltin bis-2-ethylhexyl malate, diisobutyltin bisoctyl malate, diisobutyltin bisbenzyl malate, diisopro Dibutyltin bis methyl maleate, diisopropyl tin bis-2-ethylhexyl maleate, diisopropyl tin bis-octyl maleate, diisopropyl tin bis benzyl maleate,

  Dihexyltin bismethylmalate, dihexyltin bis-2-ethylhexylmalate, dihexyltin bisoctylmalate, dihexyltin bisbenzylmalate, di-2-ethylhexyltin bismethylmalate, di-2-ethylhexyltin bis- 2-ethylhexylmalate, di-2-ethylhexyltin bisoctylmalate, di-2-ethylhexyltin bisbenzylmalate, dioctyltin bismethylmalate, dioctyltin bis-2-ethylhexylmalate, dioctyltin bisoctylmer Rate, dioctyltin bisbenzyl malate,

  Distearyl tin bismethyl malate, distearyl tin bis-2-ethylhexyl malate, distearyl tin bis octyl malate, distearyl tin bis benzyl malate, dibenzyl tin bismethyl malate, dibenzyl tin bis-2- Ethyl hexyl malate, dibenzyltin bisoctyl malate, dibenzyltin bisbenzyl malate, diphenyltin bismethyladipate, diphenyltin bis-2-ethylhexyl adipate, diphenyltin bisoctyl adipate, diphenyltin bisbenzyl adipate,

  Di-n-butyltin bismethyl adipate, di-n-butyltin bis-2-ethylhexyl adipate, di-n-butyltin bisoctyl adipate, di-n-butyltin bisbenzyl adipate, di-t-butyltin bismethyladipate, di- t-butyltin bis-2-ethylhexyl adipate, di-t-butyltin bisoctyl adipate, di-t-butyltin bisbenzyl adipate, diisobutyltin bismethyladipate, diisobutyltin bis-2-ethylhexyl adipate, diisobutyltin bisoctyl adipate, diisobutyl Tin bisbenzyl adipate, diisopropyl tin bismethyl adipate, diisopropyl tin bis-2-ethylhexyl adipate, diisopropyl tin bisoctyl adipate, dii Propyl tin bisbenzyl adipate, dihexyl tin bismethyl adipate, dihexyl tin bis-2-ethylhexyl adipate, dihexyl tin bismethyl adipate, dihexyl tin bisbenzyl adipate, di-2-ethylhexyl tin bismethyl adipate, di-2-ethylhexyl tin bis 2-ethylhexyl adipate, di-2-ethylhexyltin bisoctyl adipate, di-2-ethylhexyltin bisbenzyladipate, dioctyltin bismethyladipate, dioctyltin bis-2-ethylhexyl adipate, dioctyltin bisoctyl adipate, dioctyltin bis Benzyl adipate, distearyl tin bismethyl adipate, distearyl tin bis-2-ethylhexyl adipate, diste Lil tin bis-octyl adipate, distearyl tin bis-benzyl adipate, dibenzyl tin bis-methyl adipate, dibenzyl tin bis-2-ethylhexyl adipate, dibenzyl tin bis-octyl adipate, dibenzyl tin bis-benzyl adipate.

  In addition, as a compound other than the above-described compound represented by the general formula (14), two carboxylic acid groups such as malonic acid, malic acid, and succinic acid are contained instead of maleic acid and adipic acid of the above-mentioned compound. And derivatives using dicarboxylic acid.

  Examples of the compound represented by the general formula (15) include diphenyltin maleate, di-n-butyltin maleate, di-t-butyltin maleate, diisobutyltin maleate, diisopropyltin maleate, and dihexyltin. Malate, di-2-ethylhexyl tin malate, dioctyl tin malate, distearyl tin malate, dibenzyl tin malate, diphenyl tin adipate, di-n-butyl tin adipate, di-t-butyl tin adipate, diisobutyl tin adipate, Diisopropyltin adipate, dihexyltin adipate, di-2-ethylhexyltin adipate, dioctyltin adipate, distearyltin adipate, dibenzyltin adipate and the like can be mentioned.

  In addition, as a compound other than the above compound represented by the general formula (15), in place of maleic acid or adipic acid of the above compound, two carboxylic acid groups such as malonic acid, malic acid, succinic acid and the like are contained. And derivatives using dicarboxylic acid.

  The components (a) to (g) described so far can be used alone or in combination of two or more as a modifier. Moreover, it is preferable from a viewpoint of storage stability to use together (a) component and at least 1 type selected from the group which consists of (b)-(g) component, (a) component and (c) component Or it is more preferable to use together with (g) component. In addition, when using 2 or more types of components together, there is no restriction | limiting in particular about the order which adds (reacts) component (a)-(g).

  The usage-amount of a modifier | denaturant is 0.01-200 normally in the molar ratio with respect to an unmodified conjugated diene type polymer, Preferably it is 0.1-150. If the molar ratio with respect to the unmodified conjugated diene polymer is less than 0.01, the progress of the modification reaction may be insufficient. On the other hand, when the molar ratio with respect to the unmodified conjugated diene polymer is more than 200, the effect of improving the storage stability is saturated and a toluene insoluble matter (gel) tends to be generated.

  When using together (a) and at least 1 type selected from the group which consists of (b)-(g) component as a modifier | denaturant, the ratio of (a) component contained in a modifier | denaturant is 5-90. It is preferable that it is mol%, and it is still more preferable that it is 10-80 mol%. When the proportion of the component (a) contained in the modifier is less than 5 mol%, the storage stability tends to deteriorate. On the other hand, when it exceeds 90 mol%, the improvement effect on storage stability is saturated, and a toluene insoluble matter (gel) tends to be generated. The modification reaction is preferably performed at a temperature of 160 ° C. or lower, and more preferably at a temperature of −30 ° C. to + 130 ° C. Moreover, there is no restriction | limiting in particular about the time which performs modification | denaturation reaction, It is preferable that it is 0.1 to 10 hours, and it is still more preferable that it is 0.2 to 5 hours.

  The modification reaction is preferably a solution reaction in which monomer components are reacted in a solution. This solution reaction may be, for example, a reaction performed in a solution containing an unreacted monomer used when polymerizing an unmodified conjugated diene polymer. Moreover, there is no restriction | limiting in particular about the format of a denaturation reaction, You may carry out using a batch type reactor, and you may carry out by a continuous type using apparatuses, such as a multistage continuous type reactor and an in-line mixer. This modification reaction is after the polymerization reaction of the unmodified conjugated diene polymer is completed, and before various operations necessary for polymer isolation such as desolvation treatment, water treatment, and heat treatment are performed. It is necessary to implement. The target modified conjugated diene polymer is prepared by adding a polymerization terminator or a polymerization stabilizer to the reaction system as necessary after the modification reaction is completed, and removing a solvent known in the art in the production of a modified conjugated diene polymer, followed by drying. It can be recovered by performing the operation.

(Unmodified conjugated diene polymer)
The unmodified conjugated diene polymer used in producing the modified conjugated diene polymer can be produced according to the method for producing the conjugated diene polymer described above. However, the unmodified conjugated diene polymer is preferably obtained by polymerizing 1,3-butadiene using a catalyst mainly composed of the components (h) to (j). (H) to (j) By polymerizing using a catalyst having as a main component, an unmodified conjugated diene polymer having a narrower molecular weight distribution and a higher cis 1,4-bond content is obtained. Can do.

((H) component)
The component (h) is a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base. Specific examples of the rare earth element contained in the rare earth element-containing compound include neodymium, praseodymium, cerium, lanthanum, gadolinium, and samarium. Of these, neodymium is preferred. In addition, these rare earth elements can be used individually by 1 type or in combination of 2 or more types. Specific examples of the rare earth element-containing compound include rare earth element carboxylates, alkoxides, β-diketone complexes, phosphates, phosphites and the like. Among these, carboxylate or phosphate is preferable, and carboxylate is more preferable.

Specific examples of the carboxylate of the rare earth element include a salt of a carboxylic acid represented by (R ²³ —CO ₂ ) ₃ M (where M is a rare earth element corresponding to atomic numbers 57 to 71 in the periodic table, and R ²³ is a hydrocarbon group having 1 to 20 carbon atoms). R ²³ is preferably a saturated or unsaturated alkyl group, and more preferably a linear, branched, or cyclic alkyl group. The carboxyl group is bonded to a primary, secondary, or tertiary carbon atom. More specifically, octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, trade name “Versatic acid” (manufactured by Shell Chemical Co., Ltd.) (carboxyl group bonded to tertiary carbon atom) Carboxylic acid) and the like. Of these, salts of 2-ethylhexanoic acid, naphthenic acid, and versatic acid are preferred.

Specific examples of alkoxides of rare earth elements include those represented by (R ²⁴ O) ₃ M (where M is a rare earth element corresponding to atomic numbers 57 to 71 in the periodic table, and R ²⁴ has 1 to 20 carbon atoms. Hydrocarbon groups (preferably saturated or unsaturated, linear, branched or cyclic). The carboxyl group is bonded to a primary, secondary, or tertiary carbon atom. Specific examples of the alkoxy group represented by “R ²⁴ O” include 2-ethyl-hexylalkoxy group, oleylalkoxy group, stearylalkoxy group, phenoxy group, benzylalkoxy group and the like. Of these, a 2-ethyl-hexylalkoxy group and a benzylalkoxy group are preferable.

  Specific examples of the rare earth element β-diketone complex include acetylacetone complex, benzoylacetone complex, propionitrileacetone complex, valerylacetone complex, ethylacetylacetone complex and the like. Of these, acetylacetone complex and ethylacetylacetone complex are preferable.

  Specific examples of rare earth element phosphates or phosphites include bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, bis (p-nonylphenyl) phosphate, and phosphoric acid. Bis (polyethylene glycol-p-nonylphenyl), phosphoric acid (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl), 2-ethylhexylphosphonic acid mono-2-ethylhexyl, 2-ethylhexylphosphonic acid mono-p-nonylphenyl, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, bis (p-nonylphenyl) phosphinic acid, (1-methylheptyl) (2- Ethylhexyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, etc. Mention may be made of salt. Of these, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, and a salt of bis (2-ethylhexyl) phosphinic acid are preferred.

  Among the rare earth element-containing compounds, among those exemplified so far, neodymium phosphate or neodymium carboxylate is more preferable, and carboxylates such as neodymium 2-ethylhexanoate, neodymium versatate, etc. Is particularly preferred.

  In order to solubilize a rare earth element-containing compound in a solvent, or to store it stably for a long period of time, a mixture of a rare earth element-containing compound and a Lewis base, or a reaction product obtained by reacting a rare earth element-containing compound and a Lewis base It is also preferable to do. The amount of the Lewis base is preferably 0 to 30 mol, more preferably 1 to 10 mol, relative to 1 mol of the rare earth element. Specific examples of the Lewis base include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, a monovalent or divalent alcohol, and the like. The component (h) described so far can be used alone or in combination of two or more.

((I) component)
(I) The component is alumoxane (also referred to as “aluminoxane”) and / or AlR ²⁰ R ²¹ R ²² (wherein R ²⁰ and R ²¹ are the same or different, a hydrocarbon group having 1 to 10 carbon atoms or hydrogen an ^{atom, R 22} is a hydrocarbon group having 1 to 10 carbon ^{atoms, R 22 is} an organic aluminum compound represented by may be the same or different and ^{R 20} or ^{R 21).}

  The alumoxane is a compound whose structure is represented by the following general formula (16) or (17). In addition, Fine Chemical, 23, (9), 5 (1994), J. Org. Am. Chem. Soc. 115, 4971 (1993); Am. Chem. Soc. 117, 6465 (1995), and alumoxane aggregates.

In the general formulas (16) and (17), R ²³ is a hydrocarbon group having 1 to 20 carbon atoms, and n ′ is an integer of 2 or more. In the general formulas (16) and (17), specific examples of R ²³ include methyl, ethyl, propyl, butyl, isobutyl, t-butyl, hexyl, isohexyl, octyl, and isooctyl groups. Of these, methyl, ethyl, isobutyl and t-butyl groups are preferable, and a methyl group is more preferable. Moreover, it is preferable that n 'is an integer of 4-100 in the said General Formula (16) and (17).

  Specific examples of alumoxane include methylalumoxane (MAO), ethylalumoxane, n-propylalumoxane, n-butylalumoxane, isobutylalumoxane, t-butylalumoxane, hexylalumoxane, isohexylalumoxane and the like. Can be mentioned. Alumoxane can be produced by a known method. For example, trialkylaluminum or dialkylaluminum monochloride is added to an organic solvent such as benzene, toluene, xylene, and water, water vapor, water vapor-containing nitrogen gas, or copper sulfate pentahydrate or aluminum sulfate 16-hydrate. It can be produced by adding a salt having water of crystallization to react. In addition, alumoxane can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the organoaluminum compound represented by AlR ²⁰ R ²¹ R ²² include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t. -Butyl aluminum, tripentyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, hydrogenated Dihexyl aluminum, diisohexyl aluminum hydride, dioctyl aluminum hydride, diisooctyl aluminum hydride, ethyl aluminum Ride, n- propyl aluminum dihydride, isobutyl aluminum dihydride and the like, preferably, may be mentioned triethyl aluminum, triisobutyl aluminum, hydrogenated diethyl aluminum, diisobutyl aluminum hydride or the like. An organoaluminum compound can be used individually by 1 type or in combination of 2 or more types.

((J) component)
The component (j) is an iodine-containing compound containing at least one iodine atom in its molecular structure. By using an iodine-containing compound, there is an advantage that a conjugated diene polymer having a cis-1,4-bond content of 98.5% or more can be easily obtained. The iodine-containing compound is not particularly limited as long as it contains at least one iodine atom in its molecular structure. For example, trimethylsilyl iodide, diethylaluminum iodide, methyl iodide, butyl iodide, hexyl iodide, octyl iodide Dido, iodoform, diiodomethane, iodine, benzylidene iodide, beryllium iodide, magnesium iodide, calcium iodide, barium iodide, zinc iodide, cadmium iodide, mercury iodide, manganese iodide, rhenium iodide, iodide Examples thereof include copper, silver iodide, and gold iodide.

However, as the iodine-containing compound, the general formula (18): R ²⁶ _n SiI _4-n (in the general formula (18), R ²⁶ is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. , N is an integer of 0 to 3, or a general formula (19): R ²⁷ _n I _4-n (in the general formula (19), R ²⁷ is a carbon number of 1 It is preferable that it is an iodinated hydrocarbon compound or iodine represented by ˜20 hydrocarbon group and n is an integer of 0 to 3. Such silicon iodide compounds, iodinated hydrocarbon compounds, and iodine have good solubility in organic solvents. For this reason, operations such as handling are simple and useful as an industrial production process.

  Specific examples of the silicon iodide compound (the compound represented by the general formula (18)) include trimethylsilyl iodide, triethylsilyl iodide, dimethylsilyl diiodide, and the like. Of these, trimethylsilyl iodide is preferred. Specific examples of the iodinated hydrocarbon compound (the compound represented by the general formula (19)) include methyl iodide, butyl iodide, hexyl iodide, octyl iodide, iodoform, diiodomethane, iodine, and benzylidene iodide. Etc. Of these, methyl iodide, iodoform, diiodomethane, and iodine are preferred.

  The above iodine-containing compounds can be used alone or in combination of two or more.

  In addition, the mixture ratio of each said component ((h)-(j) component) used as the main component of such a catalyst can be suitably set as needed. The component (h) is preferably used in an amount of 0.00001 to 1.0 mmol, more preferably 0.0001 to 0.5 mmol, relative to 100 g of the conjugated diene compound. If it is less than 0.00001 mmol, the polymerization activity tends to decrease. On the other hand, if it exceeds 1.0 mmol, the catalyst concentration increases and a decalcification step may be required.

  When the component (i) is an alumoxane, the preferred amount of alumoxane contained in the catalyst can be represented by a molar ratio of the component (h) and aluminum (Al) contained in the alumoxane. That is, “component (h)”: “aluminum (Al) contained in alumoxane” (molar ratio) is preferably 1: 1 to 1: 500, more preferably 1: 3 to 1: 250. Of 1: 5 to 1: 200 is particularly preferable. Outside the above range, the catalyst activity tends to decrease, or a step of removing the catalyst residue may be required.

  Moreover, when (i) component is an organoaluminum compound, the preferable quantity of the organoaluminum compound contained in a catalyst can be represented by the molar ratio of (h) component and an organoaluminum compound. That is, “(h) component”: “organoaluminum compound” (molar ratio) is preferably 1: 1 to 1: 700, more preferably 1: 3 to 1: 500. Outside the above range, the catalyst activity tends to decrease, or a step of removing the catalyst residue may be required.

  On the other hand, the preferable amount of the component (j) contained in the catalyst composition can be represented by the molar ratio of the iodine atom contained in the component (j) and the component (h). That is, (iodine atom) / ((h) component) (molar ratio) is preferably 0.5 to 3, more preferably 1.0 to 2.5, and 1.2 to 1.8. It is particularly preferred that When the molar ratio of (iodine atom) / (component (h)) is less than 0.5, the polymerization catalyst activity tends to decrease. On the other hand, when the molar ratio of (iodine atom) / ((h) component) is more than 3, it tends to be a catalyst poison.

  In addition to the components (h) to (j), the catalyst containing the components (h) to (j) as the main component may contain a conjugated diene compound and / or a nonconjugated diene compound as required. It is preferable to contain 1000 mol or less with respect to 1 mol of components, It is more preferable to contain 150-1000 mol, It is especially preferable to contain 3-300 mol. When the catalyst composition contains a conjugated diene compound and / or a non-conjugated diene compound, the catalyst activity is further improved, which is preferable. Examples of the conjugated diene compound include 1,3-butadiene and isoprene. Examples of non-conjugated diene compounds include divinylbenzene, diisopropenylbenzene, triisopropenylbenzene, 1,4-vinylhexadiene, and ethylidene norbornene.

  The catalyst mainly composed of the components (h) to (j) is, for example, the components (h) to (j) dissolved in a solvent, and a conjugated diene compound and / or a nonconjugated diene compound added as necessary. It can be prepared by reacting a compound. In addition, the addition order of each component may be arbitrary. However, it is preferable from the viewpoints of improving polymerization activity and shortening the polymerization start induction period that each component is mixed and reacted in advance and aged. The aging temperature is preferably 0 to 100 ° C, more preferably 20 to 80 ° C. When it is lower than 0 ° C., aging tends to be insufficient. On the other hand, if it exceeds 100 ° C., the catalytic activity tends to be lowered and the molecular weight distribution tends to be widened. The aging time is not particularly limited. Each component may be brought into contact in the line before being added to the polymerization reactor. A maturing time of 0.5 minutes or more is sufficient. The prepared catalyst composition is stable for several days.

(Rubber component)
In the rubber component contained in the golf ball rubber composition of the present embodiment, the above conjugated diene polymer is 30 to 100% by mass, preferably 40 to 40% when the total rubber component is 100% by mass. 100 mass%, More preferably, 50-100 mass% is contained. When the ratio of the conjugated diene polymer in the rubber component is less than 30% by mass, it may be difficult to obtain a rubber composition having desired physical properties, and the object of the present invention may not be achieved. In addition, the conjugated diene polymer contained in the rubber component may be only one kind or a combination of two or more kinds.

  In addition to the conjugated diene polymer, the rubber component includes natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber. In addition, at least one rubber selected from the group consisting of acrylonitrile-butadiene copolymer rubber, chloroprene rubber, and halogenated butyl rubber may be included. The rubber other than these conjugated diene polymers may be a polyfunctional type, for example, one having a branched structure formed by using a modifier such as tin tetrachloride or silicon tetrachloride. .

(Inorganic filler)
The rubber composition for golf balls of this embodiment contains an inorganic filler. By containing this inorganic filler, the strength of the crosslinked rubber obtained by crosslinking the rubber composition for golf balls is improved. In addition, the weight of the solid golf ball can be adjusted by adjusting the content of the inorganic filler.

  Specific examples of the inorganic filler include zinc oxide, barium sulfate, silica, alumina, aluminum sulfate, calcium carbonate, aluminum silicate, magnesium silicate and the like. Of these, zinc oxide, barium sulfate, and silica are preferable. These inorganic fillers can be used alone or in combination of two or more.

  The ratio of the inorganic filler contained in the golf ball rubber composition of the present embodiment is 5 to 80 parts by mass, preferably 5 to 70 parts by mass with respect to 100 parts by mass of the rubber component. If it is less than 5 parts by mass, the resulting solid golf ball becomes too light. On the other hand, if it exceeds 80 parts by mass, the resulting solid golf ball becomes too heavy.

(Crosslinking agent, organic peroxide)
The golf ball rubber composition of this embodiment preferably contains a crosslinking agent or an organic peroxide as a component other than the rubber component and the inorganic filler described above.

  The crosslinking agent is a component that acts to promote the crosslinking of the rubber component while being polymerized by radicals generated by the decomposition of the organic peroxide. Specific examples of the crosslinking agent include α, β-ethylenically unsaturated carboxylic acids and monovalent or divalent metal salts of α, β-ethylenically unsaturated carboxylic acids. More specifically, the following (i) and (ii) can be mentioned. In addition, these crosslinking agents can be used individually by 1 type or in combination of 2 or more types.

(I): Acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, sorbic acid, tiglic acid, cinnamic acid, aconitic acid (ii): Zn of above (i) (unsaturated acid), Mg , Ca, Ba, and Na salts (Zinc acrylate, Zn diacrylate, Zn methacrylate, Zn dimethacrylate, Zn itaconate, Mg acrylate, Mg diacrylate, Mg methacrylate, Mg dimethacrylate, itacon) Acid Mg etc.)

  In order to contain the metal salt of α, β-ethylenically unsaturated carboxylic acid in the rubber composition, the metal salt of α, β-ethylenically unsaturated carboxylic acid itself may be mixed with a rubber component or the like. Alternatively, by adding an α, β-ethylenically unsaturated carboxylic acid and kneading the rubber composition previously kneaded with a metal oxide such as zinc oxide, the α, β-ethylenic property in the rubber composition is obtained. An unsaturated carboxylic acid and a metal oxide may be reacted to form a metal salt. In addition, these crosslinking agents can be used individually by 1 type or in combination of 2 or more types.

  The content of the cross-linking agent is preferably 10 to 50 parts by mass and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the rubber component. When the amount is less than 10 parts by mass, the resilience as a solid golf ball tends to decrease. On the other hand, if it exceeds 50 parts by mass, it tends to be too hard and the manufacturing workability tends to be reduced.

  The organic oxide is a component that can function as a radical initiator, and is a component that acts as an initiator for a crosslinking reaction, graft reaction, polymerization reaction, or the like between a rubber component and a crosslinking agent. Specific examples of the organic peroxide include dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di- ( Examples thereof include t-butylperoxy) hexane, 1,3-bis (t-butylperoxy-isopropyl) benzene and the like.

  The content ratio of the organic peroxide is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the rubber component. If it is less than 0.1 parts by mass, the resilience tends to be too soft and the resilience will be lowered. On the other hand, if it exceeds 10 parts by mass, it tends to be too hard and the manufacturing workability tends to be reduced.

(Other ingredients)
In the golf ball rubber composition of the present embodiment, as a component other than the rubber component, inorganic filler, cross-linking agent and organic peroxide described above, a cross-linking aid such as zinc oxide; a lubricant such as stearic acid, if desired. ; You may mix | blend antioxidant etc.

2. Golf Ball Next, an embodiment of the golf ball of the present invention will be described. The golf ball of the present embodiment is obtained by crosslinking and molding the above golf ball rubber composition. Therefore, the golf ball of the present embodiment has an effect that the resilience is good and can be manufactured with good workability. Hereinafter, representative examples of the golf ball (solid golf ball) of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing a one-piece solid golf ball. In FIG. 1, reference numeral 1 denotes a main body portion, and reference numeral 1a denotes a dimple. The main body portion 1 is made of rubber (that is, rubber made of a cross-linked molded product of a golf ball rubber composition according to an embodiment of the present invention).

  FIG. 2 is a schematic cross-sectional view showing a two-piece solid golf ball. In FIG. 2, reference numeral 11 denotes a core, and reference numeral 12 denotes a cover. The cover 12 covers the core 11. Reference numeral 12a indicates a dimple. The core 11 is made of rubber.

FIG. 3 is a schematic cross-sectional view showing a three-piece solid golf ball. In FIG. 3, reference numeral 21 denotes an inner layer core, reference numeral 22 denotes an outer layer core, reference numeral 23 denotes a cover, and reference numeral 23a denotes a dimple. In this three-piece solid golf ball, the inner layer core 21 and the outer layer core 22 constitute a solid core. The inner layer core 21 or the outer layer core 22 or both the inner layer core 21 and the outer layer core 22 are made of rubber. The density of the outer layer core 22 of the three-piece solid golf ball is preferably larger than the density of the inner layer core 21 in terms of flight distance and rotational speed retention. For example, by blending a filler with a large specific gravity such as W ₂ O ₅ in the outer layer core 22 and blending a filler with a small specific gravity such as ZnO _{2 in the} inner layer core 21, the density of the outer layer core 22 and the inner layer core 21 can be increased. You can make a difference.

  Next, a method for producing a solid golf ball using the rubber composition for a golf ball according to an embodiment of the present invention will be described. First, the body part of the one-piece solid golf ball, the core of the two-piece solid golf ball, and the inner layer core of the three-piece solid golf ball are molded by putting the rubber composition for the golf ball into a predetermined die according to each, and press-crosslinking. Can be obtained. The crosslinking conditions are usually preferably 130 to 180 ° C. and 10 to 50 minutes. The temperature at the time of cross-linking molding may be changed in two or more steps.

  For the solid core of the two-layer structure of the three-piece solid golf ball, a sheet of the rubber composition for the outer layer core having a desired thickness is attached to the outside of the inner layer core obtained as described above, and pressed. It can be obtained by crosslinking and molding. As for the three-piece solid golf ball, any one of the rubber compositions used for each of the inner layer core and the outer layer core may be the golf ball rubber composition according to one embodiment of the present invention. The rubber composition for golf balls in the form is preferable.

  Covers for two-piece solid golf balls and three-piece solid golf balls are for covers in which additives such as inorganic white pigments such as titanium dioxide and light stabilizers are appropriately blended with resin components mainly composed of ionomer resins. Formed by coating the core with the composition. In the coating, an injection molding method is usually employed, but is not limited thereto. For a one-piece solid golf ball, desired dimples are formed as necessary when the main body portion is molded. In addition, for two-piece solid golf balls and three-piece solid golf balls, desired dimples are formed as necessary when the cover is molded. The four-piece solid golf ball can also be manufactured using the golf ball rubber composition according to an embodiment of the present invention in the same manner as the three-piece solid golf ball.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

[Mooney viscosity (ML _{1 + 4} (100 ° C.))] Measured according to JIS K6300, using an L rotor, preheating 1 minute, rotor operating time 4 minutes, temperature 100 ° C.

[Molecular weight distribution (Mw / Mn)]: “HLC-8120GPC” manufactured by Tosoh Corporation was used, a differential refractometer was used as a detector, and measurement was performed under the following conditions, and calculated as a standard polystyrene equivalent value.
Column: Tosoh Co., Ltd. column “GMHHXL” (2)
Column temperature: 40 ° C
Mobile phase: Tetrahydrofuran Flow rate: 1.0 ml / min
Sample concentration: 10mg / 20ml

[Microstructure (cis 1,4-bond content, 1,2-vinyl bond content)]: ¹ H-NMR analysis was performed using “EX-270” manufactured by JEOL Ltd., 5.30 to 5.50 ppm. (Cis 1,4-bond) and signal intensity at 4.80 to 5.01 ppm (1,2-vinyl bond), the ratio of cis 1,4-bond to 1,2-vinyl bond in the polymer Calculated. Further, ¹³ C-NMR analysis was performed, and from the signal intensity at 27.5 ppm (cis 1,4-bond) and 32.8 ppm (trans 1,4-bond), cis 1,4-bond in the polymer was The ratio of trans 1,4-bond was calculated. From these calculated ratios, the cis 1,4-bond content (%) and the 1,2-vinyl bond content (%) were calculated.

[Roll processability] Using a 6-inch roll, a winding test was performed under the conditions of a temperature of 70 ° C, a nip width of 1.4 mm, and a rotation speed of 20 rpm / 24 rpm, and the roll processability was evaluated according to the following criteria. In addition, evaluation of roll workability is so favorable that the numerical value is large.
"5": The roll is wound neatly and the surface is smooth.
“4”: Wound around a roll and no surface roughness.
“3”: Wound on the roll, but rough on the surface.
“2”: Winding around the roll, but the surface has holes and dirty.
“1”: The roll is not wound.

[Extrusion processability]: An extrusion test using a flow tester manufactured by Shimadzu Corporation (described in Journal of the Japan Rubber Association, Vol. 76, p. 441 (2005)) was carried out under the conditions shown below. Extrusion speed was measured. The measured value of the extrusion speed of “Comparative Example 2” was converted into an index with “100”, and the extrusion processability was evaluated. It should be noted that the extrusion processability can be evaluated as “good” as the numerical value is larger and the extrusion speed is higher.
Load: 50kg
Nozzle: 2 × 2m / m
Residual heat: 180 sec, 60 ° C

  [Rebound resilience]: Using a dynamic spectrometer manufactured by Rheometrics, USA, tan δ of the molded product obtained by pressure-crosslinking the obtained rubber composition at 150 ° C. for 30 minutes 76, p. 441 (2005), the measurement was performed under the conditions of a tensile dynamic strain of 0.1%, a frequency of 15 Hz, and −20 ° C. The rebound resilience was evaluated by converting the measured value of tan δ of a predetermined molded body into an index with “100”. The rebound resilience is better as the value is larger.

(Synthesis Example 1 (Production of Polymer A))
A 5 L autoclave purged with nitrogen was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene. Cyclohexane solution of neodymium versatate (hereinafter also referred to as “Nd (ver) ₃ ”) (0.18 mmol), toluene solution of methylalumoxane (hereinafter also referred to as “MAO”) (1.8 mmol), diisobutylaluminum hydride (Hereinafter also referred to as “Al ⁱ Bu ₂ H”) (4.4 mmol) in toluene solution and trimethylsilyl iodide (hereinafter also referred to as “Me ₃ SiI”) (0.36 mmol) in toluene solution A catalyst composition (iodine atom / rare earth element-containing compound (molar ratio) = 2.0) obtained by reacting and ripening with 1,3-butadiene in a double molar amount at 30 ° C. for 60 minutes was further charged, and 2 at 30 ° C. A time polymerization reaction was carried out. The reaction conversion of 1,3-butadiene was almost 100%. Next, a methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added. After the polymerization was stopped, the solvent was removed by steam stripping, and the polymer A was dried by a roll at 110 ° C. Obtained. The polymerization conditions are shown in Table 1. Further, the obtained polymer A has a Mooney viscosity (ML _{1 + 4} (100 ° C.)) of 59, a molecular weight distribution (Mw / Mn) of 1.8, a cis 1,4-bond content of 99.6%, and 1, The 2-vinyl bond content was 0.16%.

(Synthesis Example 2 (Production of Modified Polymer B))
A 5 L autoclave purged with nitrogen was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene. Nd (ver) ₃ (0.18 mmol) in cyclohexane solution, MAO (1.8 mmol) in toluene solution, Al ⁱ Bu ₂ H (6.0 mmol) in toluene solution, and Me ₃ SiI (0.36 mmol) in toluene solution Is further charged with a catalyst composition (iodine atom / rare earth element-containing compound (molar ratio) = 2.0) obtained by reaction aging with 1,3-butadiene having a molar amount 5 times that of neodymium at 30 ° C. for 60 minutes. The polymerization reaction was carried out at 30 ° C. for 2 hours. The reaction conversion of 1,3-butadiene was almost 100%. Next, the temperature of the polymerization solution was kept at 30 ° C., and 3-glycidyloxypropyltrimethoxysilane (hereinafter also referred to as “GPMOS”) (0.37 mmol) was added and reacted for 15 minutes, and then dioctyltin bisoctylmer. A rate (hereinafter, also referred to as “DOTBOM”) (0.18 mmol) was added, and the mixture was further reacted for 15 minutes. Thereafter, a methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added. After the polymerization was stopped, the solvent was removed by steam stripping, and the polymer was dried with a roll at 110 ° C. Got. The polymerization and modification conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the resulting modified polymer B.

(Synthesis Example 3 (Production of Modified Polymer C))
A modified polymer C was obtained in the same manner as in Synthesis Example 1 except that GPMOS was not added and DOTBOM (0.55 mmol) was added. The polymerization and modification conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the resulting modified polymer C.

(Synthesis Example 4 (Production of Modified Polymer D))
A modified polymer D was obtained in the same manner as in Synthesis Example 3 except that no DOTBOM was added and GPMOS (0.55 mmol) was added. The polymerization and modification conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the resulting modified polymer D.

(Synthesis Example 5 (Production of Modified Polymer E))
A modified polymer E was obtained in the same manner as in Synthesis Example 2 except that a solution in which GPMOS and DOTBOM were mixed in advance was used. The polymerization and modification conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the resulting modified polymer E.

(Synthesis Example 6 (Production of Modified Polymer F))
A modified polymer F was obtained in the same manner as in Synthesis Example 1 except that 3-isocyanatopropyltriethoxysilane (hereinafter also referred to as “IPEOS”) was added in place of GPMOS. The polymerization and modification conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the resulting modified polymer F.

(Synthesis Example 7 (Production of Modified Polymer G))
A modified polymer G was obtained in the same manner as in Synthesis Example 1 except that dioctyltin dichloride (hereinafter also referred to as “DOTDC”) was added in place of DOTBOM. The polymerization and modification conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the resulting modified polymer G.

(Synthesis Example 8 (Production of Modified Polymer H))
Except for adding polymethylene polyphenyl polyisocyanate (trade name “PAPI * 135” (manufactured by Dow Chemical Japan), 0.72 mmol in terms of NCO) (hereinafter also referred to as “CMDI”) instead of DOTBOM. A modified polymer H was obtained in the same manner as in Synthesis Example 1 described above. The polymerization and modification conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the resulting modified polymer H.

(Synthesis Example 9 (Production of Modified Polymer I))
A modified polymer I was obtained in the same manner as in Synthesis Example 1 except that trimethylolpropane polyglycidyl ether (hereinafter also referred to as “TMMPGE”) was added in place of DOTBOM. The polymerization and modification conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the modified polymer I obtained.

(Synthesis Example 10 (Production of Modified Polymer J))
A modified polymer J was obtained in the same manner as in Synthesis Example 1 except that diethyl adipate (hereinafter also referred to as “AADE”) was added in place of DOTBOM. The polymerization and modification conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the obtained modified polymer J.

(Synthesis Comparative Example 1 (Production of Polymer K))
A 5 L autoclave purged with nitrogen was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene. Nd (ver) ₃ (0.18 mmol) in cyclohexane solution, MAO (9.0 mmol) in toluene solution, Al ⁱ Bu ₂ H (3.0 mmol) in toluene solution, and trimethylsilyl chloride (hereinafter referred to as “Me ₃ SiCl”) The catalyst composition (chlorine atom / rare earth element-containing compound (mole)) obtained by reacting and aging a toluene solution of (0.36 mmol) with 1,3-butadiene having a 5-fold molar amount of neodymium at 30 ° C. for 60 minutes. Ratio) = 2.0), and a polymerization reaction was carried out at 30 ° C. for 2 hours. The reaction conversion of 1,3-butadiene was almost 100%. Next, a methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added. After the polymerization was stopped, the solvent was removed by steam stripping, and the polymer K was dried by a roll at 110 ° C. Obtained. The polymerization conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the obtained polymer K.

(Synthesis Comparative Example 2 (Production of Modified Polymer L))
A 5 L autoclave purged with nitrogen was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene. A cyclohexane solution of Nd (ver) ₃ (0.18 mmol), a toluene solution of MAO (9.0 mmol), a toluene solution of Al ⁱ Bu ₂ H (4.2 mmol), and a toluene solution of Me ₃ SiCl (0.36 mmol) Is further charged with a catalyst composition (chlorine atom / rare earth element-containing compound (molar ratio) = 2.0) obtained by reaction aging with 1,3-butadiene having a molar amount 5 times that of neodymium at 30 ° C. for 60 minutes. The polymerization reaction was carried out at 30 ° C. for 2 hours. The reaction conversion of 1,3-butadiene was almost 100%. Next, the temperature of the polymerization solution was kept at 30 ° C., GPMOS (0.37 mmol) was added and reacted for 15 minutes, and then DOTBOM (0.18 mmol) was added and reacted for another 15 minutes. Thereafter, a methanol solution containing 1.5 g of 2,4-di-t-butyl-p-cresol was added, and after the polymerization was stopped, the solvent was removed by steam stripping, followed by drying with a roll at 110 ° C. Got. The polymerization and modification conditions are shown in Table 1. Table 1 shows the analysis results (polymerization reaction results) of the obtained polymer K. The contents of the annotations (* 1 to 4) in Table 1 are shown below.

* 1:
Nd (ver) ₃ ; Neodymium versatate MAO; Methylalumoxane Al ⁱ Bu ₂ H; Diisobutylaluminum hydride Me ₃ SiI; Trimethylsilyl iodide Me ₃ SiCl; Trimethylsilyl chloride GPMOS; 3-Glycidyloxypropyltrimethoxysilane DOTBOM; Tin bisoctyl malate IPEOS; 3-isocyanatopropyltriethoxysilane DOTDC; Dioctyltin dichloride CMDI; Polymethylene polyphenyl polyisocyanate (trade name “PAPI * 135” (manufactured by Dow Chemical Japan))
TMPPGE: Trimethylolpropane polyglycidyl ether AADE: Diethyl adipate * 2: Ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) * 3: Used after mixing GPMOS and DOTBOM * 4: Number of moles in terms of NCO Is

(Example 1)
50 parts of 100 parts of Polymer A, 25 parts of zinc diacrylate, 22 parts of zinc oxide, 1.8 parts of dicumyl peroxide, and 0.5 part of an antioxidant (trade name “Yoshinox 425” (manufactured by Yoshitomi Pharmaceutical)) A rubber composition (Example 1) was obtained by kneading using a kneader at 50 ° C. for 15 minutes. The resulting rubber composition had a roll processability of “3”, an extrusion processability of “102”, and a rebound resilience of “117”.

(Examples 2 to 10, Comparative Examples 1 and 2)
Except having set it as the compounding prescription shown in Table 2, it carried out similarly to the above-mentioned Example 1, and obtained the rubber composition (Examples 2-10, Comparative Examples 1 and 2). Table 2 shows various evaluation results of the obtained rubber composition. The contents of the annotations (* 1, 2) in Table 2 are shown below.

* 1: Brand name “Yoshinox 425” (manufactured by Yoshitomi Pharmaceutical)
* 2: Index notation with “Comparative Example 2” as 100

  As shown in Table 2, the rubber compositions of Examples 1 to 10 are excellent in the balance of roll processability and extrusion processability as compared with the rubber compositions of Comparative Examples 1 and 2. it is obvious. Moreover, the molded object obtained using the rubber composition of Examples 1-10 is excellent in rebound resilience compared with the molded object obtained using the rubber composition of Comparative Examples 1 and 2. It is clear.

(Examples 11-14, Comparative Examples 3-8)
Except having set it as the compounding prescription shown in Table 3, it carried out similarly to the above-mentioned Example 1, and obtained the rubber composition (Examples 11-14, Comparative Examples 3-8). Table 3 shows various evaluation results of the obtained rubber composition. The contents of the annotations (* 1 to 3) in Table 3 are shown below.

* 1: Polybutadiene rubber (trade name “BR51” (manufactured by JSR))
* 2: Product name “Yoshinox 425” (manufactured by Yoshitomi Pharmaceutical)
* 3: Index notation with “Comparative Example 5” as 100

  As shown in Table 3, the rubber compositions of Examples 11 to 14 are excellent in balance of roll processability and extrusion processability as compared with the rubber compositions of Comparative Examples 3 to 6. it is obvious. Moreover, the molded object obtained using the rubber composition of Examples 11-14 is excellent in rebound resilience compared with the molded object obtained using the rubber composition of Comparative Examples 3-6. It is clear. In addition, (1) Comparison between Examples 11 and 12 and Comparative Example 7, and (2) Comparison between Examples 13 and 14 and Comparative Example 8, Polymer A or Modified Polymer B contained in the entire rubber component It is clear that an excellent effect is exhibited by setting a specific ratio.

(Examples 15-18, Comparative Examples 9-14)
Except having set it as the compounding prescription shown in Table 4, it carried out similarly to the above-mentioned Example 1, and obtained the rubber composition (Examples 15-18, Comparative Examples 9-14). Table 4 shows various evaluation results of the obtained rubber composition. The contents of the annotations (* 1 to 3) in Table 4 are shown below.

* 1: Polybutadiene rubber (trade name “BR51” (manufactured by JSR))
* 2: Product name “Yoshinox 425” (manufactured by Yoshitomi Pharmaceutical)
* 3: Index notation with “Comparative Example 11” as 100

  As shown in Table 4, the rubber compositions of Examples 11 to 14 are excellent in the balance of roll processability and extrusion processability as compared with the rubber compositions of Comparative Examples 9 to 14. it is obvious. Moreover, the molded object obtained using the rubber composition of Examples 11-14 was excellent in the resilience compared with the molded object obtained using the rubber composition of Comparative Examples 9-14. It is clear. In addition, (1) Comparison between Examples 15 and 16 and Comparative Example 13, and (2) Comparison between Examples 17 and 18 and Comparative Example 14, Polymer A or Modified Polymer B contained in the entire rubber component was obtained. It is clear that an excellent effect is exhibited by setting a specific ratio.

  By using the golf ball rubber composition of the present invention, a golf ball having high rebound resilience can be manufactured with good workability.

It is a schematic sectional drawing which shows an example of a one-piece solid golf ball. It is a schematic sectional drawing which shows an example of a two-piece solid golf ball. It is a schematic sectional drawing which shows an example of a three-piece solid golf ball.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Main-body part 1a, 2a, 3a Dimple 11 Core 21 Inner layer core 22 Outer layer core 12, 23 Cover

Claims (8)

1,2-vinyl bond content of less than 0.5%, cis 1,4-bond content of 98.5% or more, and weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography A rubber component containing 30 to 100% by mass of a conjugated diene polymer having a ratio (Mw / Mn) of 3.5 or less,
An inorganic filler,
A golf ball rubber composition comprising 5 to 80 parts by mass of the inorganic filler with respect to 100 parts by mass of the rubber component. The conjugated diene polymer is a modified conjugated diene system obtained by modifying an unmodified conjugated diene polymer having an active end with at least one compound selected from the group consisting of the following components (a) to (g): The golf ball rubber composition according to claim 1, which is a polymer.
Component (a): alkoxysilane compound containing at least one epoxy group and / or isocyanate group in the molecule (b) component: halogenated represented by any one of the following general formulas (1) to (5) Organometallic compound, halogenated metal compound, or organometallic compound R ¹ _n M′X _4-n (1)
M'X ₄ (2)
M'X ₃ (3)
R ¹ _n M ′ (R ² —COOR ³ ) _4-n (4)
R ¹ _n M ′ (R ² —COR ³ ) _4-n (5)
(In the general formulas (1), (4), and (5), R ¹ and R ² are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and n is an integer of 0 to 3. In the general formulas (4) and (5), R ³ is a hydrocarbon group having 1 to 20 carbon atoms which may contain a carbonyl group or an ester group in the side chain. In (5), M ′ is a tin atom, silicon atom, germanium atom, or phosphorus atom, and X is a halogen atom in the general formulas (1) to (3).
Component (c): Y = C = Z bond (where Y is a carbon atom, oxygen atom, nitrogen atom or sulfur atom, and Z is an oxygen atom, nitrogen atom or sulfur atom) in the molecule A heterocumulene compound (d) component; a hetero 3-membered ring compound containing a bond represented by the following general formula (6) in the molecule (excluding the component (a))

(In the general formula (6), Y is an oxygen atom, a nitrogen atom or a sulfur atom)
(E) Component: Halogenated isocyano compound (f) Component: Carboxylic acid, acid halide, ester compound, carbonate compound, or acid anhydride represented by any of the following general formulas (7) to (12) ⁴ (COOH) _m (7)
R ⁵ (COX) _m (8)
R ⁶ COO-R ⁷ (9)
^{R 8 -OCOO-R 9 (10} )
R ¹⁰ (COOCO-R ¹¹ ) _m (11)

(In the general formulas (7) to (12), R ^{4 to} R ¹² are the same or different hydrocarbon groups having 1 to 50 carbon atoms. In the general formula (8), X is a halogen atom. In the general formulas (7), (8), (11), and (12), m is an integer of 1 to 5.
Component (g); the following general formula (13) to either a carboxylic acid metal salt represented by R ¹³ _l M of _{^{(15) "(OCOR 14)}} 4-l (13)
_{^{R 15 l M "(OCO-}} R 16 -COOR 17) 4-l (14)

(In the general formulas (13) to (15), R ^{13 to} R ¹⁹ are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and M ″ is a tin atom, a silicon atom, or a germanium atom. , L is an integer from 0 to 3) The unmodified conjugated diene polymer is obtained by polymerizing 1,3-butadiene using a catalyst mainly comprising the following components (h) to (j). Rubber composition for golf balls.
(H) component; a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base (i) component; alumoxane and / or AlR ²⁰ R ²¹ R ²² (provided that R ²⁰ and R ²¹ are the same or different, a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, R ²² is a hydrocarbon group having 1 to 10 carbon atoms, and R ²² is the same as R ²⁰ or R ²¹ . An organoaluminum compound represented by the formula (j): an iodine-containing compound containing at least one iodine atom in its molecular structure   The conjugated diene polymer includes a structural unit derived from at least one conjugated diene compound selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. The rubber composition for golf balls according to any one of Items 1 to 3.   The rubber composition for a golf ball according to any one of claims 1 to 4, wherein the inorganic filler is at least one selected from the group consisting of zinc oxide, barium sulfate, and silica.   From natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber, acrylonitrile-butadiene copolymer rubber, chloroprene rubber, and halogenated butyl rubber The rubber composition for a golf ball according to claim 1, wherein at least one selected from the group consisting of the rubber component is further contained in the rubber component.   Any one of Claims 1-6 containing 10-50 mass parts of crosslinking agents, 5-80 mass parts of inorganic fillers, and 0.1-10 mass parts of organic peroxides with respect to 100 mass parts of said rubber components. The rubber composition for golf balls according to one item.   A golf ball obtained by crosslinking and molding the golf ball rubber composition according to claim 1.

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