JP2011148935A - Tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tire provided with excellent abrasion resistance and wet skid resistance by adopting a rubber composition containing a specific aromatic vinyl compound-conjugated diene compound copolymer, silica and a silane coupling agent of a specific structure. <P>SOLUTION: The tire uses a rubber composition containing: an aromatic vinyl compound-conjugated diene compound copolymer (A) which is obtained by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing at least one complex represented by general formula (I) or the like, and in which a conjugated diene compound moiety has cis-1, 4 bonds in an amount of ≥80%; silica (B); and a silane coupling agent (C) represented by the formula (V): R<SP>1</SP><SB>x</SB>R<SP>2</SP><SB>y</SB>R<SP>3</SP><SB>z</SB>Si-R<SP>4</SP>-S-CO-R<SP>5</SP>. In formula (I), M denotes a lanthanoid element, scandium or yttrium; Cp<SP>R</SP>s each independently denotes unsubstituted or substituted indenyl; R<SP>a</SP>to R<SP>f</SP>each independently denotes 1-3C alkyl; L denotes a neutral Lewis base; and w denotes an integer of 0-3. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a tire using a rubber composition containing a specific aromatic vinyl compound-conjugated diene compound copolymer, silica and a silane coupling agent having a specific structure, and in particular, by using the rubber composition in a tread. The present invention relates to a tire that exhibits excellent wear resistance and wet skid resistance.

  An aromatic vinyl compound-conjugated diene compound copolymer such as a styrene-butadiene copolymer is synthesized by polymerization using ordinary anionic and radical polymerization initiators, etc., and has an isomeric structure of the conjugated diene compound portion. In general, the 1,4 structure includes many trans-1,4 structures. Further, it is difficult to control the isomer structure of the conjugated diene compound portion other than the vinyl bond amount.

  On the other hand, in order to control the stereoregularity of the conjugated diene compound portion, for example, the content of the cis-1,4 structure, an aromatic vinyl compound-conjugated using a metal catalyst composed of a ligand and a metal atom. A technique for producing a diene compound copolymer is known (for example, see Patent Documents 1 to 3). However, the aromatic vinyl compound-conjugated diene compound copolymer obtained by this method sometimes involves problems such as blocking of the aromatic vinyl compound portion and lowering of the molecular weight.

Japanese Patent No. 3207502 JP 2006-137897 A Japanese Patent No. 3738315

  By the way, an aromatic vinyl compound-conjugated diene compound copolymer having a high amount of cis-1,4 bonds in the conjugated diene compound portion is more tire-like than an aromatic vinyl compound-conjugated diene compound copolymer containing a lot of other microstructures. There is a tendency to impart wear resistance and wet skid resistance to these, and it has been found that if the workability of the rubber composition is improved by combining with other compounding agents, these wear resistance and wet skid resistance can be further improved. It was.

  Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art and employ a rubber composition containing a specific aromatic vinyl compound-conjugated diene compound copolymer, silica, and a silane coupling agent having a specific structure. It is an object of the present invention to provide a tire having excellent wear resistance and wet skid resistance.

  As a result of intensive investigations to achieve the above object, the present inventors have carried out addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing a specific metallocene complex, thereby producing a conjugated diene compound. An aromatic vinyl compound-conjugated diene compound copolymer having a cis-1,4 bond content of 80% or more is obtained, and the aromatic vinyl compound-conjugated diene compound copolymer is used as a rubber component, and silica And a rubber composition containing a silane coupling agent having a specific structure was found to be able to significantly improve the wear resistance and wet skid resistance, thereby completing the present invention.

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式(II)：

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ^’は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、並びに下記一般式(III)：

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R’は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、[Ｂ]⁻は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からなる群より選択される少なくとも１種類の錯体を含む重合触媒組成物の存在下、芳香族ビニル化合物及び共役ジエン化合物を付加重合して得られた、共役ジエン化合物部分のシス-１,４結合量が80％以上の芳香族ビニル化合物−共役ジエン化合物共重合体（Ａ）と、
シリカ（Ｂ）と、
下記式(V)：
Ｒ¹ _xＲ² _yＲ³ _zＳｉ−Ｒ⁴−Ｓ−ＣＯ−Ｒ⁵ ・・・ (V)
［式中、Ｒ¹は、Ｒ⁶Ｏ−、Ｒ⁶Ｃ(＝Ｏ)Ｏ−、Ｒ⁶Ｒ⁷Ｃ＝ＮＯ−、Ｒ⁶Ｒ⁷ＮＯ−、Ｒ⁶Ｒ⁷Ｎ−及び−(ＯＳｉＲ⁶Ｒ⁷)_n(ＯＳｉＲ⁵Ｒ⁶Ｒ⁷)から選択され且つ炭素数が１〜１８であり（但し、Ｒ⁶及びＲ⁷は、それぞれ独立してアルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基及びアリール基から選択され且つ炭素数が１〜１８であり、ｎは０〜１０である）；
Ｒ²は、水素、又は炭素数１〜１８のアルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基及びアリール基から選択され；
Ｒ³は、−[Ｏ(Ｒ⁸Ｏ)_m]_0.5−基（但し、Ｒ⁸は、アルキレン基及びシクロアルキレン基から選択され且つ炭素数が１〜１８であり、ｍは１〜４である）であり；
ｘ＋ｙ＋２ｚ＝３、０≦ｘ≦３、０≦ｙ≦２、０≦ｚ≦１であり；
Ｒ⁴は、アルキレン基、シクロアルキレン基、シクロアルキルアルキレン基、アルケニレン基、アリーレン基及びアラルキレン基から選択され且つ炭素数が１〜１８であり；
Ｒ⁵は、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アリール基及びアラルキル基から選択され且つ炭素数が１〜１８である］で表されるシランカップリング剤（Ｃ）とを含むゴム組成物を用いたことを特徴とする。 That is, the tire of the present invention has the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. And L represents a neutral Lewis base, and w represents an integer of 0 to 3), and the following general formula (II):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ^′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and the following general formula (III ):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating Obtained by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of a half metallocene cation complex represented by An aromatic vinyl compound-conjugated diene compound copolymer (A) having a cis-1,4 bond amount of 80% or more in the conjugated diene compound portion;
Silica (B),
The following formula (V):
R ¹ _x R ² _y R ³ _z Si—R ⁴ —S—CO—R ⁵ (V)
[Wherein, R ¹ represents R ⁶ O—, R ⁶ C (═O) O—, R ⁶ R ⁷ C═NO—, R ⁶ R ⁷ NO—, R ⁶ R ⁷ N— and — (OSiR ⁶ R ⁷ ) _n (OSiR ⁵ R ⁶ R ⁷ ) and having 1 to 18 carbon atoms (provided that R ⁶ and R ⁷ are each independently an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group). Selected from a group and an aryl group and having 1 to 18 carbon atoms and n being 0 to 10);
R ² is selected from hydrogen or an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group;
R ³ is a — [O (R ⁸ O) _m ] _0.5 — group (where R ⁸ is selected from an alkylene group and a cycloalkylene group and has 1 to 18 carbon atoms, and m is 1 to 4). );
x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, 0 ≦ z ≦ 1;
R ⁴ is selected from an alkylene group, a cycloalkylene group, a cycloalkylalkylene group, an alkenylene group, an arylene group, and an aralkylene group, and has 1 to 18 carbon atoms;
R ⁵ is selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group, and has a carbon number of 1 to 18, and a silane coupling agent (C) represented by A rubber composition is used.

In the aromatic vinyl compound-conjugated diene compound copolymer (A), the vinyl bond amount of the conjugated diene compound portion may be 10% or less, and the block amount in the NMR measurement of the repeating unit of the aromatic vinyl compound portion However, it may be 10% or less of the total aromatic vinyl compound portion.
In the DSC measurement of the aromatic vinyl compound-conjugated diene compound copolymer (A), it is desirable to have a melting point (Tm).
Further, the aromatic vinyl compound-conjugated diene compound copolymer (A) may be a styrene-butadiene copolymer.

The aromatic vinyl compound-conjugated diene compound copolymer (A) is a metallocene complex represented by the general formula (I) and the general formula (II), and a half metallocene cation represented by the general formula (III). It is desirable to obtain it by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of complexes.
The tire of the present invention is preferably a tire using the rubber composition as a tread.

  According to the present invention, by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing a specific metallocene complex, the microstructure of the conjugated diene compound portion is 80% or higher. , 4 Bond Aromatic Vinyl Compound-Conjugated Diene Compound Copolymer, Silica, and Rubber Composition Using Specific Structure Silane Coupling Agent A tire having excellent properties can be realized.

Hereinafter, the present invention will be described in detail.
The tire of the present invention is at least one selected from the group consisting of the metallocene complexes represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III). Aromatic vinyl compound obtained by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing a complex of which the cis-1,4 bond content of the conjugated diene compound portion is 80% or more A rubber composition containing a conjugated diene compound copolymer (A), silica (B), and a silane coupling agent (C) represented by the above formula (V) is used.

[Aromatic vinyl compound-conjugated diene compound copolymer (A)]
The aromatic vinyl compound-conjugated diene compound copolymer (A) used in the present invention has a very high cis-1,4 bond amount in the conjugated diene compound portion, and the aromatic vinyl compound-conjugated diene compound copolymer ( A rubber composition using A) as a rubber component includes a rubber composition using a conventional aromatic vinyl compound-conjugated diene compound copolymer obtained by anionic polymerization, and a conventional aromatic vinyl compound-conjugated diene. Abrasion resistance while maintaining high wet skid resistance compared to rubber compositions using a blend of a compound copolymer and a homopolymer of a conjugated diene compound having a high cis-1,4 bond content. Can be improved. The reason for this is not necessarily clear, but it seems to be due to the effect of improving the wear resistance due to the crystallinity derived from the amount of cis-1,4 bonds in the conjugated diene compound portion. Here, the amount of cis-1,4 bonds in the conjugated diene compound portion needs to be 80% or more, and preferably 90% or more. When the amount of cis-1,4 bonds in the conjugated diene compound portion is less than 80%, the cis chain is insufficient, so the melting point (Tm) is not measured, and the wear resistance decreases. The amount of cis-1,4 bonds in the conjugated diene compound portion can be determined from the integration ratio of ¹ H-NMR spectrum and ¹³ C-NMR spectrum, and the specific method is disclosed in JP-A-2004-27179. It is disclosed.

  In the aromatic vinyl compound-conjugated diene compound copolymer (A), the vinyl bond content in the conjugated diene compound portion is preferably 10% or less, and more preferably 5% or less. When the vinyl bond amount in the conjugated diene compound portion exceeds 10%, the cis-1,4 bond amount is lowered and the effect of improving the wear resistance cannot be sufficiently obtained.

  The aromatic vinyl compound-conjugated diene compound copolymer (A) is not particularly limited except that a polymerization catalyst composition described in detail later is used. For example, an addition polymer using a normal coordination ion polymerization catalyst. In the same manner as in the above production method, it can be obtained by copolymerizing a mixture of a monomeric aromatic vinyl compound and a conjugated diene compound. As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. When a solvent is used for the polymerization reaction, the solvent used may be inactive in the polymerization reaction, and the amount of the solvent used is arbitrary, but the concentration of the complex contained in the polymerization catalyst composition is 0.1 to 0.0001 mol. The amount is preferably / l. Here, examples of the aromatic vinyl compound include styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, α-methylstyrene, chloromethylstyrene, vinyltoluene and the like. Among these, styrene Is preferred. On the other hand, examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene is preferable. Therefore, a styrene-butadiene copolymer is particularly preferable as the aromatic vinyl compound-conjugated diene compound copolymer (A).

  The polymerization catalyst composition used for the synthesis of the aromatic vinyl compound-conjugated diene compound copolymer (A) includes a metallocene complex represented by the general formulas (I) and (II), and the general formula (III). It is necessary to include at least one complex selected from the group consisting of a half metallocene cation complex represented by the formula (1), and other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter It is preferable to contain.

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl, 2-methylindenyl and the like. In addition, two Cp ^R in the general formula (I) and the formula (II) may be the same or different from each other.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。） In the half metallocene cation complex represented by the above general formula (III), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. Moreover, it is preferable that R is respectively independently a hydrocarbyl group; metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton include the following.

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)

In the general formula (III), Cp ^{R ′} having the indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I), and preferred examples thereof are also the same.

In the general formula (III), Cp ^{R ′} having the fluorenyl ring as a basic skeleton can be represented by C ₁₃ H _9-X R _X or C ₁₃ H _17-X R _X. Here, X is an integer of 0-9 or 0-17. Moreover, it is preferable that R is respectively independently a hydrocarbyl group; metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.

  The central metal M in the general formula (I), formula (II) and formula (III) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) contains a bistrialkylsilylamide ligand [—N (SiR ₃ ) ₂ ]. The alkyl groups R (R ^{a to} R ^f in the general formula (I)) contained in the bistrialkylsilylamide are each independently an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group.

The metallocene complex represented by the general formula (II) contains a silyl ligand [—SiX ^′ ₃ ]. X ^′ contained in the silyl ligand [—SiX ^′ ₃ ] is a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.

  In the general formula (III), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. Here, examples of the alkoxide group include aliphatic alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group; phenoxy group and 2,6-di- -tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thio sec-butoxy group, a thio tert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group is preferable.

  In the general formula (III), the amide group represented by X includes aliphatic amide groups such as dimethylamide group, diethylamide group and diisopropylamide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamide groups such as 6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide group is preferable.

  In the general formula (III), examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like. Among these, a tris (trimethylsilyl) silyl group is preferable.

  In the general formula (III), the halogen atom represented by X may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Others: Examples include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.

  In the general formula (III), X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion. Specific examples of the tetravalent boron anion include tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaoundecaborate is exemplified, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The metallocene complex represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) are further 0 to 3, preferably 0 to 1 neutral. Contains Lewis base L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Further, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may exist as a body or higher multimer.

（式中、Ｘ^’’はハライドを示す。） The metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. The reaction examples for obtaining the metallocene complex represented by the general formula (I) are shown below.

(In the formula, X ^″ represents a halide.)

（式中、Ｘ^’’はハライドを示す。） The metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, scandium trishalide or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and a silyl salt (for example, potassium). Salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. The reaction examples for obtaining the metallocene complex represented by the general formula (II) are shown below.

(In the formula, X ^″ represents a halide.)

The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

Here, in the compound represented by the general formula (IV), M represents a lanthanoid element, scandium or yttrium, and Cp ^{R ′} independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents 0 to 3 Indicates an integer. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

Examples of the cation represented by [A] ⁺ include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation. Examples of the tri (substituted phenyl) carbonyl cation include tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used in the above reaction is a compound selected and combined from the above non-coordinating anions and cations, and is an N, N-dimethylaniline. Nitrotetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. In general formula [A] ⁺ [B] ^- ionic compounds represented by is preferably added from 0.1 to 10 mol per mol of the metallocene complex, more preferably it added about 1 molar. When the half metallocene cation complex represented by the general formula (III) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) and the general formula used in the reaction [a] ⁺ [B] ^- provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this. Further, by using a combination of a metallocene complex represented by the general formula (I) or the formula (II) and an ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A half metallocene cation complex represented by the formula (III) can also be formed.

  The structures of the metallocene complexes represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) are preferably determined by X-ray structural analysis.

  The co-catalyst that can be used in the polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst for a polymerization catalyst composition containing a normal metallocene complex. Suitable examples of the cocatalyst include aluminoxanes, organoaluminum compounds, and the above ionic compounds. These promoters may be used alone or in combination of two or more.

  The aluminoxane is preferably an alkylaluminoxane, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The content of aluminoxane in the polymerization catalyst composition is such that the element ratio Al / M between the central metal M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable.

  On the other hand, examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, the content of the organoaluminum compound in the polymerization catalyst composition is preferably 1 to 50 times mol, more preferably about 10 times mol for the metallocene complex.

  Furthermore, in the polymerization catalyst composition, each of the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) is used as an appropriate promoter. By combining them, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.

  The method for producing the aromatic vinyl compound-conjugated diene compound copolymer (A) used in the present invention includes the metallocene complex represented by the general formula (I) and the general formula (II), and the general formula (III). It can be obtained by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of represented half metallocene cation complexes. Moreover, it can be the same as that of the manufacturing method of the addition polymer by the addition polymerization reaction using the conventional coordination ion polymerization catalyst except using the polymerization catalyst composition mentioned above as a polymerization catalyst. Here, for example, (1) a component of the polymerization catalyst composition is separately provided in a polymerization reaction system containing an aromatic vinyl compound and a conjugated diene compound as monomers, and the polymerization catalyst composition is provided in the reaction system. (2) A polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition has the preferable range of 1 / 10000-1 / 100 times mole with respect to a monomer.

  Further, the number average molecular weight (Mn) of the obtained copolymer is not particularly limited, and the problem of lowering the molecular weight does not occur. Furthermore, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 3 or less, and more preferably 2 or less. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

  The addition polymerization reaction is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas.

  The polymerization temperature of the addition polymerization reaction is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. When the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. On the other hand, the reaction time of the above addition polymerization reaction is not particularly limited, and is preferably in the range of, for example, 1 second to 10 days, but may be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature. Can do.

In the aromatic vinyl compound-conjugated diene compound copolymer (A), the amount of blocks in the NMR measurement of the repeating unit of the aromatic vinyl compound portion is 10% or less of the total aromatic vinyl compound portion. Preferably, it is 7% or less, more preferably 0%. The copolymer obtained using the polymerization catalyst composition tends to polymerize the aromatic vinyl compound at random, and can block the aromatic vinyl compound. Here, the term “random” means that the amount of block in the NMR measurement of the repeating unit of the aromatic vinyl compound portion (hereinafter sometimes referred to as the block aromatic vinyl compound content) is 10% or less of the total aromatic vinyl compound portion. The block refers to an aromatic vinyl compound portion having an aromatic vinyl compound-aromatic vinyl compound bond. If the block aromatic vinyl compound content exceeds 10%, the behavior of the aromatic vinyl compound as a homopolymer appears, the glass transition temperature increases, and the wear resistance may decrease. In addition, a block aromatic vinyl compound content rate can be calculated | required from the integral ratio of a < ¹ > H-NMR spectrum.

  Further, the aromatic vinyl compound-conjugated diene compound copolymer (A) exhibits a melting point (Tm) in DSC measurement (differential scanning calorimetry). Here, the melting point (Tm) in DSC measurement refers to the melting point of a static crystal derived from a chain of conjugated diene compound portions.

[Silica (B)]
The rubber composition used in the present invention uses the above aromatic vinyl compound-conjugated diene compound copolymer (A) as a rubber component, and further contains silica (B). Here, the blending amount of silica (B) is not particularly limited, but is 10 to 200 parts by weight, preferably 100 parts by weight with respect to 100 parts by weight of the aromatic vinyl compound-conjugated diene compound copolymer (A). A range of 80 to 140 parts by mass is desirable. When the blending amount of silica (B) is less than 10 parts by mass, sufficient reinforcement may not be obtained, and when it exceeds 200 parts by mass, workability and wear resistance may be reduced. Here, as silica (B), wet silica and dry silica are preferable, and wet silica is more preferable. These silica (B) may be used individually by 1 type, and may mix and use 2 or more types.

[Silane coupling agent (C)]
The rubber composition used in the present invention further contains a silane coupling agent (C). The silica coupling agent (C) is represented by the above formula (V). In the above formula (V), R ¹ represents R ⁶ O—, R ⁶ C (═O) O—, R ⁶ R ⁷ C═NO—, R ⁶ R ⁷ NO—, R ⁶ R ⁷ N— and — (OSiR ⁶ R ⁷ ) _n (OSiR ⁵ R ⁶ R ⁷ ) and having 1 to 18 carbon atoms (provided that R ⁶ and R ⁷ are each independently an alkyl group, a cycloalkyl group, or an alkenyl group) R ² is selected from hydrogen, or an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, and an alkenyl group, selected from a cycloalkenyl group and an aryl group, and having 1 to 18 carbon atoms and n is 0 to 10); R ³ is a — [O (R ⁸ O) _m ] _0.5 — group (wherein R ⁸ is selected from an alkylene group and a cycloalkylene group and has 1 carbon atom). X + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, 0 ≦. It is ≦ 1; R ⁴ is an alkylene group, a cycloalkylene group, cycloalkylalkylene group, alkenylene group, and is selected from arylene groups and aralkylene group having a carbon number 1 to 18; R ⁵ is an alkyl group, a cycloalkyl It is selected from an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group, and has 1 to 18 carbon atoms.

In R ² , R ⁵ , R ⁶ and R ⁷ , the alkyl group may be linear or branched, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The alkenyl group may be linear or branched, and examples of the alkenyl group include a vinyl group, an allyl group, and a methanyl group. Furthermore, examples of the cycloalkyl group include a cyclohexyl group and an ethylcyclohexyl group, examples of the cycloalkenyl group include a cyclohexenyl group and an ethylcyclohexenyl group, and examples of the aryl group include a phenyl group and a tolyl group. Furthermore, in R ⁵ , examples of the aralkyl group include a phenethyl group.

In R ⁴ and R ⁸ , the alkylene group may be linear or branched, and examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Examples of the cycloalkylene group include a cyclohexylene group. Furthermore, in R ⁴ , the alkenylene group may be linear or branched, and examples of the alkenylene group include a vinylene group and a propenylene group. Examples of the cycloalkylalkylene group include a cyclohexylmethylene group, examples of the arylene group include a phenylene group, and examples of the aralkylene group include a xylylene group.

In the above R ³ , the — [O (R ⁸ O) _m ] _0.5 — group is 1,2-ethanedioxy group, 1,3-propanedioxy group, 1,4-butanedioxy group, 1,5-pentane. Dioxy group, 1,6-hexanedioxy group, etc.

The silane coupling agent (C) of the above formula (V) can be synthesized by the method described in JP-T-2001-505225, and the product name “NXT” (formula of Momentive Performance Materials) R ¹ = C ₂ H ₅ O of ^{(V), R 4 = C} 3 H 6, R 5 = C 7 H 15, x = 3, y = 0, z = 0: 3- octanoylthio - propyltriethoxysilane) Commercial products such as these can also be used.

  In addition, the compounding quantity of the said silane coupling agent (C) is 1-20 mass% of the compounding quantity of the said silica (B), It is desirable that it is the range of 5-25 mass% preferably. If the blending amount of the silane coupling agent (C) is less than 1% by mass of the blending amount of silica (B), the low heat buildup and workability of the rubber composition may be deteriorated, while exceeding 20% by mass. In such a case, the low heat generation property cannot be further improved, and the cost may increase.

[Rubber composition]
The rubber composition used in the present invention contains the above aromatic vinyl compound-conjugated diene compound copolymer (A) as a rubber component, and may further contain other rubber components. Examples of the rubber component include natural rubber (NR) or synthetic diene rubbers other than the aromatic vinyl compound-conjugated diene compound copolymer (A). Specific examples of the synthetic diene rubber include Isoprene rubber (IR), polybutadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), halogenated butyl rubber, acrylonitrile-butadiene rubber (NBR) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types. When these other rubber components are used, the aromatic vinyl compound-conjugated diene compound copolymer (A) is 10 to 90% by mass or more, preferably 30 to 70% by mass in 100% by mass of the total rubber component. It is desirable that When the aromatic vinyl compound-conjugated diene compound copolymer (A) in the rubber component total amount of 100% by mass is within the above range, the tire has excellent wear resistance and wet resistance while maintaining better workability. It is possible to impart skid properties.

  In addition to the aromatic vinyl compound-conjugated diene compound copolymer (A), silica (B), and silane coupling agent (C), the rubber composition used in the present invention is usually used in the rubber industry. Compounding agents such as carbon black, fillers, softeners, stearic acid, anti-aging agents, zinc white, vulcanization accelerators, vulcanizing agents, etc. are appropriately selected within a range that does not impair the object of the present invention. Can be blended. As these compounding agents, commercially available products can be suitably used. The rubber composition is prepared by blending an aromatic vinyl compound-conjugated diene compound copolymer (A) with silica (B) and a silane coupling agent (C) and various compounding agents appropriately selected as necessary. Then, it can be produced by kneading, heating, extruding or the like.

[tire]
The tire of the present invention is characterized by using the rubber composition, and the rubber composition is preferably used for a tread. A tire using the rubber composition as a tread is excellent in wear resistance and wet skid resistance. The tire of the present invention is not particularly limited except that the rubber composition described above is used for any of the tire members, and can be produced according to a conventional method. Moreover, as gas with which this tire is filled, inert gas, such as nitrogen, argon, helium other than normal or the air which adjusted oxygen partial pressure, can be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

First, in Production Examples 3 to 4, a commonly used half metallocene cation complex represented by the general formula (III) was synthesized, and its structure was confirmed by ¹ H-NMR and X-ray crystal structure analysis. ¹ H-NMR was measured at room temperature using THF-d8 as a solvent. X-ray crystal structure analysis was performed using RAXIS CS (Rigaku).

<Synthesis Example of [(2-MeC ₉ H ₆ ) GdN (SiMe ₃ ) ₂ (THF) ₃ ] [B (C ₆ F ₅ ) ₄ ]>
Under a nitrogen atmosphere, triethylanilinium tetrakisphenylborate (Et ₃ NHB (C ₆ H ₆ ) ₄ ) was added to 5 mL of a solution of (2-MeC ₉ H ₆ ) ₂ GdN (SiMe ₃ ) ₂ (0.150 g, 0.260 mmol) in THF. (0.110 g, 0.260 mmol) was added and stirred at room temperature for 12 hours. Thereafter, THF was distilled off under reduced pressure, and the resulting residue was washed three times with hexane to obtain an oily compound. The residue was recrystallized with a THF / hexane mixed solvent to produce [(2-MeC ₉ H ₆ ) GdN (SiMe ₃ ) ₂ (THF) ₃ ] [B (C ₆ F ₅ ) ₄ ] (150 mg as white crystals). 59%). The structure was confirmed by X-ray crystal analysis.

[Production Example 1: Production of polymer C]
In a glove box under a nitrogen atmosphere, in a well-dried 30 ml pressure-resistant glass bottle, dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) samarium [(Cp ^* ) ₂ Sm (μ-Me) ₂ AlMe ₂ ] (Cp ^* : pentamethylcyclopentadienyl ligand) was charged in an amount of 0.03 mmol and dissolved in 1 ml of toluene. Subsequently, 0.09 mmol of triisobutylaluminum and 0.03 mmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) were added and the bottle was stoppered. Thereafter, the bottle was taken out from the glove box, charged with 0.49 g of 1,3-butadiene and 2.4 ml of styrene, and polymerized at 50 ° C. for 12 hours. After polymerization, the reaction was stopped by adding 10 ml of a 10 mass% methanol solution of 2,6-bis (t-butyl) -4-methylphenol (BHT), and the polymer was separated with a large amount of methanol / hydrochloric acid mixed solvent. And dried in vacuum at 60 ° C. The yield of the obtained polymer C was 20% by mass.

[Production Example 2: Production of polymer D]
A polymer D was obtained in the same manner as in Production Example 1, except that 0.65 g of 1,3-butadiene and 2.0 ml of styrene were charged and polymerization was performed at 50 ° C. for 6 hours. The yield of the obtained polymer D was 20% by mass.

[Production Example 3: Production of polymer E]
In a glove box under a nitrogen atmosphere, 104 g (1 mol) of styrene and 50 g of toluene were added to a well-dried 1 L pressure-resistant glass bottle, and the bottle was stoppered. Thereafter, the bottle was taken out from the glove box, and 54 g (1 mol) of 1,3-butadiene was charged to obtain a monomer solution. On the other hand, in a glove box under a nitrogen atmosphere, 40 μmol of bis (2-methylindenyl) gadolinium (trimethylsilylamide) [(2-MeC ₉ H ₆ ) ₂ GdN (SiMe ₃ ) ₂ ] was added to a glass container. ₄₀ μmol of phenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) and 1 mmol of diisobutylaluminum halide were charged and dissolved in 10 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, added to the monomer solution, and polymerized at 70 ° C. for 30 minutes. After the polymerization, the reaction was stopped by adding 10 ml of a 10 mass% methanol solution of 2,6-bis (t-butyl) -4-methylphenol (BHT), and the polymer was separated with a large amount of methanol / hydrochloric acid mixed solvent. And dried in vacuum at 60 ° C. The yield of the obtained polymer E was 47 g.

[Production Example 4: Production of polymer F]
Polymerization was carried out in the same manner as in Production Example 3, except that the amount of diisobutylaluminum halide used in the catalyst solution was 0.8 mmol. The yield of the obtained polymer F was 46 g.

  Number average molecular weight (Mn), molecular weight distribution (Mw / Mn), microstructure, bound styrene content, block styrene content for polymers A to B used in comparative examples and polymers C to F produced as described above The rate, glass transition point (Tg), and melting point (Tm) were measured by the following methods. The results are shown in Table 1.

(1) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: Tosoh HLC-8020, column: Tosoh GMH-XL (two in series), detector: differential refractometer (RI)], based on monodisperse polystyrene, The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) in terms of polystyrene were determined.

(2) Microstructure and amount of bound styrene The microstructure of the polymer was determined from the integration ratio of ¹ H-NMR spectrum and ¹³ C-NMR spectrum, and the amount of bound styrene of the polymer was determined from the integration ratio of ¹ H-NMR spectrum. . ¹ H-NMR and ¹³ C-NMR were measured at 120 ° C. using 1,1,2,2-tetrachloroethane as a solvent.

(3) Block Styrene Content The ratio of the block amount (block styrene content) in the NMR measurement of the repeating unit of the styrene portion to the total styrene portion was determined from the integration ratio of the ¹ H-NMR spectrum.

(4) Glass transition point (Tg) (° C) and melting point (Tm) (° C)
After weighing 10mg ± 0.5mg of sample, putting it in an aluminum measuring pan and covering it with a DSC device (TA Instruments) from room temperature to 50 ° C and stabilizing for 10 minutes The glass transition point (Tg) and the melting point (Tm) were measured while the temperature was raised to 50 ° C. at a rate of temperature increase of 10 ° C./min.

  From the detailed NMR data of the sample, no styrene-styrene bond was particularly confirmed.

* 1: Polybutadiene, manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: NF35
* 2: Styrene-butadiene copolymer, manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Toughden 1000

  Next, using the polymers A to F, rubber compositions having the compounding recipes shown in Tables 2 to 3 are prepared, and the vulcanized rubber obtained by vulcanization under normal conditions is used. Wet skid resistance and abrasion resistance were measured by the following methods. The results are shown in Tables 2-3.

(5) Abrasion resistance The amount of abrasion was measured at room temperature using a Ramborn abrasion tester, the reciprocal of the amount of abrasion was calculated, and the index was displayed with Comparative Example 1 as 100. The larger the index value, the smaller the amount of wear and the better the wear resistance.

(6) Wet skid resistance Using a BPST (British Portable Skid Resistance Tester), the wet skid resistance of the rubber composition on a wet road surface was measured. It shows that wet skid resistance is so favorable that an index value is large.

* 3: N220, manufactured by Tokai Carbon Co., Ltd. “Seast 6”
* 4: “VN3” manufactured by Tosoh Silica Corporation
* 5: Trade name “Si75” manufactured by Evonik Degussa
* 6: Product name “NXT”, manufactured by Momentive Performance Materials
※ 7: Ouchi Shinko Chemical Industrial Co., Ltd., "NOCCELER 6C", N-(1,3-dimethylbutyl) -N ^'- phenyl -p- phenylenediamine ※ 8: Ouchi Shinko Chemical Industrial Co., Ltd., "Nocceler D ”, Diphenylguanidine * 9: Ouchi Shinsei Chemical Industry Co., Ltd.,“ Noxeller CZ ”, N-cyclohexyl-2-benzothiazylsulfenamide * 10: Ouchi Shinsei Chemical Industries Co., Ltd.“ Noxeller DM ”, Di- 2-Benzothiazolyl disulfide

  Implementation using a rubber composition containing all of the polymer E or F corresponding to the aromatic vinyl compound-conjugated diene compound copolymer (A), silica (B), and a silane coupling agent (C) having a specific structure It can be seen that Examples 1 and 2 exhibit extremely superior wet skid resistance and wear resistance as compared with Comparative Examples 1 to 10.

Claims (7)

The following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. And L represents a neutral Lewis base, and w represents an integer of 0 to 3), and the following general formula (II):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ^′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and the following general formula (III ):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating Obtained by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of a half metallocene cation complex represented by An aromatic vinyl compound-conjugated diene compound copolymer (A) having a cis-1,4 bond amount of 80% or more in the conjugated diene compound portion;
Silica (B),
The following formula (V):
R ¹ _x R ² _y R ³ _z Si—R ⁴ —S—CO—R ⁵ (V)
[Wherein, R ¹ represents R ⁶ O—, R ⁶ C (═O) O—, R ⁶ R ⁷ C═NO—, R ⁶ R ⁷ NO—, R ⁶ R ⁷ N— and — (OSiR ⁶ R ⁷ ) _n (OSiR ⁵ R ⁶ R ⁷ ) and having 1 to 18 carbon atoms (provided that R ⁶ and R ⁷ are each independently an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group). Selected from a group and an aryl group and having 1 to 18 carbon atoms and n being 0 to 10);
R ² is selected from hydrogen or an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group;
R ³ is a — [O (R ⁸ O) _m ] _0.5 — group (where R ⁸ is selected from an alkylene group and a cycloalkylene group and has 1 to 18 carbon atoms, and m is 1 to 4). );
x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, 0 ≦ z ≦ 1;
R ⁴ is selected from an alkylene group, a cycloalkylene group, a cycloalkylalkylene group, an alkenylene group, an arylene group, and an aralkylene group, and has 1 to 18 carbon atoms;
R ⁵ is selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group, and has a carbon number of 1 to 18, and a silane coupling agent (C) represented by A tire characterized by using a rubber composition.   2. The tire according to claim 1, wherein in the aromatic vinyl compound-conjugated diene compound copolymer (A), the vinyl bond content of the conjugated diene compound portion is 10% or less.   The aromatic vinyl compound-conjugated diene compound copolymer (A) is characterized in that the block amount in the NMR measurement of the repeating unit of the aromatic vinyl compound portion is 10% or less of the total aromatic vinyl compound portion. The tire according to claim 1.   The tire according to claim 1, which has a melting point (Tm) in DSC measurement of the aromatic vinyl compound-conjugated diene compound copolymer (A).   The tire according to any one of claims 1 to 4, wherein the aromatic vinyl compound-conjugated diene compound copolymer (A) is a styrene-butadiene copolymer.   The aromatic vinyl compound-conjugated diene compound copolymer (A) is a metallocene complex represented by the general formula (I) and the general formula (II), and a half metallocene cation represented by the general formula (III). 6. The method according to any one of claims 1 to 5, which is obtained by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of complexes. The tire described in Crab.   The tire according to any one of claims 1 to 6, wherein the rubber composition is used for a tread.