Resin composition and golf ball

【0001】

[Technical field to which the invention belongs]

The present invention relates to a resin composition and a golf ball that provide a molded product having excellent flexibility, impact resilience, and mechanical properties. More specifically, the present invention relates to a resin composition that is also suitable as a skin material for golf balls, and a golf ball formed of the resin composition.

【0002】

[Conventional technology]

Ionomer resin, which is a copolymer of α-olefin and α, β-unsaturated carboxylic acid, is used for automobile parts, golf balls, ski shoes, etc. by taking advantage of its excellent toughness, abrasion resistance, oil resistance, etc. There is. Among them, it is suitably used in the manufacture of golf balls by taking advantage of its excellent impact resilience. However, in the ionomer resin, there is a positive correlation between the impact resilience and the hardness, and when a high impact resilience is required, the hardness also increases accordingly. Therefore, a golf ball using an ionomer resin as a skin material has a problem that it has sufficient impact resilience but a poor shot feeling. Therefore, it is desired to impart flexibility to the ionomer resin without impairing excellent properties such as impact resilience. As one of such formulations, a method of blending a thermoplastic elastomer such as a polyester elastomer or a polyamide elastomer with an ionomer resin is known, and a composition that is flexible and gives a molded product having excellent impact resilience can be obtained. (For example, US Pat. No. 4,337,947). However, such a thermoplastic elastomer is expensive, and when the blending amount is large, the durability of the composition is lowered, so that the blending amount is desired to be as small as possible. That is, in a composition having the same flexibility and impact resilience, a formulation capable of reducing the blending amount of these thermoplastic elastomers is desired. However, when the blending amount of the ionomer resin component is increased, there is a problem that the impact resilience of the molded product is lowered and the hardness and the rigidity are too high in the conventional general-purpose ionomer resin.

【0003】

Further, it has been proposed to use an ionomer resin blended with a thermoplastic elastomer having a crystalline polyethylene block in a certain range as a skin material for a golf ball (Japanese Patent Laid-Open No. 8-767). This proposal hardness of the shot feel is a problem of a golf ball using the conventional ionomer resin skin material, non as greatly improved technology controllability it can be said that always enabled.

【0004】

However, the resin composition according to this proposal is inferior in compatibility between the ionomer resin and the thermoplastic elastomer having a crystalline polyethylene block, and as a result, cut resistance and the like may become a problem. Therefore, there is a demand for a skin material that solves such a problem and gives a golf ball having a good shot feeling and excellent impact resilience.

【0005】

[Problems to be Solved by the Invention]

The present invention has been made in view of the above problems, and provides a golf ball having excellent flexibility and mechanical properties, a good shot feeling when used for a golf ball skin, a long flight distance, and excellent cut resistance. It is an object of the present invention to provide a resin composition and a golf ball.

【0006】

[Means for solving problems]

As a result of diligent research to achieve the above object, the present inventor blended an alkoxysilyl group-containing hydrogenated diene polymer and / or an amino group-containing hydrogenated diene polymer with an ionomer resin to achieve compatibility between the two. It has good properties, excellent flexibility and mechanical properties, and when used on the skin of a golf ball, the golf ball is soft and has an excellent shot feeling, and also has high resilience, so that the initial speed and flight distance of the ball are excellent. Since it has good adhesion to the core, it has been found to have excellent cut resistance in iron shots, and the present invention has been completed. That is, the present invention provides a novel resin composition suitable for forming the following golf ball skin and a golf ball formed of the resin composition.

【0007】

[1] A resin composition containing (a) an ionomer resin and (b) an alkoxysilyl group-containing hydrogenated conjugated diene polymer and / or an amino group-containing hydrogenated conjugated diene polymer. ..

[2] The alkoxysilyl group-containing hydrogenated conjugated diene polymer polymerizes a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound, and the obtained conjugated diene polymer is combined with an alkoxysilane. The resin composition according to the above [1], which is produced by reacting a compound to obtain a modified polymer and then hydrogenating the modified polymer.

[3] The resin composition according to the above [1], wherein the amino group hydrogenated conjugated diene polymer is a polymer according to any one of the following (i) to (iii). (i) A polymer produced by polymerizing a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound having an amino group, and hydrogenating the obtained polymer. (ii) Manufactured by polymerizing an unsaturated monomer having a conjugated diene and an amino group, or an aromatic vinyl compound with these in the presence of an organic alkali metal compound, and then hydrogenating the obtained polymer. Polymer. (iii) Modification of conjugated diene or conjugated diene and aromatic vinyl compound by polymerizing in the presence of an organic alkali metal compound and reacting the obtained conjugated diene-based polymer with a compound represented by the following general formula (1). A polymer produced by preparing a polymer and then hydrogenating the modified polymer. R¹R²C = NY (1) [In the above general formula (1), R¹And R²Are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or organosiloxy groups having 1 to 100 carbon atoms. Y is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aralkyl group having 1 to 100 carbon atoms. It is an organosiloxy group of. ]

[4] The alkoxysilyl group content of the alkoxysilyl group-containing hydrogenated conjugated diene polymer is 0.0001 to 5 mmol / g, and the amino group content of the amino group-containing hydrogenated conjugated diene polymer is 0.0001 to 5 mmol. The resin composition according to any one of the above [1] to [3], which is / g.

[5] Both the alkoxysilyl group-containing hydrogenated conjugated diene polymer and the amino group-containing hydrogenated conjugated diene polymer are saturated with 80% or more of the double bonds derived from the conjugated diene [1]. ~ The resin composition according to [4].

[6] The above-mentioned conjugated diene polymer is a block copolymer containing two or more polymer blocks selected from the following polymer blocks (A) to (D) [2] to [5]. ] The resin composition according to. (A) Aromatic vinyl compound polymer block having an aromatic vinyl compound of 80% by mass or more (B) Conjugated diene polymer block having a vinyl bond content of less than 25% by mass (C) Vinyl bond content of 25% by mass or more 90 Conjugated diene polymer block of mass% or less (D) Random copolymer block of aromatic vinyl compound and conjugated diene [7] Any of the above [1] to [6] characterized by being used for a golf ball skin. The resin composition described in Crab.

[8] A golf ball characterized in that a core is coated and formed with a skin material composed of the resin composition according to the above [7].

【0008】

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the resin composition of the present invention will be specifically described. The resin composition of the present invention is characterized by containing (a) an ionomer resin and (b) an alkoxysilyl group-containing hydrogenated conjugated diene polymer and / or an amino group-containing hydrogenated conjugated diene polymer. And. Hereinafter, each component will be described in more detail.

【0009】

1. Ionomer resin As the ionomer resin used in the present invention (hereinafter, may be referred to as "component (a)"), any conventionally used skin material for golf balls can be used, and α-olefin and α-olefin can be used. The carboxyl group of the copolymer of α, β-unsaturated carboxylic acid and the copolymer of α-olefin and α, β-unsaturated carboxylic acid and its ester is a metal ion (Na, Li, Zn, Mg, K). Etc.) can be preferably used. In this case, examples of the α-olefin include those having a small number of carbon atoms such as ethylene and propylene. Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid and the like, but acrylic acid and methacrylic acid are particularly preferable. Examples of the ester include those obtained by reacting the above carboxylic acid with a lower alcohol such as methanol, ethanol, propanol, n-butanol, and isobutanol, and acrylic acid ester and methacrylic acid ester are particularly preferable. Further, in the case of a binary copolymer of α-olefin and α, β-unsaturated carboxylic acid, it is preferable to use α, β-unsaturated carboxylic acid as a copolymer in a proportion of 5 to 20% by mass. In the case of a ternary copolymer of α-olefin, α, β-unsaturated carboxylic acid and its ester, the ratio of α, β-unsaturated carboxylic acid is 1 to 10% by mass and the ester component is 12 to 45% by mass. Is preferable. Further, the degree of neutralization by the metal ion is preferably 10 to 90 mol% of the acid group.

【0010】

As such an ionomer resin, commercially available products such as "Surlyn" manufactured by DuPont and "HIMILAN" manufactured by Mitsui DuPont Polychemicals can be used. At this time, from the viewpoint of improving the resilience, it is preferable to use a mixture of the monovalent metal ionomer and the divalent metal ionomer. For example, it is preferable to mix and use the former and the latter so that the mass ratio is 20/80 to 80/20.

【0011】

2. alkoxysilyl group-containing hydrogenated conjugated diene polymer and amino group-containing hydrogenated conjugated diene polymer The alkoxysilyl group-containing hydrogenated conjugated diene polymer and / or amino group-containing hydrogenated conjugated diene used in the present invention. Among the based polymers (hereinafter, may be referred to as component (b)), the alkoxysilyl group-containing hydrogenated conjugated diene polymer is not particularly limited, but in an inert organic solvent, conjugated diene or conjugated diene. The aromatic vinyl compound is polymerized using an organic alkali metal compound as a polymerization initiator to obtain a modified polymer obtained by reacting the obtained conjugated diene polymer with an alkoxysilane compound, and then the modified polymer is hydrogenated. Can be easily obtained.

【0012】

The above-mentioned "alkoxysilyl group" is a group in which at least one alkoxyl selected from alkyloxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, and aralkyloxy having 7 to 20 carbon atoms is bonded to a silicon atom. Specific examples thereof include alkoxys such as methoxy, ethoxy, butoxy, propoxy, pentyroxy, neopentyroxy, hexyloxy, amyroxy and phenoxy, preferably methoxy, ethoxy, amyroxy and phenoxy in which an alkoxy and a silicon atom are bonded.

【0013】

Examples of the above-mentioned "conjugated diene" include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-octadien, and 1,3-. Hexadiene, 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene, chloroprene and the like can be mentioned. Of these, 1,3-butadiene and isoprene are preferable.

【0014】

Further, the monomer to be polymerized may be the above-mentioned "conjugated diene" alone, but can be polymerized together with other compounds, for example, the above-mentioned "conjugated diene" and "aromatic vinyl compound" can be polymerized. .. Examples of the above-mentioned "aromatic vinyl compound" include styrene, tert-butyl styrene, α-methyl styrene, p-methyl styrene, p-ethyl styrene, divinyl benzene, 1,1-diphenyl styrene, vinyl naphthalene, vinyl anthracene, N, Examples thereof include N-diethyl-p-aminoethylstyrene and vinylpyridine. Of these, styrene and tert-butyl styrene are preferable. In this case, the above-mentioned "conjugated diene", the above-mentioned "aromatic vinyl compound", and other compounds may be added and polymerized.

【0015】

Examples of the above-mentioned "organolithium metal compound" which is a polymerization initiator include an organic lithium compound and an organic sodium compound, and an organic lithium compound is particularly preferable. Examples of the organic lithium compound include an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound.

【0016】

Specific examples of the above organic lithium compounds include ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, pentyl lithium, hexyl lithium, cyclohexyl lithium, and phenyl lithium. Hexamethylene dilithium, cyclopentadienyl lithium, indenyl lithium, 1,1-diphenyl-n-hexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, lithium naphthalene, butadienyl dilithium, isopropenyldi Lithium, m-diisoprenyldilithium, 1,3-phenylene-bis- (3-methyl-1-phenylpentylidene) bislithium, 1,3-phenylene-bis- (3-methyl-1, [4- Methylphenyl] pentylidene) bislithium, 1,3-phenylene-bis- (3-methyl-1, [4-dodecylphenyl] pentylidene) bislithium, 1,1,4,4-tetraphenyl-1,4-dilithiobtan , Polybutadienyl Lithium, Polyisoprenyl Lithium, Polystyrene-Butadienyl Lithium, Polystylenyl Lithium, Polyethylene Lithium, Poly-1,3-Cyclohexadienyl Lithium, Polystyrene-1,3-Cyclohexadienyl Lithium, Examples thereof include polybutadiene-1,3-cyclohexadienyllithium.

【0017】

Among these, preferred organic lithium compounds are ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, cyclohexyl lithium, butadienyl lithium, and isopropenyl dilithium. , 1,3-Phenylene-bis- (3-Methyl-1-phenylpentylidene) bislithium, 1,3-Phenylene-bis- (3-methyl-1, [4-methylphenyl] pentylidene) bislithium, 1 , 3-Phenylene-bis- (3-methyl-1, [4-dodecylphenyl] pentylidene) bislithium, 1,1,4,4-tetraphenyl-1,4-dilithiobutane, polybutadienyllithium, polyiso Plenyl lithium, polystyrene-butadienyl lithium, polystyrenyl lithium, poly-1,3-cyclohexadienyl lithium, polystyrene-1,3-cyclohexadienyl lithium, polybutadiene-1,3-cyclohexadienyl lithium and the like. Be done. Further, more preferable organolithium compounds include n-butyllithium, sec-butyllithium, tert-butyllithium, 1,3-phenylene-bis- (3-methyl-1-phenylpentylidene) bislithium and the like. .. In addition, these organic alkali metal compounds can be used alone or in combination of two or more.

【0018】

The amount of the organic alkali metal compound used is not particularly limited, and various amounts can be used as needed. However, the amount is usually 0.02 to 15 parts by mass per 100 parts by mass of the monomer, preferably 0.03 to 5 parts by mass. Used in quantity.

【0019】

The structure of the alkoxysilane compound is not limited as long as it can be reacted with a conjugated diene polymer to form a modified polymer. Examples of the alkoxysilane compound include compounds represented by the following general formula (2). R³_(4-mn)Si (OR⁴)_mX¹_n (2) [In the formula, R³Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms.³If there is more than one, each R³May be the same group or different groups. Also, R⁴Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R⁴If there is more than one, each R⁴May be the same group or different groups. X¹Is a substituent having a polar group containing at least one of O atom and Si atom (however, OR⁴Is excluded. ), X¹If there is more than one, each X¹Can be the same group or different groups, and each X¹May be an independent substituent or form a cyclic structure. m is 1, 2 or 3 and n is 0, 1, 2 or 3. The sum of m and n is 1-4. In particular, m is preferably 2 or 3 and n is preferably 0 or 1. ]

【0020】

Examples of the alkoxysilane compound represented by the above general formula (2) include tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoxylisilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltriphenoxysilane, and dimethyldi. Phenoxysilane, 1-trimethylsilyl-2-dimethoxy-1-aza-2-silacyclopentane, 1-trimethylsilyl-2-diethoxy-1-aza-2-silacyclopentane, γ-glycidoxypropyltrimethoxysilane, γ -Glysidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, trimethylsiloxy Examples thereof include triphenoxysilane, trimethylsiloxytrimethoxysilane, trimethylsiloxytriethoxysilane, trimethylsiloxytributoxysilane, and 1,1,3,3-tetramethyl-1-phenoxydisiloxane.

【0021】

The modification with the alkoxysilane compound is carried out by adding the alkoxysilane compound into the polymerization system when the polymerization conversion rate of the polymerization reaction in producing the conjugated diene polymer reaches 90% to 100%. It is preferable to carry out. It may be added before the polymerization conversion rate reaches 90%, or the alkoxysilane compound may be added intermittently or continuously while the polymerization reaction is in progress to carry out the modification reaction.

【0022】

The amount of the alkoxysilane compound used is preferably 0.05 to 5 times by mole, more preferably 0.1 to 1.5 times by mole with respect to the number of moles of the active site derived from the organic alkali metal compound.

【0023】

The content of the alkoxysilyl group bonded to the modified polymer obtained by reacting the conjugated diene polymer with the alkoxysilane compound is usually 0.0001 to 5 mmol / g, preferably 0.001 to 1 mmo1 / g, more preferably 0.001 to 1 mmo1 / g. It is 0.003 to 0.1 mmo1 / g. The alkoxysilyl group is usually present at the end of the polymer chain, but may be present at the side chain. In addition, the content of the alkoxysilyl group does not change with the hydrogenation described below.

【0024】

The alkoxysilyl group-containing hydrogenated conjugated diene polymer according to the present invention can be selectively obtained by hydrogenating the modified polymer obtained as described above. The hydrogenation method and reaction conditions are not particularly limited, and are usually carried out at 20 to 150 ° C. under hydrogenation pressure of 0.1 to 10 MPa and in the presence of a hydrogenation catalyst. In this case, the hydrogenation rate can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, the reaction time, and the like. The hydrogenation rate is 80% or more, preferably 95% or more, of the double bond derived from the conjugated diene which is an unsaturated portion.

【0025】

The hydrogenated catalyst is usually a compound containing any of the elements of the Periodic Table Ib, IVb, Vb, VIb, VIIb, and Group VIII, such as Ti, V, Co, Ni, Zr, Ru, Rh, and Pd. Compounds containing Hf, Re, and Pt elements can be used. Specifically, as the hydrogenation catalyst, for example, a metallocene compound containing Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re and the like, and a metal such as Pd, Ni, Pt, Rh and Ru. A supported heterogeneous catalyst supported on a carrier such as carbon, silica, alumina, or silica soil, a homogeneous cheegler type catalyst in which an organic salt such as Ni or Co or an acetylacetone salt and a reducing agent such as organic aluminum are combined. Examples thereof include organometallic compounds or complexes such as Ru and Rh, and fullerene and carbon nanotubes in which hydrogen is stored.

【0026】

Among these, a metallocene compound containing any one of Ti, Zr, Hf, Co and Ni is preferable because it can be hydrogenated in a homogeneous system in an inert organic solvent. Further, a metallocene compound containing any of Ti, Zr and Hf is preferable. In particular, a hydrogenated catalyst obtained by reacting a titanocene compound with an alkyllithium is preferable because it is an inexpensive and industrially particularly useful catalyst. As specific examples, for example, JP-A 1-275605, JP-A-5-27136, JP-A-5-27135, JP-A-5-22115, JP-A-11-292924, JP-A-11-292924, JP-A. 2000-37632, JP-A-59-133203, JP-A-63-5401, JP-A-62-218403, JP-A-7-90017, JP-A-43-19960, JP-A. Examples thereof include hydrogenated catalysts described in Japanese Patent Publication No. 47-40473. The hydrogenation catalyst may be used alone or in combination of two or more.

【0027】

In the present invention, when an alkoxysilane compound having a substituent that can be a protecting group is used in order to react with the conjugated diene-based polymer, it can be a modified polymer having a protecting group. Therefore, when a protecting group is bonded to the modified polymer, it is preferable to remove the protecting group during and / or after the hydrogenation reaction. The method for removing the protecting group is not particularly limited, and the method may be selected according to the type of the protecting group. The method of removing the protecting group after the completion of hydrogenation is not particularly limited, and examples thereof include a method of hydrolysis and the like.

【0028】

The molecular weight of the hydrogenated conjugated diene polymer containing an alkoxysilyl group according to the present invention is not particularly limited, but the weight average molecular weight is usually 30,000 to 2,000,000, preferably 40,000 to 1,000,000, and more preferably 50,000 to 50. It is ten thousand.

【0029】

The alkoxysilyl group-containing hydrogenated conjugated diene polymer according to the present invention may have other functional groups such as an amino group, an epoxy group, a glycidyl group, a methacryloyl group and an acryloyl group.

【0030】

On the other hand, among the components (b) related to the present invention, the amino group-containing hydrogenated conjugated diene polymer is not particularly limited, and examples thereof include the polymers (i) to (iii) shown below. (i) A polymer produced by polymerizing a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound having an amino group, and hydrogenating the obtained polymer. (ii) Manufactured by polymerizing an unsaturated monomer having a conjugated diene and an amino group, or an aromatic vinyl compound with these in the presence of an organic alkali metal compound, and then hydrogenating the obtained polymer. Polymer. (iii) Modification of conjugated diene or conjugated diene and aromatic vinyl compound by polymerizing in the presence of an organic alkali metal compound and reacting the obtained conjugated diene-based polymer with a compound represented by the following general formula (1). A polymer produced by preparing a polymer and then hydrogenating the modified polymer. R¹R²C = NY (1) [In the above general formula (1), R¹And R²Are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or organosiloxy groups having 1 to 100 carbon atoms. Y is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aralkyl group having 1 to 100 carbon atoms. It is an organosiloxy group of. ]

【0031】

Examples of the organic alkali metal compound having an amino group used in the production of the polymer (i) include compounds represented by the following general formulas (3) and (4).

【0032】

[Chemical 1]<img file="JP2004123763A_D0001.tif" /> 【0033】

[In the above general formula (3), R⁵And R⁶Are both trialkylsilyl groups with 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group and the other is an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, It is an aralkyl group having 7 to 20 carbon atoms or an organosiloxy group having 1 to 100 carbon atoms. In addition, R in the above general formulas (3) and (4)⁷Is an alkylene group or an alkylidene group having 1 to 20 carbon atoms. Furthermore, R in the above general formula (4)⁸Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. ]

【0034】

Examples of the organic alkali metal compound represented by the above general formulas (3) and (4) include 3-lithio-1- [N, N-bis (trimethylsilyl)] aminopropane (CASNo.289719-98-8), 2 -Lithio-1- [N, N-bis (trimethylsilyl)] aminoethane, 3-lithio-2,2-dimethyl-1-[N, N-bis (trimethylsilyl)] aminopropane, 2,2,5,5- Tetramethyl-1- (3-lithipropyl) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (3-lithio-2,2-dimethyl-propyl) ) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (2-lithioethyl) -1-aza-2,5-disilacyclopentane, 3-lithio -1- [N- (tert-butyl-dimethylsilyl) -N-trimethylsilyl] aminopropane, 3-lithio-1- (N-methyl-N-trimethylsilyl) aminopropane, 3-lithio-1- (N-ethylsilyl) -N-trimethylsilyl) aminopropane and the like can be mentioned.

【0035】

The hydrogenation method and reaction conditions for obtaining the polymer (i) are not particularly limited, and can be carried out in the same manner as described in the above-mentioned alkoxysilyl group-containing hydrogenated conjugated diene polymer. The hydrogenation rate is 80% or more, preferably 95% or more, of the double bond derived from the conjugated diene which is an unsaturated portion.

【0036】

Examples of the unsaturated monomer having an amino group used in the production of the polymer (ii) include compounds represented by the following general formulas (5) and (6).

【0037】

[Chemical 2]<img file="JP2004123763A_D0002.tif" /> 【0038】

[In the above general formulas (5) and (6), R⁹And R¹⁰Are both trialkylsilyl groups with 3 to 18 carbon atoms, or one of them is the trialkylsilyl group and the other is an alkyl group with 1 to 20 carbon atoms and an aryl group with 6 to 20 carbon atoms. , An aralkyl group having 7 to 20 carbon atoms or an organosiloxy group having 1 to 100 carbon atoms. In addition, in the above general formula (6), R¹¹Is an alkylene group or an alkylidene group having 1 to 20 carbon atoms. Further, n in the above general formulas (5) and (6) is 1 to 3. ]

【0039】

Examples of the unsaturated monomer represented by the above general formulas (5) and (6) include p- [N, N-bis (trimethylsilyl) amino] styrene and p- [N, N-bis (trimethylsilyl) aminomethyl. ] Styrene, p- {2- [N, N-bis (trimethylsilyl) amino] ethyl} styrene, m- [N, N-bis (trimethylsilyl) amino] styrene, p- (N-methyl-N-trimethylsilylamino) Examples thereof include styrene and p- (N-methyl-N-trimethylsilylaminomethyl) styrene.

【0040】

The unsaturated monomer represented by the general formulas (5) and (6) is usually 0.01 to 100 times by mole, preferably 0.01 to 10 times by mole, based on the number of moles of the active site derived from the organic alkali metal. Particularly preferably, it is added at a ratio of 1.0 to 3.0 times by mole. The reaction time is preferably in the range of 1 second to 2 hours. Further, the unsaturated monomer can be added at any time such as at the start of polymerization, during polymerization, before completion of polymerization, and after completion of polymerization.

【0041】

The hydrogenation method and reaction conditions for obtaining the polymer (ii) are not particularly limited, and can be carried out in the same manner as described in the above-mentioned alkoxysilyl group-containing hydrogenated conjugated diene polymer. The hydrogenation rate is 80% or more, preferably 95% or more, of the double bond derived from the conjugated diene which is an unsaturated portion.

【0042】

In addition, examples of the compound of the general formula (1) used in the production of the polymer (iii) include N-benzylidenemethylamine, N-benzylideneethylamine, N-benzylidenebutylamine, N-benzylideneaniline and the like. When the compound represented by the above general formula (1) is reacted with the conjugated diene polymer, the amount used is usually 0.2 to 3 times the moles, preferably 0.2 to 3 times the number of moles of the active sites derived from the organic alkali metal compound. Add at a ratio of 0.3 to 1.5 times mol, more preferably 0.4 to 1.3 times mol.

【0043】

The hydrogenation method and reaction conditions for obtaining the polymer (iii) are not particularly limited, and can be carried out in the same manner as described above for the alkoxysilyl group-containing hydrogenated conjugated diene polymer. The hydrogenation rate is 80% or more, preferably 95% or more, of the double bond derived from the conjugated diene which is an unsaturated portion.

【0044】

The content of the amino group in the amino group-containing hydrogenated conjugated diene polymer obtained as described above is usually 0.0001 to 5 mmol / g, preferably 0.001 to 1 mmo1 / g, and more preferably 0.003 to 0.1 mmo1. / g. The position of the amino group is not particularly limited and may be present at the end of the polymer chain or at the side chain. The amino group is preferably a primary amino group and / or a secondary amino group.

【0045】

The molecular weight of the hydrogenated conjugated diene polymer containing an amino group according to the present invention is not particularly limited, but the weight average molecular weight is usually 30,000 to 2,000,000, preferably 40,000 to 1,000,000, and more preferably 50,000 to 500,000. Is.

【0046】

The amino group-containing hydrogenated conjugated diene polymer according to the present invention may have other functional groups such as an alkoxysilyl group, an epoxy group, a glycidyl group, a methacryloyl group and an acryloyl group.

【0047】

As described above, the component (b) according to the present invention may be a hydrogenated conjugated diene polymer having an alkoxysilyl group and an amino group, but the production method thereof is not particularly limited, and for example, The following methods (1) to (3) can be mentioned. (1) Conjugated diene or conjugated diene and aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound having an amino group, and the obtained conjugated diene polymer is a compound represented by the above general formula (2). To obtain a modified polymer obtained by reacting the above, and then hydrogenating the polymer. (2) An unsaturated monomer having a conjugated diene and an amino group or an aromatic vinyl compound is polymerized in the presence of an organic alkali metal compound, and the obtained conjugated diene polymer is obtained by the above general formula (2). A method in which a compound represented by (1) is reacted to obtain a modified polymer, and then the modified polymer is hydrogenated. 3 Conjugated diene or conjugated diene and aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the obtained conjugated diene polymer is reacted with an alkoxysilane compound represented by the following general formula (7). A method of preparing a modified polymer and then hydrogenating the polymer. R¹²_(4-mn)Si (OR¹³)_mX²_n (7) [In the formula, R¹²Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms.¹²If there is more than one, each R¹²May be the same group or different groups. Also, R¹³Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R¹³If there is more than one, each R¹³May be the same group or different groups. X²Is a substituent having a polar group containing at least N atoms (provided that OR¹³Is excluded. ), X²If there is more than one, each X²Can be the same group or different groups, and each X²May be an independent substituent or form a cyclic structure. m is 1, 2 or 3 and n is 0, 1, 2 or 3. The sum of m and n is 1-4. In particular, m is preferably 2 or 3 and n is preferably 0 or 1. ]

【0048】

Examples of the alkoxysilane compound represented by the above general formula (7) include N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, and N, N-bis ( Trimethylsilyl) aminopropyldimethylethoxysilane, N, N-bis (trimethylsilyl) aminopropyldimethylmethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane , N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethyldimethylethoxysilane, N, N-bis (trimethylsilyl) ) Aminoethyldimethylmethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, N-methyl-N-trimethylsilylaminopropyltrimethoxysilane, N -Methyl-N-trimethylsilylaminopropyltriethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylmethoxysilane, N-methyl-N-trimethylsilylaminopropylmethyldiethoxy Silane, N-Methyl-N-trimethylsilylaminopropylmethyldimethoxysilane, N, N-dimethylaminopropyltrimethoxysilane, N, N-dimethylaminopropyltriethoxysilane, N, N-dimethylaminopropyldimethylethoxysilane, N, N-Dimethylaminopropyldimethylmethoxysilane, N, N-dimethylaminopropylmethyldiethoxysilane, N, N-dimethylaminopropylmethyldimethoxysilane, N- (1,3-Dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propaneamine, N-ethylidene-3- (tri) Ethoxysilyl) -1-propaneamine, N- (1-methylpropanol) -3- (triethoxysilyl) -1-propaneamine, N- (4-N, N-dimethylaminobenzylidene) -3- (tri) Ethoxysilyl) -1-propaneamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propaneamine, N- (1-methylethylidene) -3- (trimethoxysilyl) -1-Propanamine, N-ethylidene-3- (trimethoxysilyl) -1-propaneamine, N- (1-methylpropanol) -3- (trimethoxysilyl) -1-propaneamine, N- (4) -N, N-dimethylaminobenzylidene) -3- (trimethoxysilyl) -1-propaneamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxysilyl) -1-propaneamine, N- (1-Methylethylidene) -3- (methyldimethoxysilyl) -1-propaneamine, N-ethylidene-3- (methyldimethoxysilyl) -1-propaneamine, N- (1-methylpropyridene) -3- ( Methyldimethoxysilyl) -1-propaneamine, N- (4-N, N-dimethylaminobenzylidene) -3- (methyldimethoxysilyl) -1-propaneamine, N- (1,3-dimethylbutylidene) -3 -(Methyldiethoxysilyl) -1-propaneamine, N- (1-methylethylidene) -3- (methyldiethoxysilyl) -1-propaneamine, N-ethylidene-3- (methyldiethoxysilyl) -1 -Propanamine, N- (1-methylpropylidene) -3- (methyldiethoxysilyl) -1-propaneamine, N- (4-N, N-dimethylaminobenzylidene) -3- (methyldiethoxysilyl) -1-Propanamine, N- (1,3-Dimethylbutylidene) -3- (dimethylmethoxysilyl) -1-propaneamine, N- (1-methylethylidene) -3- (dimethylmethoxysilyl) -1-propaneamine, N-ethylidene-3- (dimethyl) Methoxysilyl) -1-propaneamine, N- (1-methylpropyridene) -3- (dimethylmethoxysilyl) -1-propaneamine, N- (4-N, N-dimethylaminobenzylidene) -3- (dimethyl) Methoxysilyl) -1-propaneamine, N- (1,3-dimethylbutylidene) -3- (dimethylethoxysilyl) -1-propaneamine, N- (1-methylethylidene) -3- (dimethylethoxysilyl) -1-Propanamine, N-ethylidene-3- (dimethylethoxysilyl) -1-propaneamine, N- (1-methylpropylidene) -3- (dimethylethoxysilyl) -1-propaneamine, N- (4 Examples thereof include -N, N-dimethylaminobenzylidene) -3- (dimethylethoxysilyl) -1-propaneamine.

【0049】

The content of the alkoxysilyl group and the amino group in the obtained hydrogenated conjugated diene polymer having the alkoxysilyl group and the amino group is usually 0.0001 to 5 mmol / g, preferably 0.001 to 1 mmo1 / g, and further. Preferably, it is 0.003 to 0.1 mmo1 / g. These groups are usually present at the end of the polymer chain, but may be present at the side chain.

【0050】

The hydrogenated conjugated diene polymer containing an alkoxysilyl group and an amino group according to the present invention may have other functional groups such as an epoxy group, a glycidyl group, a methacryloyl group and an acryloyl group.

【0051】

The hydrogenation method and reaction conditions for obtaining a hydrogenated conjugated diene polymer containing an alkoxysilyl group and an amino group are not particularly limited, and are the same as those described above for the alkoxysilyl group-containing hydrogenated conjugated diene polymer. Can be done. The hydrogenation rate is 80% or more, preferably 95% or more, of the double bond derived from the conjugated diene which is an unsaturated portion.

【0052】

The molecular weight of the hydrogenated conjugated diene polymer having an alkoxysilyl group and an amino group is not particularly limited, but the weight average molecular weight is usually 30,000 to 2,000,000, preferably 40,000 to 1,000,000, and more preferably 50,000 to. It is 500,000.

【0053】

Here, the conjugated diene-based polymer to be reacted with an alkoxysilane compound, a compound having an amino group, or the like may be a polymer obtained by polymerizing only the conjugated diene, or a polymer obtained by polymerizing the conjugated diene and an aromatic vinyl compound. There may be. It is a block copolymer containing two or more polymer blocks selected from the following polymer blocks (A) to (D) from the viewpoint of molding processability of the obtained composition and physical properties of the molded product. Is preferable. (A) Aromatic vinyl compound polymer block having an aromatic vinyl compound of 80% by mass or more (B) Conjugated diene polymer block having a vinyl bond content of less than 25% by mass (C) Vinyl bond content of 25% by mass or more 90 Conjugated diene polymer block of mass% or less (D) Random copolymer block of aromatic vinyl compound and conjugated diene Among these, in particular, at least one or more of the polymer blocks of the above (B) or (C). A block copolymer having a block copolymer is preferable.

【0054】

The composition ratio of the "conjugated diene" and the "vinyl aromatic compound" in the "conjugated diene polymer" is not particularly limited, but usually 5 to 100% by mass of the conjugated diene and the aromatic vinyl compound 0. It can be in the range of ~ 95% by mass, preferably 5 to 95% by mass and 95 to 5% by mass, more preferably 30 to 92% by mass of conjugated diene and 70 to 8% by mass of the aromatic vinyl compound.

【0055】

The random copolymer block of (D) may also include a so-called taper type in which the content of the aromatic vinyl compound continuously changes in one molecule. Further, as an example of the above-mentioned "block copolymer containing two or more polymer blocks selected from the polymer blocks of (A) to (D)", (A)-(B), (A) -(C), (A)-(D), (C)-(D), (B)-(C), [(A)-(B)] xY, [(A)-(C) ] x-Y, [(A)-(D)] x-Y, [(C)-(D)] x-Y, [(B)-(C)] x-Y, (A)-(B) )-(C), (A)-(B)-(D), (A)-(B)-(A), (A)-(C)-(A), (A)-(D)- (A), (A)-(D)-(C), (A)-(C)-(B), (B)-(C)-(B), [(A)-(B)-( C)] x-Y, [(A)-(B)-(A)] x-Y, [(A)-(C)-(A)] x-Y, [(A)-(D)- (A)] x-Y, [(A)-(D)-(C)] x-Y, (A)-(B)-(A)-(B), (B)-(A)-( B)-(A), (A)-(C)-(A)-(C), (C)-(A)-(C)-(A), [(A)-(B)-(A) )-(B)] xY, (A)-(B)-(A)-(B)-(A), [(A)-(B)-(A)-(B)-(A) ] x-Y, [(B)-(A)] x-Y, [(C)-(A)] x-Y, [(D)-(A)] x-Y, (B)-(A) )-(B)-(C), (B)-(A)-(B)-(A), (B)-(A)-(C)-(A), (C)-(A)- (D)-(A), (C)-(A)-(D)-(C), [(C)-(A)-(B)-(C)] xY, [(D)- (A)-(B)-(A)] x-Y, [(D)-(A)-(C)-(A)] x-Y, [(D)-(A)-(D)- (A)] x-Y, [(D)-(A)-(D)-(C)] x-Y, (D)-(A)-(B)-(A)-(B), ( D)-(B)-(A)-(B)-(A), (D)-(A)-(C)-(A)-(C), (D)-(C)-(A) -(C)-(A), [(D)-(A)-(B) -(A)-(B)] xY, (D)-(A)-(B)-(A)-(B)-(A), [(D)-(A)-(B)- (A)-(B)-(A)] x-Y and the like can be mentioned (however, x 2 and Y is a residue of the coupling agent). When the pellet shape is formed, it is preferable to contain at least one (A) and / or (B) polymer block as the outer block component of the hydrogenated modified polymer.

【0056】

Examples of the coupling agent include halogen compounds, epoxy compounds, carbonyl compounds, polyvinyl compounds and the like. Specifically, as the coupling agent, methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, dibromoethane, epoxidized soybean oil, divinylbenzene, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, and bis ( Examples thereof include trichlorosilyl) ethane, diethyl adipate, dimethyl adipate, dimethyl terephthalate, diethyl terephthalate, and polyisocyanate.

【0057】

The component (b) according to the present invention may be only an alkoxysilyl group-containing hydrogenated conjugated diene polymer, or may be only an amino group-containing hydrogenated conjugated diene polymer. The alkoxysilyl group-containing hydrogenated conjugated diene polymer may be a polymer having an amino group. (The amino group-containing hydrogenated conjugated diene-based polymer may be a polymer having an alkoxysilyl group.) Further, as the component (b) according to the present invention, the alkoxysilyl group-containing hydrogenated conjugated diene-based polymer weight. It may be a mixture of a coalescence and a hydrogenated conjugated diene polymer containing an amino group. Therefore, the following combinations can be mentioned as constituents of the resin composition of the present invention. (1) A combination of an ionomer resin and an alkoxysilyl group-containing hydrogenated conjugated diene polymer (or an alkoxysilyl group-containing hydrogenated conjugated diene polymer having an amino group), (2) an ionomer resin and an amino group-containing Combination with a hydrogenated conjugated diene polymer (or an amino group-containing hydrogenated conjugated diene polymer having an alkoxysilyl group), (3) Ionomer resin and an alkoxysilyl group-containing hydrogenated conjugated diene polymer (or amino) A combination of an alkoxysilyl group-containing hydrogenated conjugated diene polymer having a group) and an amino group-containing hydrogenated conjugated diene polymer (or an amino group-containing hydrogenated conjugated diene polymer having an alkoxysilyl group).

【0058】

The resin composition of the present invention contains a component (a) and a component (b). The content ratios (a) / (b) of the components (a) and (b) are preferably 30 to 95% by mass / 70 to 5 when the total of the components (a) and (b) is 100% by mass. It is by mass%, more preferably 40 to 85% by mass / 60 to 15% by mass. (a) If the content of the component is less than 30% by mass, the tensile strength is inferior, and when it is used for the skin of a golf ball, the cut resistance at the time of hitting is impaired, and if it exceeds 95% by mass, it becomes soft. It is not done sufficiently, and the shot feeling and controllability are not sufficiently improved.

【0059】

In addition to the components (a) and (b), the resin composition of the present invention further comprises polyethylene, polypropylene, poly1-butene, a propylene / ethylene copolymer, and propylene / 1-, as long as its properties are not impaired. Butene copolymer, 1-butene / ethylene copolymer, polyolefin resin such as propylene / ethylene / 1-butene copolymer, polyamide resin such as nylon 4,6, nylon 6, nylon 6,6, polyethylene terephthalate, poly Polyester resin such as butylene terephthalate and polylactone, polycarbonate such as poly-2,2-bis (hydroxyphenyl) propanecarbonate, acrylic polymer such as polymethylmethacrylate and polyethylmethacrylate, polyoxymethylene, polystyrene, ABS, Polyphenylene ether, modified polyphenylene ether, thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, thermoplastic polyamide elastomer, α, β-unsaturated nitrile-acrylic acid ester-unsaturated diene copolymer rubber, urethane rubber and the like can be blended. ..

【0060】

Further, the resin composition of the present invention has an inorganic filler, a plasticizer, a glass fiber, a carbon fiber, a heat antiaging agent, a light stabilizer, an antistatic agent, a mold release agent, and a flame retardant for the purpose of modifying the resin composition. , Foaming agents, pigments, dyes, whitening agents and the like can also be added. Examples of the inorganic filler include titanium oxide, talc, calcium carbonate, kaolin and the like, and these can be used alone or in combination of two or more. The blending amount of the inorganic filler is preferably 0.1 to 40 parts by mass, more preferably 2 to 30 parts by mass, based on 100 parts by mass of the total of the components (a) and (b). Examples of the plasticizer include process oil, low molecular weight polyethylene, polyethylene glycol and the like.

【0061】

The resin composition of the present invention can be prepared by mixing the component (a) and the component (b), and is a kneader for a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, a roll, or the like. It is obtained by kneading each component in a heated and melted state using. The resin composition thus obtained can be molded by any molding method such as injection molding, blow molding, press molding, extrusion molding, and calendar molding.

【0062】

Since the resin composition of the present invention provides a molded product having sufficient impact resilience and excellent mechanical properties and flexibility, it can be used for various purposes by taking advantage of such features. Specifically, it can be used for automobile parts such as body panels and side seals, sports equipment such as golf balls and ski boots, food packaging materials, medical products such as syringe gaskets, leisure products, daily necessities, toy products and the like. In particular, it is preferably used as a golf ball skin material.

【0063】

When the resin composition of the present invention is used as a golf ball skin material, the hardness of the molded product obtained by using the resin composition is preferably in the range of 40 to 62 in shore D hardness, more preferably 45 to. It is 60.

【0064】

The golf ball of the present invention has a core coated with a skin material made of the above resin composition. The core covered with the skin material may be either a solid golf ball core or a pincushion golf ball core. In the case of a core for a solid golf ball (solid core), a core for a two-piece golf ball or a core for a multiple solid golf ball such as a three-piece may be used, and these solid cores may be manufactured by a known composition and manufacturing method. it can. On the other hand, in the case of a pincushion golf ball core (pincushion core), a thread rubber is wound around the center, and the center may be either a liquid center or a solid center, and these pincushion cores also have a known composition and manufacturing method. The manufactured one can be used.

【0065】

The method of coating and forming the skin material on the core is not particularly limited. For example, a method of directly injection molding the skin material composition on the core, or two hemispherical shell-shaped half cups are formed in advance with the skin material composition. , A method in which the core is covered with these cups and pressure-heat molded at 110 to 160 ° C. for 2 to 10 minutes can be adopted. The golf ball of the present invention is formed in a size and weight according to the golf ball rules, but in this case, the thickness of the skin material is preferably in the range of 1 to 3 mm.

【0066】

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples. The parts and% in Examples and Comparative Examples are based on mass unless otherwise specified. In addition, various measurements were based on the following methods.

【0067】

(1) Vinyl bond (1,2 and 3,4 bond) content Obtained by infrared absorption spectroscopy (Morero method). (2) A calibration curve was prepared and obtained by the combined styrene content infrared absorption spectroscopy. 3 Weight average molecular weight Gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120) was used to determine in polystyrene conversion. 4 Si-OC based on the alkoxysilyl group content (mmol / g) infrared absorption spectrum₆H₅1250 cm due to binding^-1Quantification was performed from the calibration curve prepared based on the amount of absorption in the vicinity. In addition, the alkoxysilyl group is Si-OCH.₃, Si-OC₂H₅, Si-OC (CH)₃)₂(C₂H₅) For binding, 1100 cm^-1Quantification was performed from the calibration curve prepared based on the amount of absorption in the vicinity. However, the quantified value was divided by the polystyrene-equivalent number average molecular weight Mn obtained by the GPC method and the molecular weight of the alkoxysilyl group to obtain the number of moles of the alkoxysilyl group. 5 Amino group content (mmol / g) was determined by the amine titration method (see Anal.Chem. (1952) p.564). That is, after purifying the hydrogenated polymer, dissolve it in an organic solvent, use methyl violet as an indicator, and HClO until the color of the solution changes from purple to light blue.₄/ CH₃Obtained by titrating COOH. 6 Hydrogenation rate of conjugated diene Using carbon tetrachloride as a solvent, 270 MHz,¹Calculated from 1 H-NMR spectrum.

【0068】

[1] Synthesis of Alkoxysilyl Group and / or Amino Group-Containing Hydrogenated Conjugated Diene Polymer A alkoxysilyl group and / or amino group-containing hydrogenated conjugated diene polymer was synthesized by the method described below. Synthesis Example 1 To a reaction vessel having an internal volume of 10 liters substituted with nitrogen, 5000 g of cyclohexane, 150 g of styrene, 150 g of tetrahydrofuran, and 0.9 g of n-butyllithium were added, and the first stage polymerization was carried out at a polymerization initiation temperature of 50 ° C. After completion, 690 g of 1,3-butadiene was added at a temperature of 20 ° C, and the second stage polymerization was carried out by heat insulation. After 30 minutes, 150 g of styrene was added to carry out the third-stage polymerization, and after the reaction was completed, 10 g of 1,3-butadiene was added to further carry out the fourth-stage polymerization. This block polymer partially taken out contained 80% of vinyl bonds, and the weight average molecular weight measured by GPC was about 110,000. Then, 3.93 g of methyltriphenoxysilane was added as a denaturant into this system, and the mixture was reacted for 30 minutes. After the reaction, set the reaction solution to 70 ° C and bis (η).⁵-Cyclopentadienyl) Titanium (tetrahydrofurfuryloxy) chloride 0.4 g and n-butyllithium 0.15 g were added, and the mixture was reacted at a hydrogen pressure of 1.0 MPa for 60 minutes. After the reaction, the reaction solution was returned to normal temperature and pressure, withdrawn from the reaction vessel, stirred into water, and the solvent was removed by steam distillation to obtain an alkoxysilyl group-containing hydrogenated conjugated diene polymer (b-1). It was. The obtained polymer (b-1) had a hydrogenation rate of 98%, a weight average molecular weight of about 120,000, and an alkoxysilyl group content of 0.0161 mmol / g. An alkoxysilyl group and / or amino group-containing hydrogenated conjugated diene polymer (b-2) as shown in Table 1 by changing the type of modifier, the amount of monomer, etc. according to the polymer (b-1). ) ~ (B-5) was obtained. The polymer (b-6) was obtained without the use of an alkoxysilane compound. The polymer structure A shown in Table 1 indicates a styrene polymer block, and C indicates a butadiene polymer block having a vinyl bond content of 25% by mass or more and 90% by mass or less.

【0069】

Synthesis Example 2 To a reaction vessel having an internal volume of 10 liters substituted with nitrogen, 5000 g of cyclohexane, 300 g of butadiene, 0.25 g of tetrahydrofuran, and 0.9 g of n-butyllithium were added, and the first stage polymerization was carried out at a polymerization initiation temperature of 70 ° C. After the reaction was completed, the vinyl bond of this block polymer partially taken out was 10%. Then, at a temperature of 20 ° C., 75 g of tetrahydrofuran was added, 700 g of 1,3-butadiene was added, and the second stage polymerization was carried out by heat insulation. The second-stage vinyl bond of this partially extracted block polymer contained 80%, and the weight average molecular weight measured by GPC was about 140,000. Then, 2.1 g of methyltriphenoxysilane was added to this system, and the reaction was carried out for 30 minutes. After the reaction, set the reaction solution to 70 ° C and bis (η).⁵-Cyclopentadienyl) Titanium (flufuryloxy) chloride 0.4 g and n-butyllithium 0.15 g were added, and the mixture was reacted at a hydrogen pressure of 1.0 MPa for 60 minutes. After the reaction, the temperature was returned to normal temperature and pressure, the mixture was withdrawn from the reaction vessel, and the solvent was removed by steam distillation with stirring in water to obtain an alkoxysilyl group-containing hydrogenated conjugated diene polymer (b-7). The obtained polymer (b-7) had a hydrogenation rate of 95%, a weight average molecular weight of about 270,000, and an alkoxysilyl group content of 0.003 mmol / g. A hydrogenated conjugated diene polymer (b-8) containing an alkoxysilyl group and an amino group as shown in Table 2 was obtained by changing the type of modifier, the amount of monomer, etc. according to the polymer (b-7). Obtained. The polymer (b-9) was obtained without the use of an alkoxysilane compound.

【0070】

Synthesis Example 3 To a reaction vessel having an internal volume of 10 liters substituted with nitrogen, 5000 g of cyclohexane, 150 g of butadiene, 0.25 g of tetrahydrofuran, and 0.95 g of n-butyllithium were added, and the first stage polymerization was carried out at a polymerization start temperature of 70 ° C. After completion, the vinyl bond of this block polymer partially taken out was 10%, the temperature was set to 20 ° C., 25 g of tetrahydrofuran was added, and 690 g of 1,3-butadiene was added, and the second stage polymerization was carried out by heat insulation. After 30 minutes, 150 g of styrene was added to carry out the third-stage polymerization, and after the reaction was completed, 10 g of 1,3-butadiene was added to further carry out the fourth-stage polymerization. This block polymer partially taken out contained 65% of vinyl bonds, and the weight average molecular weight measured by GPC was about 120,000. Then, 4.03 g of methyltriphenoxysilane was added to this system, and the reaction was carried out for 30 minutes. After the reaction, set the reaction solution to 70 ° C and bis (η).⁵-Cyclopentadienyl) Titanium (tetrahydrofurfuryloxy) chloride 0.4 g and n-butyllithium 0.15 g were added, and the mixture was reacted at a hydrogen pressure of 1.0 MPa for 60 minutes. After the reaction, the reaction solution was returned to normal temperature and pressure, withdrawn from the reaction vessel, stirred into water, and the solvent was removed by steam distillation to remove the alkoxysilyl group-containing hydrogenated conjugated diene polymer (b-10). Obtained. The obtained polymer (b-10) had a hydrogenation rate of 95%, a weight average molecular weight of about 130,000, and an alkoxysilyl group content of 0.0148 mmol / g. A hydrogenated conjugated diene polymer (b-11) containing an alkoxysilyl group and an amino group as shown in Table 2 was obtained by changing the type of modifier, the amount of monomer, etc. according to the polymer (b-10). Obtained. (b-12) was obtained without using an alkoxysilane compound. The polymer structures A shown in Table 2 are "styrene polymer blocks", B is "butadiene polymer blocks having a vinyl bond content of less than 25% by mass", and C is "vinyl bond content of 25% by mass or more 90". "Butadiene polymer block of mass% or less" is shown.

【0071】

Synthesis Example 4 To a reaction vessel having an internal volume of 10 liters substituted with nitrogen, 5000 g of cyclohexane, 150 g of tetrahydrofuran, 400 g of styrene, and 2.88 g of 3-lithio-1-N, N-bis (trimethylsilyl) aminopropane were added, and the polymerization initiation temperature was increased. Polymerized at 50 ° C. After the reaction was completed, 500 g of 1,3-butadiene was added at a temperature of 20 ° C. and polymerization was carried out by adiabatic insulation. After 30 minutes, 100 g of styrene was added and further polymerization was carried out. Then, the reaction solution was set to 80 ° C. or higher, and hydrogen was introduced into the system. Then the screw (η)⁵-Cyclopentadienyl) Titanium (tetrahydrofurfuryloxy) chloride 0.32 g and tetrachlorosilane 0.39 g were added, and the mixture was reacted for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution was returned to normal temperature and pressure and withdrawn from the reaction vessel, and then the reaction solution was stirred into water and the solvent was removed by steam distillation to remove the amino group-containing hydrogenated conjugated diene polymer (b). -13) was obtained. The obtained polymer (b-13) had a hydrogenation rate of 98%, a weight average molecular weight of about 100,000, and an amino group content of 0.0095 mmol / g.

【0072】

Synthesis Example 5 Cyclohexane 5000 g, tetrahydrofuran 150 g, styrene 100 g, and 2,2,5,5-tetramethyl-1- (3-lithiopropyl) -1-aza- in a reaction vessel having a nitrogen-substituted internal volume of 10 liters. 2.89 g of 2,5-disilacyclopentane was added, and the mixture was polymerized at a polymerization initiation temperature of 50 ° C. After the reaction was completed, 850 g of 1,3-butadiene was added at a temperature of 20 ° C. and polymerization was carried out by adiabatic insulation. After 30 minutes, 50 g of styrene was added and further polymerization was carried out. Then, the reaction solution was set to 80 ° C. or higher, and hydrogen was introduced into the system. Then the screw (η)⁵-Cyclopentadienyl) Titanium (flufuryloxy) chloride 0.55 g and tetrachlorosilane 0.39 g were added, and the reaction was carried out for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution was returned to normal temperature and pressure and withdrawn from the reaction vessel, and then the reaction solution was stirred into water and the solvent was removed by steam distillation to remove the amino group-containing hydrogenated conjugated diene polymer (b). -14) was obtained. The obtained polymer (b-14) had a hydrogenation rate of 97%, a weight average molecular weight of about 120,000, and an amino group content of 0.0083 mmol / g.

【0073】

Synthesis Example 6 Using n-BuLi as the polymerization initiator, the amount of the polymerization initiator, the type of the monomer, the amount of the monomer, the polymerization temperature, and the like so as to obtain the polymer structure shown in (b-15) of Table 3. A block copolymer was obtained according to Synthesis Example 1 by changing the polymerization time and the like. Then, 7.4 g of p- {2- [N, N-bis (trimethylsilyl) amino] ethyl} styrene was added to the active site of the polymer, and the mixture was reacted for 30 minutes. Then, the reaction solution was set to 80 ° C. or higher, and hydrogen was introduced into the system. Then, 2.97 g of dichlorotris (triphenylphosphine) ruthenium was added, and the reaction was carried out for 1 hour while maintaining a hydrogen pressure of 2.0 MPa. After the reaction, the reaction solution was returned to normal temperature and pressure and withdrawn from the reaction vessel, and then the reaction solution was stirred into water and the solvent was removed by steam distillation to remove the amino group-containing hydrogenated conjugated diene polymer (b). -15) was obtained. The obtained polymer (b-15) had a hydrogenation rate of 99%, a weight average molecular weight of about 120,000, and an amino group content of 0.045 mmol / g.

【0074】

Synthesis Example 7 Using n-BuLi as the polymerization initiator, the amount, monomer type, monomer amount, and polymerization temperature of the polymerization initiator so as to obtain the copolymer structure shown in (b-16) of Table 3. , The polymerization time and the like were changed to obtain a block copolymer according to Synthesis Example 1. Then, 1.56 g of N-benzylideneethylamine was added to the active site of the polymer, and the mixture was reacted for 30 minutes. Then, the reaction solution was set to 80 ° C. or higher, and hydrogen was introduced into the system. Then Pd-BaSO₄2.60 g was added and the reaction was carried out for 1 hour while maintaining a hydrogen pressure of 2.0 MPa. After the reaction, the reaction solution was returned to normal temperature and pressure and withdrawn from the reaction vessel, and then the reaction solution was stirred into water and the solvent was removed by steam distillation to remove the amino group-containing hydrogenated conjugated diene polymer (b). -16) was obtained. The obtained polymer (b-16) had a hydrogenation rate of 98%, a weight average molecular weight of about 130,000, and an amino group content of 0.007 mmol / g. The polymer structure A shown in Table 3 indicates a styrene polymer block, and C indicates a butadiene polymer block having a vinyl bond content of 25% by mass or more and 90% by mass or less.

【0075】

[table 1]<img file="JP2004123763A_D0003.tif" /> 【0076】

[Table 2]<img file="JP2004123763A_D0004.tif" /> 【0077】

[Table 3]<img file="JP2004123763A_D0005.tif" /> 【0078】

[2] Examples and Comparative Examples The various components used in the Examples and Comparative Examples are as follows. (a) Ionomer resin; [DuPont, 1/1 blend of Sarlin 9945 and Sarlin 8945]

(b) Hydrokoxysilyl group and / or amino group-containing hydrogenated conjugated diene-based polymers; Polymers having the structures shown in Tables 1 to 3 (b-1) to (b-16) [0079]

Example 1 A twin-screw extruder with a cylinder diameter of 45 mm and L / D = 32 (manufactured by Ikegai Corp.) in which 80 parts of (a) component and 20 parts of (b-1) as component (b) are set at 200 ° C. ) Was melt-kneaded at 200 rpm and then pelletized, and a test piece for physical property evaluation having a thickness of 2 mm was prepared at 200 ° C. by press molding with a thickness of 2 mm using this pelletized product. The tensile strength at break, the elongation at break and the hardness were measured by the methods described below. The results are shown in Table 4.

【0080】

Using the formulation shown in Examples 2 to 11 and Comparative Examples 1 to 3 Tables 4 and 5, test pieces were prepared in the same manner as in Example 1 and their physical properties were evaluated. The results are shown in Tables 4 and 5 below.

【0081】

Examples 12 to 15 Using the formulation shown in Table 6, test pieces were prepared in the same manner as in Example 1 and their physical properties were evaluated. The results are shown in Table 6 below.

【0082】

&lt;Evaluation method&gt; 1 Tensile breaking strength and tensile elongation at breaking JIS C3005 was measured by conducting a tensile test with a No. 3 dumbbell under a temperature condition of 23 ° C. 2 Hardness (Shore D) Measured in accordance with JIS-K6253 as an index of flexibility.

【0083】

[Table 4]<img file="JP2004123763A_D0006.tif" /> 【0084】

[Table 5]<img file="JP2004123763A_D0007.tif" /> 【0085】

[Table 6]<img file="JP2004123763A_D0008.tif" /> 【0086】

From Table 5, Comparative Examples 1 to 3 use hydrogenated polymers that do not contain an alkoxysilyl group and an amino group, and therefore have sufficient hardness, but are inferior in tensile strength and tensile elongation, and inferior in flexibility. On the other hand, from Tables 4 to 6, Examples 1 to 15 have an excellent balance between tensile strength and tensile elongation and hardness.

【0087】

Examples 16 to 30, Comparative Examples 4 to 6 Polybutadiene (BR01 manufactured by JSR) 100 parts by mass, zinc diacrylate 25 parts by mass, zinc oxide 22 parts by mass, dicumyl peroxide 1.8 parts by mass and antioxidant 0.5 parts by mass. Was kneaded with a roll, and the obtained core composition was pressure crosslinked at 150 ° C. for 30 minutes to obtain a core having a diameter of 38.5 mm.

【0088】

Next, the obtained core is coated by an injection molding method with a composition for a skin material consisting of a mixture of 100 parts by mass of the polymer composition and 2 parts by mass of titanium dioxide shown in Tables 7 to 9 to cover the skin. A material was formed to produce a two-piece solid golf ball with an outer diameter of 42.7 mm.

【0089】

The weight, hardness, initial velocity of the ball, flight distance, and cut resistance of the obtained two-piece solid golf ball were measured. The results are shown in Tables 7 to 9. In addition, the obtained golf ball was actually hit with the Wood No. 1 club, and the shot feeling was examined. The results are also shown in Tables 7 to 9.

【0090】

The method for measuring the hardness, the initial velocity of the ball, and the flight distance, and the method for evaluating the shot feeling and the cut resistance are as follows. (1) Hardness; The amount of deflection (mm) when a 100 kg load was applied to the ball was measured. The larger the number, the softer the ball. (2) Initial ball velocity; Wood No. 1 club was attached to a swing robot manufactured by Trutemper, and the ball was hit at a head speed of 45 m / sec, and the initial ball velocity (m / sec) at that time was measured. (3) Flying distance; Wood No. 1 club was attached to a swing robot manufactured by Trutemper, and the distance (yard) to the falling point of the ball when the ball was hit at a head speed of 45 m / sec was measured. (4) Shot feeling; evaluated by actual hit test. In the evaluation of the shot feeling, the shot feeling was evaluated using the ball of Comparative Example 4 as a comparison target. The evaluation criteria are as follows, and when the evaluation results are displayed in the table, they are displayed with the same symbols. The evaluation criteria are as follows. ; The shot feeling is softer and better than the ball of Comparative Example 4. Δ; The shot feeling is the same as that of the ball of Comparative Example 4. ×; The shot feeling is harder and worse than the ball of Comparative Example 4.

【0091】

(5) Cut resistance; The ball was kept warm at 23 ° C, a pitching wedge was attached to the swing robot machine, the top was hit at a head speed of 32 m / sec, and the presence or absence of cut scratches was examined. The evaluation criteria are as follows. ; No scratches. ×; There are scratches.

【0092】

[Table 7]<img file="JP2004123763A_D0009.tif" /> 【0093】

[Table 8]<img file="JP2004123763A_D0010.tif" /> 【0094】

[Table 9]<img file="JP2004123763A_D0011.tif" /> 【0095】

[3] Effect of Examples From Table 8, in Comparative Examples 4 to 6, the initial velocity of the hit ball was 64 to 65 m / sec and the flight distance did not reach 230 yards because the impact resilience of the molded product was inferior. In addition, scratches were confirmed in the cut resistance test. On the other hand, from Tables 7 to 9, in Examples 16 to 30, the initial velocity of the hit ball exceeded 65 m / sec, and the flight distance also exceeded 230 yards. In addition, the shot feeling of the ball was excellent, and the cut resistance was also good.

【0096】

[Effect of the invention]

The resin composition of the present invention contains an ionomer resin and an alkoxysilyl group-containing hydrogenated conjugated diene polymer and / or an amino group-containing hydrogenated conjugated diene polymer, thereby providing flexibility, impact resilience, and mechanical properties. It is possible to provide an excellent molded product. Further, if such a property is utilized, it is useful as a golf ball skin material. Further, the golf ball coated with the golf ball skin material has a good shot feeling, a long flight distance, and an excellent cut resistance.