JP2010260920A - Tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tire using as a tread a rubber composition satisfying all of low heat build-up, abrasion resistance and wet grip performance, preventing the generation of a volatile organic compound (VOC) under operation, and having good processability. <P>SOLUTION: The tire obtained by using as the tread the rubber composition comprising (A) a rubber component containing ≥10 mass% of a modified conjugated diene polymer having a silanol group, and a functional group present at the vicinity of the silanol group and promoting the reaction of the silanol group with a reinforcing filler at the molecular terminals of the conjugated diene polymer, (B) the reinforcing filler at least containing silica, and (C) a silane coupling agent of 1-25 pts.mass based on 100 pts.mass of the rubber component (A). At least one selected from compounds (c-1), (c-2), (c-3), (c-4) and (c-5) having specific structures is used as the silane coupling agent (C). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention includes a specific modified conjugated diene polymer, a reinforcing filler containing at least silica, and a specific silane coupling agent, and particularly prevents the generation of volatile organic compounds (VOC) during operation. The present invention relates to a tire having a low heat build-up, wear resistance, and wet grip performance, wherein a rubber composition having good processability is used for a tire tread.

2. Description of the Related Art In recent years, with the reduction in fuel consumption of tires, a rubber composition having low heat generation has been demanded for tire rubber members. In order to obtain a rubber composition with low exothermicity, development of a polymer having a functional group that interacts with a filler such as silica or carbon black has been progressing. For example, a modified polymer having an alkoxysilyl group is Known (for example, see Patent Documents 1 and 2).
However, in these techniques, a rubber composition having low heat build-up (suppressing tan δ) can be obtained by using a modified polymer. However, a volatile organic compound (VOC) is generated during the operation, and as a result Further, since bubbles are generated in the rubber composition, there has been a problem that processability is lowered.

Further, in recent years, there has been a demand for a rubber composition having lower heat build-up, and a rubber composition that can maintain heat resistance as usual.
On the other hand, in recent years, with increasing interest in safety of automobiles, there has been a demand not only for low fuel consumption performance and wear resistance, but also for wet grip performance (operation stability on wet road surfaces).
As a method of obtaining a rubber composition that gives tires such good fuel economy and good wet performance at the same time, silica is used instead of carbon black, which is a reinforcing filler generally used so far. Although the method has already been performed, there is a problem that wear resistance is lowered by using silica instead of carbon black.

Japanese Examined Patent Publication No. 6-57767 WO2003 / 029299 pamphlet

  The present invention has been made under such circumstances, and can satisfy low heat build-up, wear resistance, and wet grip performance, and can prevent generation of volatile organic compounds (VOC) during operation. An object of the present invention is to provide a tire using a rubber composition having good processability as a tread.

  As a result of intensive research to achieve the above object, the present inventors have found that in the molecule, a silanol group having an interaction with a filler such as silica or carbon black, and a primary amino group, for example, The object is achieved by using a rubber composition containing a rubber component containing a modified conjugated diene polymer having a certain ratio or more, a reinforcing filler containing at least silica, and a silane coupling agent having a specific structure. I found out that I could do it. The present invention has been completed based on such findings.

That is, the present invention
[1] (A) a silanol group and a functional group in the vicinity of the silanol group at the molecular end of the conjugated diene polymer, the functional group promoting the reaction between the silanol group and the reinforcing filler; A rubber component containing 10% by mass or more of a modified conjugated diene-based polymer having: (B) a reinforcing filler containing at least silica; and (A) 100 parts by mass of the rubber component, (C) silane coupling A tire using a rubber composition containing 1 to 25 parts by mass of an agent for a tread,
The (C) silane coupling agent is (c-1) a compound represented by the following general formula (1), (c-2) a compound represented by the following general formula (2), (c-3) A compound represented by the general formula (3), (c-4) a compound represented by the following general formula (4), and (c-5) a compound represented by the following general formula (5). A tire characterized by being at least one compound;

［式中、Ｒ¹⁵は−Ｃｌ、−Ｂｒ、Ｒ²⁰Ｏ−、Ｒ²⁰Ｃ(＝Ｏ)Ｏ−、Ｒ²⁰Ｒ²¹Ｃ＝ＮＯ−、Ｒ²⁰Ｒ²¹Ｎ−又は−（ＯＳｉＲ²⁰Ｒ²¹）_m（ＯＳｉＲ¹⁹Ｒ²⁰Ｒ²¹）（ただし、Ｒ²¹及びＲ²¹は、それぞれ独立に水素原子又は炭素数１〜１８の一価の炭化水素基である。）、Ｒ¹⁶はＲ¹⁵、水素原子又は炭素数１〜１８の一価の炭化水素基、Ｒ¹⁷はＲ¹⁵、Ｒ¹⁶又は−［Ｏ（Ｒ²²Ｏ）_a］_0.5−基（ただし、Ｒ²²は炭素数１〜１８のアルキレン基、ａは１〜４の整数である。）、Ｒ¹⁸は炭素数１〜１８の二価の炭化水素基、Ｒ¹⁹は炭素数１〜１８の一価の炭化水素基を示し、ｘ、ｙ及びｚは、ｘ＋ｙ＋２ｚ＝３、０≦ｘ≦３、０≦ｙ≦２、０≦ｚ≦１の関係を満たす数である。］

[Wherein R ¹⁵ represents —Cl, —Br, R ²⁰ O—, R ²⁰ C (═O) O—, R ²⁰ R ²¹ C═NO—, R ²⁰ R ²¹ N— or — (OSiR ²⁰ R ^{21 _{) m (OSiR 19 R 20 R}} 21) ( provided that, R ²¹ and R ²¹ are each independently a hydrogen atom or a C1-18 monovalent hydrocarbon group.), R ¹⁶ is R ^15, hydrogen An atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, R ¹⁷ is R ¹⁵ , R ¹⁶ or — [O (R ²² O) _a ] _0.5 — group (where R ²² is alkylene having 1 to 18 carbon atoms) Group, a is an integer of 1 to 4), R ¹⁸ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ¹⁹ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, x, y and z are numbers satisfying the relationship of x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, and 0 ≦ z ≦ 1. ]

［式中Ｒ²³は炭素数１〜２０の直鎖もしくは、分岐、環状のアルキル基であり、Ｇはそれぞれ独立して炭素数１〜９のアルカンジイル基又はアルケンジイル基であり、Ｚ^aはそれぞれ独立して二つの珪素原子と結合することのできる基で、[−Ｏ−]_0.5、[−Ｏ−Ｇ−]_0.5又は［−Ｏ−Ｇ−Ｏ−］_0.5から選ばれる基であり、Ｚ^bはそれぞれ独立して二つの珪素原子と結合することのできる基で、［−Ｏ−Ｇ−Ｏ−］_0.5で表される官能基であり、Ｚ^cはそれぞれ独立して−Ｃｌ、−Ｂｒ、−ＯＲ²⁴、Ｒ²⁴Ｃ(＝Ｏ)Ｏ−、Ｒ²⁴Ｒ²⁵Ｃ＝ＮＯ−、Ｒ²⁴Ｒ²⁵Ｎ−，Ｒ²⁴−，ＨＯ−Ｇ−Ｏ−で表される官能基であり、Ｒ，Ｇは上記表記と一致する。
ｍ、ｎ、ｕ、ｖ、ｗはそれぞれ独立して１≦ｍ≦２０、０≦ｎ≦２０、０≦ｕ≦３、０≦ｖ≦２、０≦ｗ≦１であり、かつ１／２ｕ＋ｖ＋２ｗ＝２又は３である。
Ａ部が複数である場合、複数のＡ部におけるＺ^a _u、Ｚ^b _v及びＺ^c _wそれぞれにおいて、同一でも異なっていてもよく、Ｂが複数である場合、複数のＢ部におけるＺ^a _u、Ｚ^b _v及びＺ^c _wそれぞれにおいて、同一でも異なってもよい。］

[Wherein R ²³ is or straight chain having 1 to 20 carbon atoms, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a are each independently a group capable of binding with two silicon _{atoms, [- O-] 0.5, [} - O-G-] is a group selected from _0.5, or _{[-O-G-O-] 0.5} , Z ^b is a group that can independently bond to two silicon atoms, and is a functional group represented by [—O—G—O—] _0.5 ; Z ^c is independently —Cl, —Br; ^{, -OR 24, R 24 C (} = O) O-, R 24 R 25 C = NO-, R 24 R 25 N-, R 24 -, a functional group represented by HO-G-O-, R and G coincide with the above notation.
m, n, u, v, and w are independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, and 1 / 2u + v + 2w = 2 or 3.
When there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, Z ^a _u in the plurality of B parts , Z ^b _v and Z ^c _w may be the same or different. ]

R ^1a R ^2a R ^3a Si-R ^4a -SH (3)
[Wherein, R ^1a represents a methyl group or an ethyl group, R ^2a represents a methoxy group, an ethoxy group, or —O— (YO) _m —X, Y represents a divalent hydrocarbon group, and X represents a carbon number of 1 -15 alkyl groups, m is a number from 1-40. R ^3a represents a methyl group, an ethyl group or R ^2a , and R ^4a represents a divalent hydrocarbon group having 1 to 12 carbon atoms. ]

_{^{(R 31 O) 3-p}} (R 32) p Si-R 33 -S m -R 34 -S m -R 33 -Si (R 32) p (OR 31) 3-p ··· (4)
[R ³¹ and R ³² are each a hydrocarbon group having 1 to 4 carbon atoms, R ³³ is a divalent hydrocarbon group having 1 to 15 carbon atoms, p is an integer of 0 to 2, m is an average value of 1 or more and 4 below, R ³⁴ is ^{-S-R 35 -S -, -} R 36 -S x -R 37 -, or ^{_{-R 38 -S y -R 39 -S z}} -R 40 - (R 35 ~R 40 carbon A divalent hydrocarbon group of 1 to 20 or a divalent organic group containing a hetero element other than S and O, which may be the same or different, and x, y, and z are average values, respectively. 1 or more and less than 4.]

［式中、Ｒ⁴¹は炭素数１〜４のアルキル基又は炭素数２〜８のアルコキシアルキル基を示し、Ｒ⁴²及びＲ⁴³は、それぞれ独立に、炭素数１〜６のアルキル基又はフェニル基、あるいはその一つがＲ⁴¹Ｏを示し、各Ｒ⁴¹Ｏは同一でも異なっていてもよく、ｘは３〜５の数である。］
［２］（Ｂ）補強性充填材中のシリカ含有量が２０質量％以上である、上記［１］に記載のタイヤ、
［３］（Ａ）ゴム成分１００質量部に対し、シリカを１０〜１５０質量部の割合で含む、上記［２］に記載のタイヤ、
［４］変性共役ジエン系重合体が、下記一般式（６）又は（７）により表される構造を有する、請求項１〜３のいずれかに記載のタイヤ

[Wherein, R ⁴¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms, and R ⁴² and R ⁴³ each independently represents an alkyl group or phenyl group having 1 to 6 carbon atoms. Or one of them represents R ⁴¹ O, each R ⁴¹ O may be the same or different, and x is a number from 3 to 5. ]
[2] The tire according to [1] above, wherein the silica content in the reinforcing filler (B) is 20% by mass or more.
[3] (A) The tire according to [2], including silica in a proportion of 10 to 150 parts by mass with respect to 100 parts by mass of the rubber component.
[4] The tire according to any one of claims 1 to 3, wherein the modified conjugated diene polymer has a structure represented by the following general formula (6) or (7).

［式中、Ｒ¹は単結合又は炭素数１〜２０の二価の炭化水素基；Ｒ²及びＲ³はそれぞれ独立に水素原子又は炭素数１〜２０の一価の炭化水素基；Ａ³は単結合、炭素数１〜２０の炭化水素基又はシラノール基と補強性充填材との反応を促進する官能基であり、ｍは１〜１０の整数である］

[Wherein, R ¹ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms; R ² and R ³ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; A ³ Is a functional group that promotes the reaction between a single bond, a hydrocarbon group having 1 to 20 carbon atoms or a silanol group and the reinforcing filler, and m is an integer of 1 to 10.]

［式中、Ｒ⁴は単結合又は炭素数１〜２０の炭化水素基；Ｒ⁵及びＲ⁶はそれぞれ独立に単結合、水素原子又は炭素数１〜２０の炭化水素基；Ａ⁴は単結合、炭素数１〜２０の炭化水素基又はシラノール基と補強性充填材との反応を促進する官能基；Ｂ及びＤはそれぞれ独立にシラノール基と補強性充填材との反応を促進する官能基を少なくとも一つ含む基であり；ｐ及びｑはそれぞれ独立に０〜５の整数であり、（ｐ＋ｑ）が１以上であり、ｎは１〜１０の整数である］
［５］一般式（６）又は一般式（７）において、前記シラノール基と補強性充填材との反応を促進する官能基Ａ³及びＡ⁴が、それぞれ独立に（チオ）エーテル結合、（チオ）ウレタン結合、イミノ結合及びアミド結合の中から選ばれる少なくとも一種の結合を有する二価の官能基、並びにニトリル基、ピリジル基、Ｎ−アルキルピロリドニル基、Ｎ−アルキルイミダゾリル基、Ｎ−アルキルピラゾリル基、（チオ）ケトン基、（チオ）アルデヒド基、イソシアヌル酸トリエステル残基、炭素数１〜２０の（チオ）カルボン酸ヒドロカルビルエステル残基、炭素数１〜２０の（チオ）カルボン酸金属塩の残基、炭素数１〜２０のカルボン酸無水物残基、炭素数１〜２０のカルボン酸ハロゲン化物残基及び炭酸ジヒドロカルビルエステル残基の中から選ばれる官能基由来の二価の官能基からなる群から選ばれる少なくとも一種の二価の官能基である、上記［４］に記載のタイヤ、
［６］一般式（７）において、前記シラノール基と補強性充填材との反応を促進する官能基を少なくとも一つ含む基Ｂ及びＤが、それぞれ独立に第一アミノ基、第二アミノ基、保護された第一もしくは第二アミノ基、第三アミノ基、環状アミノ基、オキサゾリル基、イミダゾリル基、アジリジニル基、（チオ）ケトン基、（チオ）アルデヒド基及びアミド基、（チオ）エポキシ基、（チオ）イソシアネート基、ニトリル基、ピリジル基、Ｎ−アルキルピロリドニル基、Ｎ−アルキルイミダゾリル基、Ｎ−アルキルピラゾリル基、イミノ基、アミド基、ケチミン基、イミン残基、イソシアヌル酸トリエステル残基、炭素数１〜２０の（チオ）カルボン酸ヒドロカルビルエステル残基、炭素数１〜２０の（チオ）カルボン酸金属塩の残基、炭素数１〜２０のカルボン酸無水物残基、炭素数１〜２０のカルボン酸ハロゲン化物残基、炭酸ジヒドロカルビルエステル残基及び一般式−Ｅ−Ｆ−Ｇで表される官能基の中から選ばれる少なくとも一種の官能基である、上記［４］又は［５］に記載のタイヤ、
［式中、Ｅはイミノ基、２価のイミン残基、２価のピリジン残基又は２価のアミド残基、Ｆは炭素数１〜２０のアルキレン基、フェニレン基又は炭素数８〜２０のアラルキレン基、Ｇは第一アミノ基、第二アミノ基、イミダゾリル基、アジリジニル基、ケチミン基、ニトリル基、アミド基、ピリジン基又は（チオ）イソシアネート基である］
［７］変性共役ジエン系重合体が、ポリブタジエン、ポリイソプレン、ブタジエン−イソプレン共重合体、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体又はスチレン−イソプレン−ブタジエン三元共重合体の変性化物である、上記［１］〜［６］のいずれかに記載のタイヤ、
［８］一般式（１）で表される（ｃ−１）化合物が、下記式（１−１）

Wherein R ⁴ is a single bond or a hydrocarbon group having 1 to 20 carbon atoms; R ⁵ and R ⁶ are each independently a single bond, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; A ⁴ is a single bond , A functional group that promotes the reaction between the hydrocarbon group having 1 to 20 carbon atoms or the silanol group and the reinforcing filler; and B and D are each independently a functional group that promotes the reaction between the silanol group and the reinforcing filler. A group containing at least one; p and q are each independently an integer of 0 to 5, (p + q) is 1 or more, and n is an integer of 1 to 10]
[5] In the general formula (6) or (7), the functional groups A ³ and A ⁴ that promote the reaction between the silanol group and the reinforcing filler are each independently a (thio) ether bond, (thio ) Divalent functional group having at least one bond selected from urethane bond, imino bond and amide bond, as well as nitrile group, pyridyl group, N-alkylpyrrolidonyl group, N-alkylimidazolyl group, N-alkyl Pyrazolyl group, (thio) ketone group, (thio) aldehyde group, isocyanuric acid triester residue, (thio) carboxylic acid hydrocarbyl ester residue having 1 to 20 carbon atoms, (thio) carboxylic acid metal having 1 to 20 carbon atoms Among salt residues, carboxylic acid anhydride residues having 1 to 20 carbon atoms, carboxylic acid halide residues having 1 to 20 carbon atoms and carbonic acid dihydrocarbyl ester residues The tire according to the above [4], which is at least one divalent functional group selected from the group consisting of divalent functional groups derived from functional groups selected from
[6] In the general formula (7), the groups B and D containing at least one functional group that promotes the reaction between the silanol group and the reinforcing filler are independently a primary amino group, a secondary amino group, Protected primary or secondary amino group, tertiary amino group, cyclic amino group, oxazolyl group, imidazolyl group, aziridinyl group, (thio) ketone group, (thio) aldehyde group and amide group, (thio) epoxy group, (Thio) isocyanate group, nitrile group, pyridyl group, N-alkylpyrrolidonyl group, N-alkylimidazolyl group, N-alkylpyrazolyl group, imino group, amide group, ketimine group, imine residue, isocyanuric acid triester residue Group, (thio) carboxylic acid hydrocarbyl ester residue having 1 to 20 carbon atoms, residue of (thio) carboxylic acid metal salt having 1 to 20 carbon atoms, carbon number -20 carboxylic acid anhydride residue, C1-20 carboxylic acid halide residue, carbonic acid dihydrocarbyl ester residue and at least selected from the functional groups represented by the general formula -EFG The tire according to the above [4] or [5], which is a kind of functional group,
[In the formula, E is an imino group, a divalent imine residue, a divalent pyridine residue or a divalent amide residue, F is an alkylene group having 1 to 20 carbon atoms, a phenylene group, or 8 to 20 carbon atoms. Aralkylene group, G is primary amino group, secondary amino group, imidazolyl group, aziridinyl group, ketimine group, nitrile group, amide group, pyridine group or (thio) isocyanate group]
[7] The modified conjugated diene polymer is a modified product of polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, or styrene-isoprene-butadiene terpolymer. The tire according to any one of the above [1] to [6],
[8] The compound (c-1) represented by the general formula (1) is represented by the following formula (1-1):

で示される構造を有するシランカップリング剤である、上記［１］〜［７］のいずれかに記載のタイヤ、
［９］一般式（２）で表される（ｃ−２）化合物が、下記式（２−１）、式（２−２）又は式（２−３）

The tire according to any one of the above [1] to [7], which is a silane coupling agent having a structure represented by:
[9] The compound (c-2) represented by the general formula (2) is represented by the following formula (2-1), formula (2-2), or formula (2-3).

［式中Ｌはそれぞれ独立して炭素数１〜９のアルカンジイル基又はアルケンジイル基を示し、ｘは１〜２０の数、ｙは０〜２０の数を示す。］
で示される構造を有するシランカップリング剤である、上記［１］〜［７］のいずれかに記載のタイヤ、
［１０］（Ｃ）シランカップリング剤が、式（２−２）及び式（２−３）で表される（ｃ−２）化合物、並びに一般式（３）で表され、かつＲ^2aが−Ｏ（Ｙ−Ｏ）_m−Ｘであって、Ｘが炭素数６〜１５のアルキル基である（ｃ−３）化合物の中から選ばれる少なくとも１種である、上記［１］〜［７］のいずれかに記載のタイヤ、
［１１］一般式（３）で表される（ｃ−３）化合物が、下記式（３−１）

[In formula, L shows a C1-C9 alkanediyl group or alkenediyl group each independently, x shows the number of 1-20, y shows the number of 0-20. ]
The tire according to any one of the above [1] to [7], which is a silane coupling agent having a structure represented by:
[10] The (C) silane coupling agent is represented by the compound (c-2) represented by the formula (2-2) and the formula (2-3), and the general formula (3), and R ^2a is -O (YO) _m- X, wherein X is at least one selected from compounds (c-3) in which the alkyl group has 6 to 15 carbon atoms, [1] to [7 ] The tire according to any one of
[11] The compound (c-3) represented by the general formula (3) is represented by the following formula (3-1):

で示される構造を有する、上記［１０］に記載のタイヤ、
［１２］補強性充填材が、シリカと共にカーボンブラックを含む上記［１］〜［１１］に記載のタイヤ、
を提供するものである。

The tire according to [10] above, which has a structure represented by:
[12] The tire according to [1] to [11], wherein the reinforcing filler contains carbon black together with silica.
Is to provide.

  According to the present invention, a rubber composition containing a rubber component containing a specific modified conjugated diene polymer, a reinforcing filler containing at least silica, and a silane coupling agent having a specific structure is used for the tread. Thus, it is possible to provide a tire that can prevent the generation of a volatile organic compound (VOC) during work and can satisfy low heat build-up, wear resistance, and wet grip performance.

  The tire of the present invention has a silanol group and a functional group in the vicinity of the silanol group at the molecular end of the (A) conjugated diene polymer, and promotes the reaction between the silanol group and the reinforcing filler. A rubber component containing 10% by mass or more of a modified conjugated diene polymer having a functional group, (B) a reinforcing filler containing at least silica, and (A) 100 parts by mass of the rubber component, (C) At least one silane coupling selected from the following compounds (c-1), (c-2), (c-3), (c-4) and (c-5) A rubber composition containing 1 to 25 parts by mass of an agent is used for the tread.

[(A) Rubber component]
In the rubber composition used in the tire of the present invention, the rubber component used as the component (A) contains 10% by mass or more of a modified conjugated diene polymer having the following specific functional group.
(Modified conjugated diene polymer)
As the modified conjugated diene polymer, one having a structure represented by the following general formula (6) or (7) can be used.

ここで、Ｒ¹は単結合又は炭素数１〜２０の二価の炭化水素基；Ｒ²及びＲ³はそれぞれ独立に水素又は炭素数１〜２０の一価の炭化水素基；Ａ³は単結合、炭素数１〜２０の炭化水素基又はシラノール基と補強性充填材との反応を促進する官能基であり、ｍは１〜１０の整数である。

Wherein, R ¹ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms; monovalent hydrocarbon group of R ² and R ³ are hydrogen or a C 1-20 independently; A ³ is a single It is a functional group that promotes the reaction between the bond, the hydrocarbon group having 1 to 20 carbon atoms or the silanol group, and the reinforcing filler, and m is an integer of 1 to 10.

ここで、Ｒ⁴は単結合又は炭素数１〜２０の炭化水素基；Ｒ⁵及びＲ⁶はそれぞれ独立に単結合、水素又は炭素数１〜２０の炭化水素基；Ａ⁴は単結合、炭素数１〜２０の炭化水素基又はシラノール基と補強性充填材との反応を促進する官能基；Ｂ及びＤはそれぞれ独立にシラノール基と補強性充填材との反応を促進する官能基を少なくとも一つ含む基；ｐ及びｑはそれぞれ独立に０〜５の整数であり、（ｐ＋ｑ）が１以上である。ｎは１〜１０の整数であり、好ましくは１〜６の整数である。
なお、（Polymer）− は変性共役ジエン系重合体のポリマー鎖である。

Here, R ⁴ is a single bond or a hydrocarbon group having 1 to 20 carbon atoms; R ⁵ and R ⁶ are each independently a single bond, hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; A ⁴ is a single bond or carbon Functional groups that promote the reaction between the hydrocarbon group or silanol group of formulas 1 to 20 and the reinforcing filler; B and D are each independently at least one functional group that promotes the reaction between the silanol group and the reinforcing filler. P and q are each independently an integer of 0 to 5, and (p + q) is 1 or more. n is an integer of 1 to 10, preferably an integer of 1 to 6.
Here, (Polymer) − is a polymer chain of a modified conjugated diene polymer.

In the said General formula (6) and the said General formula (7), R < ¹ >, R < ⁴ >, R < ⁵ > in case p is 1, or R < ⁶ > in case q is 1, C1-C20 bivalent Specific examples of the hydrocarbon group include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,3-diyl. Group, pentane-1,5-diyl group, hexane-1,3-diyl group, hexane-1,6-diyl group, heptane-1,3-diyl group, heptane-1,7-diyl group, octane-1 , 8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group and the like. Of these, a propane-1,3-diyl group is particularly preferred.
Here, R ⁵ when p is 0 and R ⁶ when q is 0 are a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms in the same manner as R ² and R ³ . That is, the valence of R ⁵ is (p + 1), and the valence of R ⁶ is (q + 1).

In the general formula (6) and the general formula (7), R ² , R ³ , R ⁵ when p is 0, or R ⁶ when q is 0, Specific examples of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n -A heptyl group, n-octyl group, a stearyl group etc. are mentioned. Among these, a methyl group or an ethyl group is particularly preferable.

In the general formula (6) and the general formula (7), as the functional groups A ³ and A ⁴ that promote the reaction between the silanol group and the reinforcing filler, each independently, for example, a (thio) ether bond, A divalent functional group having at least one bond selected from (thio) urethane bond, imino bond and amide bond, nitrile group (cyano group), pyridyl group, N-alkylpyrrolidonyl group, N-alkyl Imidazolyl group, N-alkylpyrazolyl group, (thio) ketone group, (thio) aldehyde group, isocyanuric acid triester residue, (thio) carboxylic acid hydrocarbyl ester residue having 1 to 20 carbon atoms, 1 to 20 carbon atoms Residues of (thio) carboxylic acid metal salts, carboxylic acid anhydride residues having 1 to 20 carbon atoms, carboxylic acid halide residues having 1 to 20 carbon atoms and dihydric carbonate It is at least one divalent functional group selected from the group consisting of divalent functional groups derived from functional groups selected from locarbyl ester residues.
Here, the divalent functional group having at least one bond selected from (thio) ether bond, (thio) urethane bond, imino bond and amide bond is (thio) ether bond, (thio) urethane bond, It may be an imino bond or an amide bond, or may be a C1-C20 divalent hydrocarbon group having a (thio) ether bond, a (thio) urethane bond, an imino bond and / or an amide bond. . Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include the same specific example as R ⁵ when R ¹ , R ⁴ and p are 1 or R ⁶ when q is 1. .

A ³ and A ⁴ in the general formula (6) and the general formula (7) each represent a functional group bonded to the active site of the modified conjugated diene polymer, and formed in the hydrolysis reaction step described later. It has the effect of promoting the reaction between the base and the reinforcing filler.

In the general formula (7), the groups B and D containing at least one functional group that promotes the reaction between the silanol group and the reinforcing filler are each independently a primary amino group, a secondary amino group, or a protected group. Primary or secondary amino group, tertiary amino group, cyclic amino group, oxazolyl group, imidazolyl group, aziridinyl group, (thio) ketone group, (thio) aldehyde group and amide group, (thio) epoxy group, glycidoxy group (Thio) isocyanate group, nitrile group (cyano group), pyridyl group, N-alkylpyrrolidonyl group, N-alkylimidazolyl group, N-alkylpyrazolyl group, imino group, amide group, ketimine group, imine residue, Isocyanuric acid triester residue, (thio) carboxylic acid hydrocarbyl ester residue having 1 to 20 carbon atoms, (thio) carbon having 1 to 20 carbon atoms Residues of boronic acid metal salts, carboxylic acid anhydride residues having 1 to 20 carbon atoms, carboxylic acid halide residues having 1 to 20 carbon atoms, carbonic acid dihydrocarbyl ester residues and the general formula -E-F-G Examples include at least one functional group selected from the functional groups represented.
Here, E is an imino group, a divalent imine residue, a divalent pyridine residue or a divalent amide residue, F is an alkylene group having 1 to 20 carbon atoms, a phenylene group or an aralkylene having 8 to 20 carbon atoms. Group G is primary amino group, secondary amino group, protected primary or secondary amino group, tertiary amino group, cyclic amino group, oxazolyl group, imidazolyl group, aziridinyl group, ketimine group, nitrile group (cyano Group), an amide group, a pyridine group or a (thio) isocyanate group.
Specific examples of the functional group represented by formula -E-F-G -NH-C 2 H 4 -NH 2 -NH-C 2 H 4 -N (CH 3) 2, and these -C ₂ H ₄ - or a functional group which replaces a phenylene group - -C ₆ H ₁₂ the.
In addition, the functional group which can remove | eliminate the protected primary or secondary amino group may remain in the modified conjugated diene polymer without being deprotected.

  As shown in the general formula (6) or the general formula (7), the modified conjugated diene polymer preferably has only one silanol group in the molecular chain. This is because if two or more silanol groups are present in the molecular chain, the silanol groups are condensed with each other, and the viscosity of the modified conjugated diene polymer is increased, which may make the kneading operation difficult.

  In addition, the modified conjugated diene polymer has both a silanol group and a functional group that promotes the reaction between the silanol group and the reinforcing filler in the vicinity of the silanol group. Modified conjugated diene polymer that does not have a functional group that promotes the reaction between the group and the reinforcing filler, or has only a functional group that promotes the reaction between the silanol group and the reinforcing filler, and does not have a silanol group Compared with the modified conjugated diene-based polymer, both the silica-containing rubber composition and the carbon black-containing rubber composition improve the low heat build-up.

The modified conjugated diene polymer does not limit the vinyl bond content of the conjugated diene part, but is preferably 70% or less. If it is 70% or less, the fracture characteristics and the wear characteristics are improved when used for a tire tread.
Moreover, it is preferable that styrene content is 0-50 mass%. This is because if it is 50% by mass or less, the balance between low heat build-up and wet skid performance is improved.
Incidentally, the vinyl bond content, by an infrared method (Morello method), styrene content was determined by calculating the integral ratio of the spectra in ¹ H-NMR.
Next, a method for producing the modified conjugated diene polymer will be described.

<Production of Modified Conjugated Diene Polymer>
The modified conjugated diene polymer includes a characteristic group that generates a silanol group by hydrolysis at the active site of a conjugated diene polymer having an active site, and (i) an addition to the active site in the vicinity of the characteristic group. Alternatively, a functional group that binds the organosilane compound and the conjugated diene polymer by performing a substitution reaction and promotes the reaction between the silanol group and the reinforcing filler after the reaction, or (ii) the silanol group A modification reaction step of reacting an organosilane compound having a functional group that promotes the reaction with the reinforcing filler, a hydrolysis step performed after completion of the modification reaction step, and preferably in the presence of a condensation accelerator. It can be produced by a method including a condensation reaction step for carrying out a condensation reaction. Through such a process, a silanol group is imparted to the molecular chain terminal of the modified conjugated diene polymer.
In the present invention, the characteristic group that generates a silanol group by hydrolysis is an alkoxysilane group, and 10% or more of the characteristic group generates a silanol group by hydrolysis. From the point of view, it is preferable.

  The characteristic group that generates a silanol group by hydrolysis needs to become a silanol group by reaction when reacting with a reinforcing filler, particularly silica, but if it is a silanol group from the beginning, the reactivity with silica is more This increases the dispersibility of the silica in the rubber composition, and has the great effect of improving the low heat build-up of the rubber composition. Furthermore, when the characteristic group that generates a silanol group by hydrolysis is an alkoxy group, a volatile organic compound (VOC, particularly alcohol) is generated, but a silanol group is not generated.

  A characteristic group that generates a silanol group by the hydrolysis, and (i) an organic silane compound and the conjugated diene polymer are bonded by performing an addition or substitution reaction on the active site in the vicinity of the characteristic group, and An organosilane compound having a functional group that promotes the reaction between the silanol group and the reinforcing filler after the reaction or (ii) a functional group that promotes the reaction between the silanol group and the reinforcing filler is represented by the following general formula: It is preferable that it is an organosilane compound represented by (8) or following General formula (9).

ここで、Ｒ¹、Ｒ²、Ｒ³及びｍは、前記一般式（６）と同じである。−ＯＬ¹は加水分解によりＳｉと共にシラノール基を生成する加水分解性官能基；Ａ¹は前記活性部位に付加もしくは置換反応を行う事によって前記有機シラン化合物と前記共役ジエン系重合体とを結合させ、且つ該反応後に該シラノール基と前記補強性充填材との反応を促進する官能基である。

Here, R ¹ , R ² , R ³ and m are the same as in the general formula (6). -OL ¹ is a hydrolyzable functional group that forms a silanol group with Si by hydrolysis; A ¹ binds the organosilane compound and the conjugated diene polymer by performing an addition or substitution reaction on the active site. And a functional group that promotes the reaction between the silanol group and the reinforcing filler after the reaction.

ここで、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｂ、Ｄ、ｎ、ｐ及びｑは、前記一般式（７）と同じである。−ＯＬ²は加水分解によりＳｉと共にシラノール基を生成する加水分解性官能基；Ａ²は前記活性部位と反応する官能基又は前記活性部位に付加もしくは置換反応を行う事によって前記有機シラン化合物と前記共役ジエン系重合体とを結合させる官能基である。

Here, R ⁴ , R ⁵ , R ⁶ , B, D, n, p and q are the same as in the general formula (7). -OL ² is a hydrolyzable functional group that generates a silanol group together with Si by hydrolysis; A ² is a functional group that reacts with the active site or an addition or substitution reaction on the active site to form the organosilane compound and the It is a functional group that binds to a conjugated diene polymer.

Here, as the hydrolyzable functional group that generates a silanol group together with Si by hydrolysis, for example, an alkoxy group having 1 to 20 carbon atoms, a phenoxy group, a benzyloxy group, -OM _{(1 / x), and the} like are preferable. Can be mentioned. An alkoxy group having 1 to 20 carbon atoms is more preferable, and an alkoxy group having 1 to 12 carbon atoms is particularly preferable. Specific examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group.
In the above formula -OM _{(1 / x)} , M is a group 1 element excluding hydrogen (ie, alkali metal); a group 2-12 element; a group 13 element excluding boron; a group excluding carbon and silicon. Group 14 element: a metal atom selected from Group 15 elements and rare earth elements excluding nitrogen, phosphorus and arsenic, and x is the valence of the metal atom. Group 2 elements are Be, Mg and alkaline earth metals. Among these metal atoms, alkali metal, Mg, alkaline earth metal, Sn, Al, Ti, and Fe are more preferable, and Li, Na, K, Mg, Ca, Ba, Sn, Al, Ti, and Fe are particularly preferable. .

In the general formula (8), the organosilane compound and the conjugated diene polymer are bonded by performing an addition or substitution reaction on the active site, and the silanol group and the reinforcing filler are bonded after the reaction. Examples of the functional group A ¹ that promotes the reaction of ¹ include a hydrocarbyloxy group having 1 to 20 carbon atoms, a (thio) epoxy group (including a glycidoxy group), a (thio) isocyanate group, a nitrile group (cyano group), and a pyridyl group. Group, N-alkylpyrrolidonyl group, N-alkylimidazolyl group, N-alkylpyrazolyl group, (thio) ketone group, (thio) aldehyde group, imine residue, amide group, ketimine group, isocyanuric acid triester residue , A (thio) carboxylic acid hydrocarbyl ester residue having 1 to 20 carbon atoms, and a (thio) carboxylic acid metal salt having 1 to 20 carbon atoms Group, a carboxylic anhydride residue having 1 to 20 carbon atoms and an acyl halide residues or carbonate dihydrocarbyl ester residue having 1 to 20 carbon atoms. The halogen of the carboxylic acid halide residue having 1 to 20 carbon atoms is preferably chlorine, bromine or fluorine. As a C1-C20 carboxylic anhydride residue, a maleic anhydride residue, a phthalic anhydride residue, an acetic anhydride residue, etc. are preferable. These are a group that binds to the active site of the conjugated diene polymer and a group that promotes the reaction with silica.

In the general formula (9), as a functional group that reacts with the active site or a functional group A ² that binds the organosilane compound and the conjugated diene polymer by performing an addition or substitution reaction on the active site, The following formula (9-a)
-R ^d SiX ₃ (9-a)
[Wherein R ^d represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or —OR ^e (R ^e is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms); X represents a halogen atom or an alkoxy group having 1 to 10 carbon atoms, and a plurality of X may be the same or different. Or a (thio) epoxy group, (thio) isocyanate group, nitrile group, imidazolyl group, ketimine group, (thio) ketone group or protected primary or secondary amino group Can do.

Moreover, the the functional group A ² which reacts with the active site of the conjugated diene polymer in the method for producing a modified conjugated diene polymer refers to a functional group A ² which may be the active site chemically react, for example, carbon Preferable examples include an alkoxy group of 1 to 20, a phenoxy group, a benzyloxy group, a halogen group and the like. An alkoxy group having 1 to 20 carbon atoms is more preferable, and an alkoxy group having 1 to 12 carbon atoms is particularly preferable. Specific examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an n-butoxy group, and a tert-butoxy group. As the halogen, chlorine, bromine or fluorine is preferable.

In the general formula (9), a silicon-containing group in which a halogen atom or an alkoxy group is bonded to a silicon atom, and a —R ^d SiX ₃ group represented by the formula (9-a) are present in the active site of the conjugated diene polymer. While the (thio) epoxy group, (thio) isocyanate group, nitrile group, imidazolyl group, ketimine group, (thio) ketone group or protected primary or secondary amino group is bonded to the silica It is a group that promotes the reaction.

  If a functional group that promotes the reaction between the silanol group and the reinforcing filler exists in the vicinity of the silanol group, the reinforcing filler, particularly the hydroxy group on the silica surface, the silanol group, and the silanol group react with the reinforcing filler. It can be considered that a stable structure is formed by the three atoms (oxygen atom, sulfur atom or nitrogen atom) having unpaired electrons in the functional group to be promoted, and the reactivity of the silanol group to silica is improved. Thereby, the low exothermic property of the rubber composition using the modified conjugated diene polymer is improved.

  Specific examples of the organic silane compounds represented by the general formula (8) include (2-glycidoxyethyl) dimethylmethoxysilane, (2-glycidoxyethyl) diethylmethoxy as (thio) epoxy group-containing silane compounds. Silane, (2-glycidoxyethyl) dimethylethoxysilane, (2-glycidoxyethyl) diethylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) diethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) diethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (dimethyl) methoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyl (diethyl) methoxysilane, 2- ( It may include those obtained by replacing the 4-epoxycyclohexyl) ethyl (dimethyl) ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (diethyl) ethoxysilane, and epoxy group in these compounds thioepoxy group. Among these, in particular, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) diethylmethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (dimethyl) methoxysilane and 2- ( 3,4-epoxycyclohexyl) ethyl (diethyl) methoxysilane is preferred.

  As another specific example of the organic silane compound represented by the general formula (8), as the imine residue-containing silane compound, N- (1,3-dimethylbutylidene) -3- (dimethylethoxysilyl)- 1-propanamine, N- (1,3-dimethylbutylidene) -3- (diethylethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (dimethylethoxysilyl) -1-propane Amine, N- (1-methylethylidene) -3- (diethylethoxysilyl) -1-propanamine, N-ethylidene-3- (dimethylethoxysilyl) -1-propanamine, N-ethylidene-3- (diethylethoxy Silyl) -1-propanamine, N- (1-methylpropylidene) -3- (dimethylethoxysilyl) -1-propanami N- (1-methylpropylidene) -3- (diethylethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (dimethylethoxysilyl) -1-propanamine N- (4-N, N-dimethylaminobenzylidene) -3- (diethylethoxysilyl) -1-propanamine, N- (cyclohexylidene) -3- (dimethylethoxysilyl) -1-propanamine, N Examples include-(cyclohexylidene) -3- (diethylethoxysilyl) -1-propanamine. Among these, in particular, N- (1-methylpropylidene) -3- (dimethylethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (diethylethoxysilyl) -1-propane Amine, N- (1,3-dimethylbutylidene) -3- (dimethylethoxysilyl) -1-propanamine and N- (1,3-dimethylbutylidene) -3- (diethylethoxysilyl) -1-propane Amines are preferred.

  As another specific example of the organosilane compound represented by the general formula (8), as the imino (amidine) group-containing compound, 1- [3- (dimethylethoxysilyl) propyl] -4,5-dihydroimidazole, 1 -[3- (diethylethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (dimethylmethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (diethylmethoxysilyl) propyl ] -4,5-dihydroimidazole, 3- [10- (dimethylethoxysilyl) decyl] -4-oxazoline, 3- [10- (diethylethoxysilyl) decyl] -4-oxazoline, 3- (1-hexamethylene) Imino) propyl (dimethylethoxy) silane, 3- (1-hexamethyleneimino) propyl (die) (Luethoxy) silane, (1-hexamethyleneimino) methyl (dimethylmethoxy) silane, (1-hexamethyleneimino) methyl (diethylmethoxy) silane, 1- [3- (dimethylethoxysilyl) propyl] -4,5-dihydro Imidazole, 1- [3- (diethylethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (dimethylmethoxysilyl) propyl] -4,5-dihydroimidazole and 1- [3- (diethylmethoxy) Silyl) propyl] -4,5-dihydroimidazole and the like, among which 3- (1-hexamethyleneimino) propyl (dimethylethoxy) silane, 3- (1-hexamethyleneimino) propyl (Diethylethoxy) silane, (1-hexamethyleneimino) methyl (Dimethylmethoxy) silane, (1-hexamethyleneimino) methyl (diethylmethoxy) silane, 1- [3- (dimethylethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (diethylethoxysilyl) Propyl] -4,5-dihydroimidazole, 1- [3- (dimethylmethoxysilyl) propyl] -4,5-dihydroimidazole and 1- [3- (diethylmethoxysilyl) propyl] -4,5-dihydroimidazole Preferable examples can be given.

  As another specific example of the organic silane compound represented by the general formula (8), as a carboxylic acid ester group-containing compound, (3-methacryloyloxypropyl) dimethylethoxysilane, (3-methacryloyloxypropyl) Diethylethoxysilane, (3-methacryloyloxypropyl) dimethylmethoxysilane, (3-methacryloyloxypropyl) diethylmethoxysilane, (3-methacryloyloxypropyl) dimethylisopropoxysilane, (3-methacryloyloxypropyl) diethyl Examples thereof include isopropoxysilane, and among these, (3-methacryloyloxypropyl) dimethylmethoxysilane and (3-methacryloyloxypropyl) diethylmethoxysilane are preferable.

  Furthermore, as another specific example of the organic silane compound represented by the general formula (8), as the isocyanate group-containing compound, (3-isocyanatopropyl) dimethylmethoxysilane, (3-isocyanatopropyl) diethylmethoxysilane, (3-isocyanatopropyl) dimethylethoxysilane, (3-isocyanatopropyl) diethylethoxysilane, (3-isocyanatopropyl) dimethylisopropoxysilane, (3-isocyanatopropyl) diethylisopropoxysilane, etc. Of these, (3-isocyanatopropyl) dimethylethoxysilane and (3-isocyanatopropyl) diethylethoxysilane are preferred.

  Further, as another specific example of the organic silane compound represented by the general formula (8), as the carboxylic acid anhydride-containing compound, 3- (dimethylethoxy) silylpropylsuccinic anhydride, 3- (diethylethoxy) silyl Propyl succinic anhydride, 3- (dimethylmethoxy) silylpropyl succinic anhydride, 3- (diethylmethoxy) silylpropyl succinic anhydride, and the like. Among these, 3- (dimethylethoxy) silyl is preferable. Propyl succinic anhydride and 3- (diethylethoxy) silylpropyl succinic anhydride.

Examples of the organosilane compound represented by the general formula (9) include trialkylsilyl groups in which ^a protecting group is represented by —SiR ^a R ^b R ^c (wherein R ^a , R ^b and R ^c are each independently a carbon number). And a hydrocarbyloxysilane compound having a protected primary amino group having 2 alkyl groups of 1 to 12 alkyl groups, preferably a methyl group, an ethyl group, a propyl group, a propyl group or a butyl group. Specific examples of the hydrocarbyloxysilane compound having a protected primary amino group include N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N , N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane and the like can be preferably exemplified. Among these, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane or N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane is particularly preferable.

As another example of the organic silane compound represented by the general formula (9), a trialkylsilyl group (R ^a , R ^b and R ^c are the same as above) in which the protecting group is represented by —SiR ^a R ^b R ^c And a hydrocarbyloxysilane compound having a protected secondary amino group. Specific examples of the hydrocarbyloxysilane compound having a protected secondary amino group include N, N-methyl (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-ethyl (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N N-methyl (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-ethyl (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-methyl (trimethylsilyl) aminoethylmethyldimethoxysilane, N, N-ethyl (trimethylsilyl) Preferred examples include aminoethylmethyldimethoxysilane, N, N-methyl (trimethylsilyl) aminoethylmethyldiethoxysilane, N, N-ethyl (trimethylsilyl) aminoethylmethyldiethoxysilane, and the like. That.

  Moreover, as another specific example of the organosilane compound represented by the general formula (9), for example, N- (1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (methyldiethoxysilyl) -1-propanamine, N-ethylidene-3- (methyldiethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (cyclohexylidene) -3- (methyldiethoxysilyl) -1-propanamine and methyldimethoxysilyl compounds corresponding to these methyldiethoxysilyl compounds, Preferred examples include imine residue-containing hydrocarbyloxysilane compounds such as rudiethoxysilyl compounds and ethyldimethoxysilyl compounds. Among these, N- (1-methylpropylidene) -3- (methyldiethoxysilyl) is particularly preferable. ) -1-propanamine and N- (1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine are preferred.

  Furthermore, as another specific example of the organic silane compound represented by the general formula (9), for example, 3-dimethylaminopropyl (diethoxy) methylsilane, 3-dimethylaminopropyl (dimethoxy) methylsilane, 3-diethylaminopropyl (diethoxy) Preferred examples include non-cyclic tertiary amino group-containing hydrocarbyloxysilane compounds such as methylsilane, 3-diethylaminopropyl (dimethoxy) methylsilane, 2-dimethylaminoethyl (diethoxy) methylsilane, and 2-dimethylaminoethyl (dimethoxy) methylsilane. Of these, 3-dimethylaminopropyl (dimethoxy) methylsilane and 3-dimethylaminopropyl (diethoxy) methylsilane are particularly preferable.

  Moreover, as another specific example of the organic silane compound represented by the general formula (9), for example, 3-methylaminopropyl (diethoxy) methylsilane, 3-methylaminopropyl (dimethoxy) methylsilane, 3-ethylaminopropyl ( Preferred examples include non-cyclic secondary amino group-containing hydrocarbyloxysilane compounds such as diethoxy) methylsilane, 3-ethylaminopropyl (dimethoxy) methylsilane, 2-methylaminoethyl (diethoxy) methylsilane, and 2-methylaminoethyl (dimethoxy) methylsilane. Among these, 3-methylaminopropyl (diethoxy) methylsilane and 3-methylaminopropyl (dimethoxy) methylsilane are particularly preferable.

  Moreover, as another specific example of the organosilane compound represented by the general formula (9), for example, 3- (1-hexamethyleneimino) propyl (methyldiethoxy) silane, 3- (1-hexamethyleneimino) Propyl (methyldimethoxy) silane, (1-hexamethyleneimino) methyl (methyldimethoxy) silane, (1-hexamethyleneimino) methyl (methyldiethoxy) silane, 2- (1-hexamethyleneimino) ethyl (methyldiethoxy) ) Silane, 2- (1-hexamethyleneimino) ethyl (methyldimethoxy) silane, 3- (1-pyrrolidinyl) propyl (methyldiethoxy) silane, 3- (1-pyrrolidinyl) propyl (methyldimethoxy) silane, 3- (1-Heptamethyleneimino) propyl (methyldiethoxy) silane, 3 (1-dodecamethyleneimino) propyl (methyldiethoxy) silane, 3- (1-hexamethyleneimino) propyl (ethyldiethoxy) silane, 3- [10- (methyldiethoxysilyl) decyl] -4-oxazoline, etc. Of these, the cyclic tertiary amino group-containing hydrocarbyloxysilane compounds are preferably exemplified, among which 3- (1-hexamethyleneimino) propyl (methyldiethoxy) silane and (1-hexamethyleneimino) methyl ( More preferred is methyldimethoxy) silane. In particular, 3- (1-hexamethyleneimino) propyl (methyldiethoxy) silane is preferable.

  As another specific example of the organosilane compound represented by the general formula (9), for example, N- (3-methyldimethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-methyldiethoxy) Examples include amidine group-containing hydrocarbyloxysilane compounds such as silylpropyl) -4,5-dihydroimidazole, and among them, N- (3-methyldiethoxysilylpropyl) -4,5-dihydroimidazole is preferable.

Moreover, as another specific example of the organosilane compound represented by the general formula (9), for example, (2-glycidoxyethyl) methyldimethoxysilane, (2-glycidoxyethyl) methyldiethoxysilane, ( 2-glycidoxyethyl) ethyldimethoxysilane, (2-glycidoxyethyl) ethyldiethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, ( 3-glycidoxypropyl) ethyldimethoxysilane, (3-glycidoxypropyl) ethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyldimethoxy) silane, 2- (3,4-exicyclohexyl) ) Ethyl (methyldiethoxy) silane 2- (3,4-epoxycyclohexyl) Preferred examples include epoxy group-containing hydrocarbyloxysilane compounds such as ethyl (ethyldimethoxy) silane and 2- (3,4-exicyclohexyl) ethyl (ethyldiethoxy) silane, and among these, (3 -Glycidoxypropyl) methyldimethoxysilane and (3-glycidoxypropyl) methyldiethoxysilane are preferred.
An epithio group-containing hydrocarbyloxysilane compound obtained by replacing the epoxy group of the epoxy group-containing hydrocarbyloxysilane compound with an epithio group can also be preferably exemplified.

  Moreover, as another specific example of the organosilane compound represented by the general formula (9), for example, (3-isocyanatopropyl) methyldimethoxysilane, (3-isocyanatopropyl) methyldiethoxysilane, (3- Isocyanatopropyl) ethyldimethoxysilane, (3-isocyanatopropyl) ethyldiethoxysilane, (3-isocyanatopropyl) methyldiisopropoxysilane, 3- (isocyanatopropyl) ethyldiisopropoxysilane-containing isocyanate groups Examples thereof include hydrocarbyloxysilane compounds, among which (3-isocyanatopropyl) methyldiethoxysilane is preferred.

  Other specific examples of the organic silane compound represented by the general formula (9) include, for example, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, and 3-methacryloyloxy. Examples include hydrocarbyloxysilane compounds containing carboxylic acid hydrocarbyl ester residues such as propylethyldimethoxysilane, 3-methacryloyloxypropylethyldiethoxysilane, and 3-methacryloyloxypropylmethyldiisopropoxysilane. Loyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropylmethyldiethoxysilane are preferred.

Other specific examples of the organic silane compound represented by the general formula (9) include, for example, 3- (methyldiethoxysilyl) propyl succinic anhydride, 3- (methyldimethoxysilyl) propyl succinic anhydride Carboxylic acid anhydride residue-containing hydrocarbyloxysilane compounds such as 3- (methyldiethoxysilyl) propyl succinic anhydride are preferable.
Furthermore, 2- (methyldimethoxysilylethyl) pyridine, 2- (methyldiethoxysilylethyl) pyridine, 2-cyanoethylmethyldiethoxysilane and the like can be mentioned.

  Among the various organic silane compounds represented by the above general formula (9), a hydrocarbyloxysilane compound having an amino group or an imine residue is preferable from the viewpoint of improving low heat build-up, and among them, the above-mentioned protected A hydrocarbyloxysilane compound having a primary amino group is particularly preferred. This is because introduction of a primary amino group into the molecular chain terminal of the modified conjugated diene polymer greatly improves the low heat buildup of the rubber composition containing the modified conjugated diene polymer.

When producing the modified conjugated diene polymer, if necessary, pre-modification of the hydrocarbyloxysilane compound with the active site of the conjugated diene polymer before the modification reaction step of reacting the organosilane compound. A reaction step may be further included.
Here, the hydrocarbyloxysilane compound used in the preliminary modification reaction step preferably has a plurality of hydrocarbyloxysilyl groups. Even if one hydrocarbyloxysilyl group is consumed by the reaction with the active site of the conjugated diene polymer, the remaining hydrocarbyloxysilyl group is used to perform a modification reaction step necessary for producing the modified conjugated diene polymer. It is because it can be implemented.

In the production of the modified conjugated diene polymer, examples of the conjugated diene monomer used in the conjugated diene polymer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1, Examples include 3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene. These may be used alone or in combination of two or more, and among these, 1,3-butadiene is particularly preferable.
Examples of the aromatic vinyl monomer used in the conjugated diene polymer include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, and 4-cyclohexylstyrene. 2,4,6-trimethylstyrene and the like. These may be used alone or in combination of two or more, but among these, styrene is particularly preferred.

  In the production of the modified conjugated diene polymer of the present invention, the conjugated diene polymer may be polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer or styrene-isoprene- A butadiene terpolymer is preferred, and among these, polybutadiene and a styrene-butadiene copolymer are particularly preferred.

  A method for producing the modified conjugated diene polymer will be described in detail. In order to react the active site of the conjugated diene polymer and the organosilane compound represented by the general formula (8) or the general formula (9) in the modification reaction step of the production method, the conjugated diene system to be used is used. The polymer is preferably such that at least 10% of the polymer chains have living property or pseudo-living property. As such a polymerization reaction having a living property, anionic polymerization or coordinated anionic polymerization is preferable, and anionic polymerization is particularly preferable in that it does not require the above-described preliminary modification reaction step.

  In the modification reaction step of the production method, the active site of the conjugated diene polymer means the active end of the conjugated diene polymer (active site at the end of the molecular chain), the active site in the main chain, and the active site in the side chain. However, when the active site of the conjugated diene polymer is obtained by anionic polymerization or coordinated anionic polymerization, the active end is preferable.

  As the organic alkali metal compound used as an initiator for the above-mentioned anionic polymerization, an organic lithium compound is preferable. The organolithium compound is not particularly limited, but hydrocarbyl lithium and lithium amide compounds are preferably used. When the former hydrocarbyl lithium is used, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal has polymerization activity. A terminal conjugated diene (co) polymer is obtained. When the latter lithium amide compound is used, a conjugated diene polymer having a nitrogen-containing group at the polymerization initiation terminal and the other terminal being the polymerization active terminal is obtained.

  As the hydrocarbyl lithium, those having a hydrocarbyl group having 2 to 20 carbon atoms are preferable, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl. Examples include lithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclobenthyllithium, a reaction product of diisopropenylbenzene and butyllithium, and the like. Of these, n-butyllithium is particularly preferred.

  On the other hand, examples of the lithium amide compound include lithium hexamethylene imide, lithium pyrrolidide, lithium piperide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, lithium dipropyl amide, lithium di Heptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiverazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide, lithium methylphenethylamide, etc. Is mentioned. Among these, from the viewpoint of the interaction effect on carbon black and the ability of initiating polymerization, cyclic lithium amides such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, and lithium dodecamethylene imide are preferable. In particular, lithium hexamethylene imide and lithium pyrrolidide are suitable.

  In general, these lithium amide compounds prepared in advance from a secondary amine and a lithium compound can be used for polymerization, but they can also be prepared in-situ. The amount of the polymerization initiator used is preferably selected in the range of 0.2 to 20 mmol per 100 g of monomer.

A method for producing a conjugated diene polymer by anionic polymerization using the organolithium compound as a polymerization initiator is not particularly limited, and a conventionally known method can be used.
Specifically, in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic, or aromatic hydrocarbon compound, a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl are used. The monomer is anionically polymerized with the lithium compound as a polymerization initiator in the presence of a randomizer to be used, if desired, to obtain a conjugated diene polymer having a target active end.
Further, when an organolithium compound is used as a polymerization initiator, not only a conjugated diene polymer having an active terminal but also a conjugated compound having an active terminal is used, compared to the case where a catalyst containing a lanthanum series rare earth element compound is used. A diene-aromatic vinyl copolymer can also be obtained efficiently.

The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans-2. -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These may be used singly or in combination of two or more.
The monomer concentration in the solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When copolymerization is performed using a conjugated diene monomer and an aromatic vinyl monomer, the content of the aromatic vinyl monomer in the charged monomer mixture is preferably in the range of 55% by mass or less.

  The randomizer used as desired is a control of the microstructure of the conjugated diene polymer, such as an increase in 1,2 bonds in the butadiene portion in the styrene-butadiene copolymer, an increase in 3,4 bonds in the isoprene polymer, or the like. It is a compound having an action of controlling the composition distribution of monomer units in the conjugated diene / aromatic vinyl copolymer, for example, randomizing butadiene units and styrene units in the styrene-butadiene copolymer. The randomizer is not particularly limited, and any one of known compounds generally used as a conventional randomizer can be appropriately selected and used. Specifically, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-bis (2-tetrahydrofuryl) -propane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, Examples thereof include ethers such as N′-tetramethylethylenediamine and 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium t-amylate and potassium t-butoxide, and sodium salts such as sodium t-amylate can also be used.

  One of these randomizers may be used alone, or two or more thereof may be used in combination. The amount used is preferably selected in the range of 0.01 to 1000 molar equivalents per mole of the lithium compound.

  The temperature in this polymerization reaction is preferably selected in the range of 0 to 150 ° C, more preferably 20 to 130 ° C. The polymerization reaction can be carried out under generated pressure, but it is usually desirable to operate at a pressure sufficient to keep the monomer in a substantially liquid phase. That is, the pressure depends on the particular material being polymerized, the polymerization medium used and the polymerization temperature, but higher pressures can be used if desired, such pressure being a gas that is inert with respect to the polymerization reaction. Can be obtained by an appropriate method such as pressurizing.

Next, a polymerization catalyst system for coordination anion polymerization will be described. As a polymerization catalyst system for coordination anionic polymerization, a catalyst containing a lanthanum series rare earth element compound in an organic solvent is used.
As a catalyst containing a lanthanum series rare earth element compound,
(A) component: a rare earth element-containing compound having an atomic number of 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base,
(B) Component: the following general formula (10):
AlR ^7a R ^8a R ^9a (10)
(Wherein R ^7a and R ^8a are the same or different and are a hydrocarbyl group having 1 to 10 carbon atoms or a hydrogen atom, and R ^9a is a hydrocarbyl group having 1 to 10 carbon atoms, provided that R ^9a is the above R ^7a or And may be the same as or different from R ^8a ), and component (c): at least one of a complex compound of Lewis acid, metal halide and Lewis base, and an organic compound containing an active halogen It is preferred to polymerize the conjugated diene monomer with a catalyst system comprising:

  In the present invention, an organoaluminum oxy compound, so-called aluminoxane, is added as a component (d) in addition to the components (a) to (c) above to the catalyst system containing a lanthanum series rare earth element compound. preferable. Here, it is more preferable that the catalyst system is preliminarily prepared in the presence of the component (a), the component (b), the component (c), the component (d) and the conjugated diene monomer.

  In the present invention, the component (a) of the catalyst system containing a lanthanum series rare earth element compound is a compound containing a rare earth element having an atomic number of 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base. . Here, among the rare earth elements having atomic numbers 57 to 71, neodymium, praseodymium, cerium, lanthanum, gadolinium, samarium, or a mixture thereof is preferable, and neodymium is particularly preferable.

The rare earth element-containing compound is preferably a salt soluble in a hydrocarbon solvent, and specific examples thereof include carboxylates, alkoxides, β-diketone complexes, phosphates and phosphites of the rare earth elements. Of these, carboxylates and phosphates are preferable, and carboxylates are particularly preferable.
Here, examples of the hydrocarbon solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane, saturated alicyclic hydrocarbons having 5 to 20 carbon atoms such as cyclopentane and cyclohexane, -Monoolefins such as butene, 2-butene, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene, etc. A halogenated hydrocarbon is mentioned.

As the rare earth element carboxylate, the following general formula (11):
(R ^10a -CO ₂ ) ₃ M ¹ (11)
(Wherein, R ^10a is a hydrocarbyl group having 1 to 20 carbon atoms, and M ¹ is a rare earth element having an atomic number of 57 to 71 in the periodic table). Here, R ^10a may be saturated or unsaturated, is preferably an alkyl group or an alkenyl group, and may be linear, branched or cyclic. The carboxyl group is bonded to a primary, secondary or tertiary carbon atom. Specifically, as the carboxylate, octanoic acid, 2-ethylhexanoic acid, oleic acid, neodecanoic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid [trade names of Shell Chemical Co., Ltd. , A carboxylic acid in which a carboxyl group is bonded to a tertiary carbon atom], and the like. Among these, salts of 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, and versatic acid are preferable.

As the alkoxide of the rare earth element, the following general formula (12):
(R ^11a O) ₃ M ² (12)
(Wherein, R ^11a is a hydrocarbyl group having 1 to 20 carbon atoms, and M ² is a rare earth element having an atomic number of 57 to 71 in the periodic table). ^Examples of the alkoxy group represented by R ^11a O include 2-ethyl-hexyloxy group, oleyloxy group, stearyloxy group, phenoxy group, benzyloxy group and the like. Among these, 2-ethyl-hexyloxy group and benzyloxy group are preferable.

  Examples of the rare earth element β-diketone complex include the rare earth element acetylacetone complex, benzoylacetone complex, propionitrileacetone complex, valerylacetone complex, ethylacetylacetone complex, and the like. Among these, an acetylacetone complex and an ethylacetylacetone complex are preferable.

  Examples of the rare earth element phosphate and phosphite include the rare earth element, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl phosphate), bis (p-nonylphenyl) phosphate, phosphorus Acid bis (polyethylene glycol-p-nonylphenyl), phosphoric acid (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl), 2-ethylhexylphosphonic acid mono-2-ethylhexyl 2-ethylhexylphosphonic acid mono-p-nonylphenyl, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, bis (p-nonylphenyl) phosphinic acid, (1-methylheptyl) (2 -Ethylhexyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphine Among these, the rare earth elements, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, bis A salt with (2-ethylhexyl) phosphinic acid is preferred.

  Among the rare earth element-containing compounds, neodymium phosphate and neodymium carboxylate are more preferable, and in particular, neodymium branch such as neodymium 2-ethylhexanoate, neodymium neodecanoate, neodymium versatate, etc. Carboxylate is most preferred.

  The component (a) may be a reaction product of the rare earth element-containing compound and a Lewis base. The reaction product has improved solubility of the rare earth element-containing compound in the solvent due to the Lewis base, and can be stably stored for a long period of time. In order to easily solubilize the rare earth element-containing compound in a solvent and to store stably for a long period of time, the Lewis base is used in a proportion of 0 to 30 mol, preferably 1 to 10 mol, per mol of rare earth element. Or as a mixture of the two or as a product obtained by reacting both in advance. Here, examples of the Lewis base include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, and a monovalent or divalent alcohol.

  The rare earth element-containing compound as the component (a) described above or the reaction product of these compounds and a Lewis base can be used singly or as a mixture of two or more.

  In the present invention, the organoaluminum compound represented by the above general formula (10) that is the component (b) of the catalyst system used for the polymerization of the terminal active polymer includes trimethylaluminum, triethylaluminum, tri-n-propylaluminum, Triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propyl hydride Aluminum, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, diisohexylaluminum hydride, dioctylaluminum hydride, hydrogenated Isooctyl aluminum, ethyl aluminum dihydride, n- propyl aluminum dihydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as component (b) described above can be used alone or in combination of two or more.

  In the present invention, the component (c) of the catalyst system used for the polymerization of the terminally active polymer is at least selected from the group consisting of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen. It is a kind of halogen compound.

The Lewis acid has Lewis acidity and is soluble in hydrocarbons. Specifically, methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide, butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylbromide Aluminum, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquibromide, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, Examples include antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, and silicon tetrachloride. Of these, diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide are preferred.
Alternatively, a reaction product of an alkylaluminum and a halogen such as a reaction product of triethylaluminum and bromine can be used.

  Examples of the metal halide constituting the complex compound of the above metal halide and Lewis base include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred.

  Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.

The Lewis base is usually reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
Examples of the organic compound containing the active halogen include benzyl chloride.

  Examples of the aluminoxane as component (d) include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, chloroaluminoxane, and the like. By adding aluminoxane as the component (d), the molecular weight distribution becomes sharp and the activity as a catalyst is improved.

The amount or composition ratio of each component of the catalyst system used in the present invention is appropriately selected according to its purpose or necessity. Of these, the component (a) is preferably used in an amount of 0.00001 to 1.0 mmol, more preferably 0.0001 to 0.5 mmol, per 100 g of 1,3-butadiene. By making the amount of component (a) used within the above range, excellent polymerization activity can be obtained, and the need for a deashing step is eliminated.
Moreover, the ratio of (a) component and (b) component is molar ratio, (a) component: (b) component is usually 1: 1-1: 700, Preferably it is 1: 3-1: 500.
Furthermore, the ratio of the halogen in the component (a) and the component (c) is, as a molar ratio, usually 1: 0.1 to 1:30, preferably 1: 0.2 to 1:15, more preferably 1: 2.0 to 1: 5.0.
Moreover, the ratio of the aluminum in (d) component and (a) component is molar ratio, and is 1: 1-700: 1 normally, Preferably it is 3: 1-500: 1. By making the amount of these catalysts within the range of the component ratio, it is preferable because it acts as a highly active catalyst and there is no need for a step of removing the catalyst residue.
In addition to the above components (a) to (c), the polymerization reaction may be carried out in the presence of hydrogen gas for the purpose of adjusting the molecular weight of the polymer.

  As the catalyst component, in addition to the component (a), the component (b), the component (c) and the component (d) used as necessary, a conjugated diene monomer such as 1,3-butadiene may be used as necessary. A small amount, specifically, a ratio of 0 to 1000 moles per mole of the component (a) compound may be used. A conjugated diene monomer such as 1,3-butadiene as a catalyst component is not essential, but when used in combination, there is an advantage that the catalytic activity is further improved.

In the production of the catalyst, for example, the components (a) to (c) are dissolved in a solvent, and a conjugated diene monomer such as 1,3-butadiene is reacted as necessary.
In that case, the addition order of each component is not specifically limited, Furthermore, you may add aluminoxane as (d) component. From the viewpoint of improving the polymerization activity and shortening the polymerization initiation induction period, it is preferable that these components are mixed in advance, reacted and aged.
Here, the aging temperature is about 0 to 100 ° C, and preferably 20 to 80 ° C. When the temperature is less than 0 ° C, aging is not sufficiently performed, and when the temperature exceeds 100 ° C, the catalytic activity may be reduced or the molecular weight distribution may be broadened.
The aging time is not particularly limited, and can be ripened by contacting in the line before adding to the polymerization reaction tank. Usually, 0.5 minutes or more is sufficient, and stable for several days.

In the production of the conjugated diene polymer having terminal activity, in the organic solvent using the catalyst system containing the lanthanum series rare earth element-containing compound, the conjugated diene monomer alone or the conjugated diene monomer and other It can be obtained by solution polymerization of a conjugated diene monomer. Here, an inert organic solvent is used as the polymerization solvent. Examples of the inert organic solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane, saturated alicyclic hydrocarbons having 5 to 20 carbon atoms such as cyclopentane and cyclohexane, 1- Monoolefins such as butene and 2-butene, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chloro And halogenated hydrocarbons such as toluene.
Among these, a C5-C6 aliphatic hydrocarbon and alicyclic hydrocarbon are especially preferable. These solvents may be used alone or in a combination of two or more.
The monomer concentration in the solvent used for the coordination anionic polymerization is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.

  In the present invention, the temperature in the coordination anionic polymerization reaction is preferably selected in the range of -80 to 150 ° C, more preferably -20 to 120 ° C. The polymerization reaction can be carried out under generated pressure, but it is usually desirable to operate at a pressure sufficient to keep the monomer in a substantially liquid phase. That is, the pressure depends on the particular material being polymerized, the polymerization medium used and the polymerization temperature, but higher pressures can be used if desired, such pressure being a gas that is inert with respect to the polymerization reaction. Can be obtained by an appropriate method such as pressurizing.

  When the active terminus of the conjugated diene polymer having an active terminus obtained by the coordination anion polymerization reaction is modified, the hydrocarbyloxysilane compound is reacted in advance in the above-described pre-denaturation reaction step, and then silanol is obtained by hydrolysis. (I) an organic silane compound and the conjugated diene (co) polymer are bonded by performing an addition or substitution reaction on the active site in the vicinity of the characteristic group, and after the reaction, A functional group that promotes the reaction between the silanol group and the reinforcing filler or (ii) an organosilane compound having a functional group that promotes the reaction between the silanol group and the reinforcing filler facilitates the modification reaction. From the viewpoint of proceeding to.

In the above-mentioned anionic polymerization and coordination anionic polymerization, all the raw materials involved in the polymerization such as polymerization initiator, solvent, monomer, and the like have removed reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds. It is desirable to use one.
The polymerization reaction may be carried out either batchwise or continuously.
In this way, a conjugated diene polymer having an active end is obtained.

In the modification reaction step in the method for producing the modified conjugated diene polymer, the conjugated diene polymer having an active terminal obtained as described above is converted into the above general formula (8) or general formula (9). The organosilane compound represented is added to the active end of the conjugated die-based polymer, preferably in a stoichiometric amount or in excess, and reacted with the active end bound to the polymer.
The modification reaction step and the preliminary modification reaction step in the present invention are usually carried out under the same temperature and pressure conditions as in the polymerization reaction.

Next, the hydrolysis step in the method for producing the modified conjugated diene polymer will be described. In the hydrolysis step, after completion of the modification reaction step, the hydrolysis reaction is performed in the presence of water under acidic, neutral or alkaline conditions. Thereby, the hydrolyzable functional group bonded to the modified conjugated diene polymer is efficiently hydrolyzed, and a silanol group is generated at the terminal or side chain of the modified conjugated diene polymer.
The amount of water used in this hydrolysis reaction is preferably a molar amount that is excessive, for example, 2 to 4 times the molar amount of the initiator such as Li. The hydrolysis time is usually about 10 minutes to several hours.
When the hydrolysis reaction is performed under alkaline conditions, it is desirable to add an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, preferably sodium hydroxide as the basic compound, and the hydrolysis reaction under acidic conditions. In the case of carrying out, it is desirable to add as the acidic compound an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, a carboxylic acid such as acetic acid or formic acid, silicon tetrachloride or the like.

  In the present invention, a condensation reaction step for performing a condensation reaction in the presence of a condensation accelerator may be provided between the modification reaction step and the hydrolysis step or after the hydrolysis step.

The condensation accelerator used in the condensation reaction is preferably added after the modification reaction and before the start of the condensation reaction. When added before the denaturation reaction, a direct reaction with the active end may occur, and a hydrocarboxy group may not be introduced at the active end. Further, when added after the start of the condensation reaction, the condensation accelerator may not be uniformly dispersed and the catalyst performance may be lowered.
As the addition time of the condensation accelerator, when a condensation reaction step is provided between the modification reaction step and the hydrolysis step, usually 5 minutes to 5 hours after the start of the modification reaction, preferably 15 minutes to 1 hour after the start of the modification reaction. Later. When a condensation reaction step is provided after the hydrolysis step, it is usually 5 minutes to 5 hours, preferably 10 minutes to 2 hours after the start of the hydrolysis reaction.

As the condensation accelerator, one containing a metal element is preferable, and a compound containing at least one metal belonging to Groups 2 to 15 of the periodic table is more preferable.
The condensation accelerator containing the metal element preferably contains at least one selected from Ti, Sn, Bi, Zr and Al and is an alkoxide, carboxylate or acetylacetonate complex of the metal. is there.

As the condensation accelerator containing Ti as a metal component, an alkoxide of titanium (Ti), a carboxylate, and an acetylacetonate complex salt are preferably used.
Specifically, tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-methyl-1,3-hexanediolato) titanium, tetrakis (2-propyl-1,3-hexanediolato) ) Titanium, tetrakis (2-butyl-1,3-hexanediolato) titanium, tetrakis (1,3-hexanediolato) titanium, tetrakis (1,3-pentanediolato) titanium, tetrakis (2-methyl-1) , 3-pentanediolato) titanium, tetrakis (2-ethyl-1,3-pentanediolato) titanium, tetrakis (2-propyl-1,3-pentanediolato) titanium, tetrakis (2-butyl-1,3) -Pentanediolato) titanium, tetrakis (1,3-heptanediolato) titanium, tetrakis (2-methyl-1,3-heptanediolato) Titanium, Tetrakis (2-ethyl-1,3-heptanediolato) titanium, Tetrakis (2-propyl-1,3-heptanediolato) titanium, Tetrakis (2-butyl-1,3-heptanediolato) titanium, Tetrakis (2-ethylhexoxy) Titanium, tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy titanium oligomer, tetraisobutoxy titanium, tetra-sec-butoxy titanium, tetra -Tert-butoxy titanium, bis (oleate) bis (2-ethylhexanoate) titanium, titanium dipropoxy bis (triethanolamate), titanium dibutoxy bis (triethanolamate), titanium tributoxy Tearate, titanium tripropoxy systemate, titanium tripropoxyacetylacetonate, titanium dipropoxybis (acetylacetonate), titanium tripropoxy (ethylacetoacetate), titanium propoxyacetylacetonatebis (ethylacetoacetate), titanium tributoxyacetyl Acetonate, titanium dibutoxy bis (acetylacetonate), titanium tributoxyethyl acetoacetate, titanium butoxyacetylacetonate bis (ethyl acetoacetate), titanium tetrakis (acetylacetonate), titanium diacetylacetonate bis (ethyl acetoacetate) Bis (2-ethylhexanoate) titanium oxide, bis (laurate) titanium oxide, bis (naphthenate) titanium oxide Id, bis (stearate) titanium oxide, bis (oleate) titanium oxide, bis (linoleate) titanium oxide, tetrakis (2-ethylhexanoate) titanium, tetrakis (laurate) titanium, tetrakis (naphthenate) titanium, tetrakis (stear) Rate) titanium, tetrakis (oleate) titanium, tetrakis (linoleate) titanium, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium oxide bis (stearate), titanium oxide bis (tetramethylheptanedionate) ), Titanium oxide bis (pentanedionate), titanium tetra (lactate), and the like.
Of these, tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-ethylhexoxy) titanium, and titanium di-n-butoxide (bis-2,4-pentanedionate) are preferable.

As a condensation accelerator containing Sn as a metal component, a tin compound having an oxidation number of 2 represented by Sn (OCOR ³¹ ) ₂ (wherein R ³¹ is an alkyl group having 2 to 19 carbon atoms), R ³² _x SnA ⁵ _y B ¹ _4-yx oxidation number 4 tin compound (wherein R ³² is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, x is an integer of 1 to 3, y is 1 or 2) , A ⁵ is a carboxyl group having 2 to 30 carbon atoms, a β-dicarbonyl group having 5 to 20 carbon atoms, a hydrocarbyloxy group having 3 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms and / or 1 carbon atom. A group selected from siloxy groups tri-substituted with ˜20 hydrocarbyloxy groups, B ¹ is a hydroxyl group or a halogen).

  More specifically, the tin carboxylate includes divalent tin dicarboxylate, tetravalent dihydrocarbyltin dicarboxylate (including bis (hydrocarbyldicarboxylic acid) salt), bis (β -Diketonate), alkoxy halide, monocarboxylate hydroxide, alkoxy (trihydrocarbylsiloxide), alkoxy (dihydrocarbylalkoxysiloxide), bis (trihydrocarbylsiloxide), bis (dihydrocarbylalkoxysiloxide), etc. It can be used suitably. The hydrocarbyl group bonded to tin preferably has 4 or more carbon atoms, and particularly preferably has 4 to 8 carbon atoms.

  Moreover, the following (a)-(e) is mentioned as a condensation promoter (for example, alkoxide, carboxylic acid, or acetylacetonate complex salt of these metals) which contains Zr, Bi, or Al as a metal component.

(A) Bismuth carboxylate (b) Zirconium alkoxide (c) Zirconium carboxylate (d) Aluminum alkoxide (e) Aluminum carboxylate

  Specifically, tris (2-ethylhexanoate) bismuth, tris (laurate) bismuth, tris (naphthenate) bismuth, tris (stearate) bismuth, tris (oleate) bismuth, tris (linoleate) bismuth,

Tetraethoxyzirconium, tetran-propoxyzirconium, tetraisopropoxyzirconium, tetran-butoxyzirconium, tetrasec-butoxyzirconium, tetratert-butoxyzirconium, tetra (2-ethylhexoxy) zirconium, zirconium tributoxy systemate, zirconium tributoxy Acetyl acetonate, zirconium butoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis (ethylacetoacetate), zirconium tetrakis (acetylacetonate), zirconium diacetylacetonate bis (ethylacetoacetate) Bis (2-ethylhexanoate) zirconium oxide Bis (laurate) zirconium oxide, bis (naphthenate) zirconium oxide, bis (stearate) zirconium oxide, bis (oleate) zirconium oxide, bis (linoleate) zirconium oxide, tetrakis (2-ethylhexanoate) zirconium, tetrakis ( Laurate) zirconium, tetrakis (naphthenate) zirconium, tetrakis (stearate) zirconium, tetrakis (oleate) zirconium, tetrakis (linoleate) zirconium,

Triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, trisec-butoxyaluminum, tritert-butoxyaluminum, tri (2-ethylhexoxy) aluminum, aluminum dibutoxy systemate, aluminum dibutoxy Acetylacetonate, aluminum butoxybis (acetylacetonate), aluminum dibutoxyethyl acetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), tris (2-ethylhexanoate) aluminum, tris (laurate) ) Aluminum, Tris (naphthenate) aluminum, Tris (stearate) aluminum, Tris (olee) G) aluminum, tris (linolate) aluminum, and the like.

  Among these, tris (2-ethylhexanoate) bismuth, tetra n-propoxyzirconium, tetra n-butoxyzirconium, bis (2-ethylhexanoate) zirconium oxide, bis (oleate) zirconium oxide, triisopropoxy Aluminum, trisec-butoxyaluminum, tris (2-ethylhexanoate) aluminum, tris (stearate) aluminum, zirconium tetrakis (acetylacetonate), and aluminum tris (acetylacetonate) are preferred.

  The amount (consumption amount) of the condensation accelerator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component in the rubber composition described later, and is 0.5 to 5 parts by mass. Part is more preferred. By setting the use amount of the condensation accelerator within the above range, the condensation reaction proceeds efficiently.

  The condensation reaction is preferably carried out in an aqueous solution, and the temperature during the condensation reaction is preferably 85 to 180 ° C, more preferably 100 to 170 ° C, and particularly preferably 110 to 150 ° C. By setting the temperature during the condensation reaction within the above range, the condensation reaction can be progressed and completed efficiently, and the deterioration of the quality due to the aging reaction of the polymer due to changes over time of the resulting modified conjugated diene polymer is suppressed. Can do.

The condensation reaction time is preferably about 5 minutes to 10 hours, more preferably about 15 minutes to 5 hours. By setting the condensation reaction time within the above range, the condensation reaction can be completed smoothly.
The pressure of the reaction system during the condensation reaction is preferably 0.01 to 20 MPa, more preferably 0.05 to 10 MPa.
There is no restriction | limiting in particular about the form of a condensation reaction, You may carry out by a continuous type using apparatuses, such as a batch type reactor and a multistage continuous type reactor. Moreover, you may perform this condensation reaction and desolvation simultaneously.

After completing the hydrolysis step or the hydrolysis step and the condensation reaction step, an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) is added to the polymerization reaction system to stop the polymerization reaction. To do.
Thereafter, the modified conjugated diene polymer is obtained through a desolvation process such as steam stripping, which lowers the partial pressure of the solvent by blowing water vapor, and a vacuum drying process.
Here, in the modification reaction step, when the hydrocarbyloxysilane compound having a protected primary amino group is used as the organic silane compound represented by the general formula (9), the hydrolysis step, steam stripping, etc. described above are used. In the desolvation treatment step using water vapor, deprotection treatment is performed simultaneously to remove the protected nitrogen atom protecting group to produce a primary amino group. From the hydrocarbyloxysilane compound, it is converted to the free primary amino group by hydrolyzing the protecting group on the primary amino group by various methods as needed at any stage until it becomes a dry polymer. The deprotection treatment of the protected primary amino group can be performed.

  In the rubber composition used in the tire of the present invention, the rubber component used as the component (A) is a modified conjugate having a structure represented by the general formula (6) or (7) obtained as described above. It contains 10% by mass or more of diene polymer. The rubber component that can be contained in a proportion of 90% by mass or less includes diene rubber such as polybutadiene, polyisoprene, polybutadiene-polyisoprene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, Examples thereof include styrene-isoprene-butadiene terpolymer, ethylene-propylene-diene terpolymer, butyl rubber, and halogenated butyl rubber.

The rubber composition used for the tire of the present invention contains a reinforcing filler as the component (B).
[(B) Reinforcing filler]
In the rubber composition, the reinforcing filler used as the component (B) contains at least silica, and the silica content in the reinforcing filler is preferably 20% by mass or more, and 40% by mass or more. More preferably, 60 mass% or more is further more preferable.
The reinforcing filler that can be used in combination with the silica is preferably carbon black, but inorganic reinforcing fillers other than silica can also be used.

(silica)
In the present invention, any commercially available silica can be used as the reinforcing filler, and wet silica, dry silica, and colloidal silica are particularly preferable, and wet silica is particularly preferable. The BET specific surface area (measured according to ISO 5794/1) of silica is preferably 100 m ² / g or more, more preferably 150 m ² / g or more, particularly preferably 170 m ² / g or more. Examples of such silica are those manufactured by Tosoh Silica Co., Ltd., trade names “Nipsil AQ” (BET specific surface area = 190 m ² / g), “Nipsil KQ”, and Degussa's trade name “Ultra Gil VN3” (BET specific surface area = 175 m ^2. / G) and other commercial products can be used.
This silica may be used individually by 1 type, and may be used in combination of 2 or more type.

(Carbon black)
The carbon black that can be used in combination with the silica is not particularly limited. For example, GPF, FEF, SRF, HAF, N339, IISAF, ISAF, SAF, and the like are used, and a nitrogen adsorption specific surface area (N ₂ SA, JIS K 6217- 2: measured in accordance with 2001) is preferably ²⁰ to 250 m ² / g. This carbon black may be used individually by 1 type, and may be used in combination of 2 or more type.

(Inorganic reinforcing fillers other than silica)
As the inorganic reinforcing filler other than silica, a compound represented by the following general formula (13) can be used.
dM ³ · xSiO _y · zH ₂ O (13)
Here, in the general formula (13), M ³ is a metal selected from the group consisting of aluminum, magnesium, titanium, calcium, and zirconium, an oxide or hydroxide of these metals, and a hydrate thereof. Or at least one selected from carbonates of these metals, and d, x, y and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10 is there.
In the general formula (13), when both x and z are 0, the inorganic compound is at least one metal, metal oxide or metal hydroxide selected from aluminum, magnesium, titanium, calcium and zirconium. It becomes.
As the inorganic filler represented by the general formula (13), .gamma.-alumina, alumina (Al ₂ O ₃₎ such as α- alumina, boehmite, alumina monohydrate such as diaspore (Al ₂ O ₃ · H ₂ O), Gibbsite, Bayerite, etc. Aluminum hydroxide [Al (OH) ₃ ], Aluminum carbonate [Al ₂ (CO ₃ ) ₂ ], Magnesium hydroxide [Mg (OH) ₂ ], Magnesium oxide (MgO), Carbonic acid Magnesium (MgCO ₃ ), talc (3MgO · 4SiO ₂ · H ₂ O), attapulgite (5MgO · 8SiO ₂ · 9H ₂ O), titanium white (TiO ₂ ), titanium black (TiO _2n-1 ), calcium oxide (CaO ), calcium hydroxide [Ca (OH) _2], magnesium aluminum oxide _{(MgO · Al 2 O 3)} , clay _{(Al 2 O 3 · 2SiO 2} ), kaolin _{Al 2 O 3 · 2SiO 2 ·} 2H 2 O), pyrophyllite _{(Al 2 O 3 · 4SiO 2} · H 2 O), bentonite _{(Al 2 O 3 · 4SiO 2} · 2H 2 O), aluminum silicate (Al ₂ SiO ₅ , Al ₄ .3SiO ₄ .5H ₂ O, etc.), magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ etc.), calcium silicate (Ca ₂ · SiO ₄ etc.), aluminum calcium silicate (Al ₂ O ₃ · CaO · 2SiO ₂ etc.), magnesium calcium silicate (CaMgSiO ₄ ), calcium carbonate (CaCO ₃ ), zirconium oxide (ZrO ₂ ), zirconium hydroxide [ZrO (OH) ₂ · nH ₂ O], zirconium carbonate [ Zr (CO _{3) 2],} hydrogen to correct electric charge as various zeolites, such as crystalline aluminosilicates including alkali metal or alkaline earth metal You can use. Further, it is preferable that M ³ in the general formula (13) is at least one selected from aluminum metal, aluminum oxide or hydroxide, hydrates thereof, and aluminum carbonate.
These inorganic compounds represented by the general formula (13) may be used alone or in combination of two or more. The average particle diameter of these inorganic reinforcing fillers is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 5 μm, from the viewpoint of kneading workability, wear resistance and wet grip performance balance. More preferred.

  In the rubber composition used for the tire of the present invention, in order to satisfy low heat build-up, wear resistance and wet grip performance, the content of the silica is (A) 100 parts by mass of the rubber component. A range of 10 to 150 parts by mass is preferred.

[(C) Silane coupling agent]
In the rubber composition used for the tire of the present invention, the silane coupling agent used as the component (C) includes the following (c-1) compound, (c-2) compound, (c-3) compound, ( At least one compound selected from c-4) compounds and (c-5) compounds is used.

((C-1) Compound)
As the compound (c-1), the following general formula (1)

［式中、Ｒ¹⁵は−Ｃｌ、−Ｂｒ、Ｒ²⁰Ｏ−、Ｒ²⁰Ｃ（＝Ｏ）Ｏ−、Ｒ²⁰Ｒ²¹Ｃ＝ＮＯ−、Ｒ²⁰Ｒ²¹Ｎ−又は−（ＯＳｉＲ²⁰Ｒ²¹）_m（ＯＳｉＲ¹⁹Ｒ²⁰Ｒ²¹）（ただし、Ｒ²⁰及びＲ²¹は、それぞれ独立に水素原子又は炭素数１〜１８の一価の炭化水素基である。）、Ｒ¹⁶はＲ¹⁵、水素原子又は炭素数１〜１８の一価の炭化水素基、Ｒ¹⁷はＲ¹⁵、Ｒ¹⁶又は−［Ｏ（Ｒ²²Ｏ）_a］_0.5−基（ただし、Ｒ²²は炭素数１〜１８のアルキレン基、ａは１〜４の整数である。）、Ｒ¹⁸は炭素数１〜１８の二価の炭化水素基、Ｒ¹⁹ は炭素数１〜１８の一価の炭化水素基を示し、ｘ、ｙ及びｚは、ｘ＋ｙ＋２ｚ＝３、０≦ｘ≦３、０≦ｙ≦２、０≦ｚ≦１の関係を満たす数である。］
で表されるシランカップリング剤が用いられる。
前記一般式（１）において、炭素数１〜１８の一価の炭化水素基としては、例えば炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数６〜１８のアリール基、炭素数７〜１８のアラルキル基等を挙げることができる。ここで、上記アルキル基及びアルケニル基は直鎖状、枝分かれ状、環状のいずれであってもよく、前記アリール基及びアラルキル基は、芳香環上に低級アルキル基などの置換基を有していてもよい。

[Wherein R ¹⁵ represents —Cl, —Br, R ²⁰ O—, R ²⁰ C (═O) O—, R ²⁰ R ²¹ C═NO—, R ²⁰ R ²¹ N— or — (OSiR ²⁰ R ^{21 _{) m (OSiR 19 R 20 R}} 21) ( provided that, R ²⁰ and R ²¹ are each independently a hydrogen atom or a C1-18 monovalent hydrocarbon group.), R ¹⁶ is R ^15, hydrogen An atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, R ¹⁷ is R ¹⁵ , R ¹⁶ or — [O (R ²² O) _a ] _0.5 — group (where R ²² is alkylene having 1 to 18 carbon atoms) Group, a is an integer of 1 to 4), R ¹⁸ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ¹⁹ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, x, y and z are numbers satisfying the relationship of x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, and 0 ≦ z ≦ 1. ]
The silane coupling agent represented by these is used.
In the general formula (1), examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms. And an aralkyl group having 7 to 18 carbon atoms. Here, the alkyl group and alkenyl group may be linear, branched or cyclic, and the aryl group and aralkyl group have a substituent such as a lower alkyl group on the aromatic ring. Also good.

In the general formula (1), the alkylene group having 1 to 18 carbon atoms represented by R ²² may be linear, branched, or cyclic, and is preferably linear. is there. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group.
Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms represented by R ¹⁸ include an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, and a cycloalkylene having 5 to 18 carbon atoms. Group, a cycloalkylalkylene group having 6 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, and an aralkylene group having 7 to 18 carbon atoms. The alkylene group and alkenylene group may be linear or branched, and the cycloalkylene group, cycloalkylalkylene group, arylene group, and aralkylene group may have a substituent such as a lower alkyl group on the ring. You may have.
As R ¹⁸ , an alkylene group having 1 to 6 carbon atoms is preferable, and a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group is particularly preferable. it can.

Examples of the silane coupling agent represented by the general formula (1) include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3 -Lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexa Noylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2- Kuta Neu Lucio ethyltrimethoxysilane, 2- deca Neu thio ethyltrimethoxysilane, and the like of 2-lauroyl thio ethyltrimethoxysilane.
Among these silane coupling agents, the following formula (1-1)

で表される３−オクタノイルチオプロピルトリエトキシシランは、商標「ＮＸＴ」としてＧｅｎｅｒａｌ Ｅｌｅｃｔｒｉｃ社が上市している。
本発明におけるゴム組成物に、当該（ｃ−１）シランカップリング剤を用いることにより、ゴム加工時の作業性に優れると共に、ウェットグリップ性能及び耐摩耗性の良好な空気入りタイヤを与えることができる。

Is sold by General Electric under the trademark “NXT”.
By using the (c-1) silane coupling agent in the rubber composition of the present invention, it is possible to provide a pneumatic tire having excellent workability during rubber processing and good wet grip performance and wear resistance. it can.

((C-2) Compound)
As the compound (c-2), the following general formula (2)

[式中Ｒ²³は炭素数１〜２０の直鎖もしくは、分岐、環状のアルキル基であり、Ｇはそれぞれ独立して炭素数１〜９のアルカンジイル基又はアルケンジイル基であり、Ｚ^aはそれぞれ独立して二つの珪素原子と結合することのできる基で、 [−Ｏ−]_0.5、[−Ｏ−Ｇ−]_0.5又は[−Ｏ−Ｇ−Ｏ−] _0.5から選ばれる基であり、Ｚ^bはそれぞれ独立して二つの珪素原子と結合することのできる基で、 [−Ｏ−Ｇ−Ｏ−] _0.5で表される官能基であり、Ｚ^cはそれぞれ独立して−Ｃｌ、−Ｂｒ、−ＯＲ²⁴、Ｒ²⁴Ｃ(＝Ｏ)Ｏ−、Ｒ²⁴Ｒ²⁵Ｃ＝ＮＯ−、Ｒ²⁴Ｒ²⁵Ｎ−，Ｒ²⁴−，ＨＯ−Ｇ−Ｏ−で表される官能基であり、Ｒ，Ｇは上記表記と一致する。
ｍ、ｎ、ｕ、ｖ、ｗはそれぞれ独立して１≦ｍ≦２０、０≦ｎ≦２０、０≦ｕ≦３、０≦ｖ≦２、０≦ｗ≦１であり、かつ１／２ｕ＋ｖ＋２ｗ＝２又は３である。
Ａ部が複数である場合、複数のＡ部におけるＺ^a _u、Ｚ^b _v及びＺ^c _wそれぞれにおいて、同一でも異なっていてもよく、Ｂが複数である場合、複数のＢ部におけるＺ^a _u、Ｚ^b _v及びＺ^c _wそれぞれにおいて、同一でも異なってもよい。]
で表されるシランカップリング剤が用いられる。

[Wherein R ²³ is or straight chain having 1 to 20 carbon atoms, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a are each independently a group capable of binding with two silicon _{atoms, [-O-] 0. 5, [} - O-G-] is a group selected from _0.5, or [-O-G-O-] _0.5 , Z ^b each independently represents a group capable of bonding to two silicon atoms, and is a functional group represented by [—O—G—O—] _0.5 , and Z ^c each independently represents —Cl, ^{-Br, -OR 24, R 24 C} (= O) O-, R 24 R 25 C = NO-, R 24 R 25 N-, R 24 -, a functional group represented by HO-G-O- Yes, R and G agree with the above notation.
m, n, u, v, and w are independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, and 1 / 2u + v + 2w = 2 or 3.
When there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, Z ^a _u in the plurality of B parts , Z ^b _v and Z ^c _w may be the same or different. ]
The silane coupling agent represented by these is used.

  Specific examples of the silane coupling agent represented by the general formula (2) include the following formula (2-1), formula (2-2), or formula (2-3).

［式中Ｌはそれぞれ独立して炭素数１〜９のアルカンジイル基又はアルケンジイル基を示し、ｘは１〜２０の数、ｙは０〜２０の数を示す。］
で示される構造を有するシランカップリング剤を挙げることができる。
上記式（２−１）で表されるシランカップリング剤としては、Ｍｏｍｅｎｔｉｖｅ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ社が、商標「ＮＸＴ Ｌｏｗ−Ｖ Ｓｉｌａｎｅ」として、また、式（２−２）で表されるシランカップリング剤としては、Ｍｏｍｅｎｔｉｖｅ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ社が、商標「ＮＸＴ Ｕｌｔｒａ Ｌｏｗ−Ｖ Ｓｉｌａｎｅ」として、さらに、化学式（２−３）で表されるシランカップリング剤としては、Ｍｏｍｅｎｔｉｖｅ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ社が、商標、「ＮＸＴ_-Ｚ」として上市している。

[In formula, L shows a C1-C9 alkanediyl group or alkenediyl group each independently, x shows the number of 1-20, y shows the number of 0-20. ]
The silane coupling agent which has a structure shown by can be mentioned.
As the silane coupling agent represented by the above formula (2-1), Momentive Performance Materials, Inc. has the trademark “NXT Low-V Silane” and the silane coupling agent represented by the formula (2-2). the, Momentive Performance Materials Inc., under the trademark "NXT Ultra Low-V silane" further, as the silane coupling agent represented by the chemical formula (2-3), Momentive Performance Materials Inc., trade, "NXT _- It is marketed as “Z”.

  In the silane coupling agent represented by the general formula (1) and the general formula (2), since the mercapto group is protected, it is necessary to perform deprotection to couple the polymer, and thus DPG (diphenylguanidine). It is preferable to mix a proton donor typified by) in the final kneading step as a deprotecting agent. The amount used is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, per 100 parts by weight of the rubber component (A).

((C-3) Compound)
As the compound (c-3), the following general formula (3)
R ^1a R ^2a R ^3a Si-R ^4a -SH (3)
[Wherein, R ^1a represents a methyl group or an ethyl group, R ^2a represents a methoxy group, an ethoxy group, or —O— (YO) _m —X, Y represents a divalent hydrocarbon group, and X represents a carbon number of 1 -15 alkyl groups, m is a number from 1-40. R ^3a represents a methyl group, an ethyl group or R ^2a , and R ^4a represents a divalent hydrocarbon group having 1 to 12 carbon atoms. ]
The silane coupling agent represented by these is used.
In the general formula (3), Y represents a linear or branched saturated or unsaturated divalent hydrocarbon group, for example, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ )-, -CH ₂ CH ₂ CH _2- and the like. m is a number of 1 to 40, preferably 3 to 25, more preferably 4 to 20, and still more preferably 10 to 20.
The divalent hydrocarbon group having 1 to 12 carbon atoms represented by R ^4a may be, for example, any of an alkylene group, an alkenylene group, an arylene group, and an aralkylene group. Specifically, CH ₂ , CH ₂ CH _{2 , CH 2 CH 2 CH 2,} CH 2 CH 2 CH 2 CH 2, CH (CH 3), CH 2 CH (CH 3), CH (CH 3) CH 2, C (CH 3) 2, CH (C 2 H ₅ ), CH ₂ CH ₂ CH (CH ₃ ), CH ₂ CH (CH ₃ ) CH _{2 and the} like.
As the silane coupling agent represented by the general formula (3), those in which R ^2a is —O (YO) _m —X and X is an alkyl group having 6 to 15 carbon atoms are preferable. For example, the following formula (3-1)

で表されるシランカップリング剤を挙げることができる。
この式（３−１）で表されるシランカップリング剤は、デグッサ社が、商標「Ｓｉ３６３」として上市している。

The silane coupling agent represented by these can be mentioned.
The silane coupling agent represented by the formula (3-1) is marketed by Degussa under the trademark “Si363”.

((C-4) Compound)
As the compound (c-4), the following general formula (4)
_{^{(R 31 O) 3-p}} (R 32) p Si-R 33 -S m -R 34 -S m -R 33 -Si (R 32) p (OR 31) 3-p ··· (4)
[R ³¹ and R ³² are each a hydrocarbon group having 1 to 4 carbon atoms, R ³³ is a divalent hydrocarbon group having 1 to 15 carbon atoms, p is an integer of 0 to 2, m is an average value of 1 or more and 4 below, R ³⁴ is ^{-S-R 35 -S -, -} R 36 -S x -R 37 -, or ^{_{-R 38 -S y -R 39 -S z}} -R 40 - (R 35 ~R 40 carbon A divalent hydrocarbon group of 1 to 20 or a divalent organic group containing a hetero element other than S and O, which may be the same or different, and each of x, y and z is 1 or more as an average value Less than 4.]
The silane coupling agent represented by these is used.

The silane coupling agent represented by the general formula (4) is a compound having an organooxysilyl group at both ends of the molecule and a sulfide or polysulfide at the center of the molecule.
In the general formula (4), R ³¹ and R ³² are each a hydrocarbon group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Group, t-butyl group, vinyl group, allyl group, isopropenyl group and the like. Incidentally, R ³¹ and R ³² may be the same or different. R ³³ is a divalent hydrocarbon group having 1 to 15 carbon atoms, for example, methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, hexylene group, decylene group, phenylene group, Examples thereof include a methylphenylethylene group. p shows the integer of 0-2, m is 1 or more and less than 4 as an average value. m may have an average value within this range, or may be a mixture of a plurality of silane compounds having different m. From the viewpoint of the effect of the present invention, m is preferably 1 or more and less than 2 as an average value, and more preferably m is 1.

R ^{34 in the} general formula (4) is represented by —S—R ³⁵ —S—, —R ³⁶ —S _x —R ³⁷ —, or —R ³⁸ —S _y —R ³⁹ —S _z —R ⁴⁰ —. a divalent functional group, but from the viewpoint of the effect of the present _{^{invention, -R 38 -S y -R 39 -S}} z -R 40 - is preferably.
Here, R ^{35 to} R ⁴⁰ are linear or branched divalent hydrocarbon groups having 1 to 20 carbon atoms, divalent aromatic groups, or divalent organic groups containing hetero elements other than sulfur and oxygen. For example, methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, hexylene group, decylene group, phenylene group, methylphenylethylene group and the like, and nitrogen which is a hetero element other than sulfur and oxygen, Examples thereof include a group into which phosphorus or the like has been introduced. R ^{35 to} R ^{40 in} R ³⁴ in the general formula (4) may be the same or different, and are preferably a hexylene group from the viewpoint of the effect of the present invention and the production cost.
R ³⁴ must contain a sulfur atom, and x, y, and z are 1 or more and less than 4 as average values. From the viewpoint of the effect of the present invention, x, y, and z are each 2 or more as average values. It is preferably less than 4, more preferably 2 or more and 3 or less.

The (c-4) silane coupling agent preferably has a purity of 60% or more at the time of blending, more preferably 70% or more, and particularly preferably 80% or more.
In addition, the (c-4) silane coupling agent may produce a multimer such as a dimer or a trimer of the general formula (4) at the time of production, and 3 or more of these in one molecule. The silane coupling agent containing a silicon atom may adversely affect the effects of the present invention. In the present invention, when the (c-4) silane coupling agent is blended, the content of the compound having 3 or more silicon atoms per molecule is 30% by mass or less based on the rubber composition. More preferably, it is most preferably 10% by mass or less, and most preferably not substantially contained.

((C-5) Compound)
As said (c-5) compound, following General formula (5)

［式中、Ｒ⁴¹は炭素数１〜４のアルキル基又は炭素数２〜８のアルコキシアルキル基を示し、Ｒ⁴²及びＲ⁴³は、それぞれ独立に炭素数１〜６のアルキル基又はフェニル基、あるいはその一つがＲ⁴¹Ｏを示し、各Ｒ⁴¹Ｏは同一でも異なっていてもよく、ｘは３〜５の数である。］
で表されるシランカップリング剤が用いられる。
前記一般式（５）において、Ｒ⁴¹の内の炭素数１〜４のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基及びｔｅｒｔ−ブチル基が挙げられ、一方、炭素数２〜８のアルコキシアルキル基としては、メトキシエチル基、メトキシプロピル基、メトキシブチル基、エトキシエチル基、エトキシプロピル基、エトキシブチル基などを挙げることができる。
Ｒ⁴²及びＲ⁴³は、それぞれ独立に、炭素数１〜６のアルキル基又はフェニル基、あるいはその一つがＲ⁴¹Ｏである。上記炭素数１〜６のアルキル基としては、メチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、各種ペンチル基、各種ヘキシル基を挙げることができる。

[Wherein, R ⁴¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms, and R ⁴² and R ⁴³ each independently represents an alkyl group or phenyl group having 1 to 6 carbon atoms, Alternatively, one of them represents R ⁴¹ O, each R ⁴¹ O may be the same or different, and x is a number from 3 to 5. ]
The silane coupling agent represented by these is used.
In the general formula (5), the alkyl group having 1 to 4 carbon atoms in R ⁴¹ is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. On the other hand, examples of the alkoxyalkyl group having 2 to 8 carbon atoms include a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxyethyl group, an ethoxypropyl group, and an ethoxybutyl group. Can do.
R ⁴² and R ⁴³ are each independently an alkyl group having 1 to 6 carbon atoms or a phenyl group, or one of them is R ⁴¹ O. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, and various hexyl groups. be able to.

  Specific examples of the silane coupling agent represented by the general formula (5) include, for example, bis [3- (ethoxydimethylsilyl) propyl] tetrasulfide, bis [3- (ethoxydiethylsilyl) propyl] tetrasulfide, bis [3- (diethoxymethylsilyl) propyl] tetrasulfide, bis [3- (diethoxyethylsilyl) propyl] tetrasulfide and the like can be mentioned.

In the present invention, the silane coupling agent of the component (C) described above may be used alone or in combination of two or more, and the blending amount is the effect of the present invention. That is, in order to satisfy both the low heat generation property, the wear resistance and the wet grip performance, it is selected in the range of 1 to 25 parts by mass with respect to 100 parts by mass of the (A) rubber component.
In addition, when a rubber composition having good processability is obtained by suppressing the generation of volatile organic compounds (VOC) during work as much as possible, the generation of VOCs as the silane coupling agent of the component (C) It is preferable that there is no or very little even if it occurs.
Examples of such a silane coupling agent include the compound (c-2) represented by the above formula (2-2) and formula (2-3), and the general formula (3), and R ^2a is -O (YO) _m- X, wherein X is an alkyl group having 6 to 15 carbon atoms, and includes at least one selected from compounds (c-3).

[Preparation of rubber composition]
The rubber composition used in the tire of the present invention is preferably sulfur crosslinkable, and sulfur is suitably used as a vulcanizing agent. As the amount used, it is preferable to blend 0.1 to 10 parts by mass of sulfur (total amount of sulfur and sulfur donors) with respect to 100 parts by mass of the rubber component. This is because within this range, the necessary elastic modulus and strength of the vulcanized rubber composition can be ensured and fuel efficiency can be obtained. In this respect, it is more preferable to incorporate 0.2 to 8 parts by mass of the sulfur content.

  In the rubber composition, the (A) component, the (B) component, the (C) component, the vulcanizing agent, and various kinds usually used in the rubber industry as desired, as long as the object of the present invention is not impaired. Chemicals such as vulcanizing agents other than sulfur, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scorching agents, zinc white, stearic acid, thermosetting resins, thermoplastic resins and the like can be included. .

  The vulcanization accelerator that can be used in the present invention is not particularly limited, and examples thereof include M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazyl). Sulfenamide) and other guanidine vulcanization accelerators such as DPG (diphenylguanidine) can be used, and the amount used is 0.1-5. 0 mass part is preferable, More preferably, it is 0.2-3.0 mass part.

  Examples of the process oil used as a softening agent that can be used in the rubber composition of the present invention include paraffinic, naphthenic, and aromatic oils. Aromatics are used for applications that emphasize tensile strength and wear resistance, and naphthenic or paraffinic systems are used for applications that emphasize hysteresis loss and low-temperature characteristics. The amount used is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component, and if it is 100 parts by mass or less, the deterioration of the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber is suppressed. can do.

  Furthermore, examples of the anti-aging agent that can be used in the rubber composition of the present invention include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine, 6C [N- (1,3-dimethylbutyl) -N′- Phenyl-p-phenylenediamine], AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), high-temperature condensate of diphenylamine and acetone, etc. The amount used is rubber. 0.1-6.0 mass parts is preferable with respect to 100 mass parts of components, More preferably, it is 0.3-5.0 mass parts.

The rubber composition can be prepared by kneading the above components using a kneader such as an open kneader such as a roll or a closed kneader such as a Banbury mixer.
The rubber composition thus obtained satisfies low heat build-up, wear resistance and wet grip performance, prevents generation of volatile organic compounds (VOC) during work, and has good processability. It is.

[tire]
The tire of the present invention is characterized by using the above-described rubber composition for a tread. A tire using the rubber composition as a tread is a tire satisfying low heat buildup, wear resistance, and wet grip performance. In addition, as gas with which the tire of the present invention is filled, normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen is exemplified. When the rubber composition is used for a tread, for example, the rubber composition is extruded into a tread member, and is pasted and molded by a usual method on a tire molding machine to form a raw tire. The green tire is heated and pressed in a vulcanizer to obtain a tire.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the various characteristics in each example were calculated | required by the method shown below.
(1) Bonded vinyl content and bound styrene content of unmodified or modified styrene-butadiene rubber (SBR) (a) Bonded vinyl content of conjugated diene moiety (mol% relative to the total diene moiety)
Obtained by 270 MHz ¹ H-NMR.
(B) Bonded styrene content (mass% in polymer)
Obtained by 270 MHz ¹ H-NMR.
(2) Weight average molecular weight (Mw) of unmodified or modified SBR
It measured using GPC [the Tosoh make, HLC-8020] using the refractometer as a detector, and showed it by polystyrene conversion which used the monodisperse polystyrene as the standard. The column is GMHXL [manufactured by Tosoh], and the eluent is tetrahydrofuran.
(3) Tire performance evaluation (tire size 195 / 65R15)
(A) Rolling resistance Rolling resistance is obtained when a tire is rotated at a speed of 80 km under the action of a load of 4500 N (460 kg) using a rotating drum having an outer diameter of 1707.6 mm and a width of 350 mm having a steel smooth surface. Measured by lameness method.
(B) Abrasion resistance After traveling 10,000 km on a paved road surface with a real vehicle, the remaining groove was measured, and the distance traveled for 1 mm of wear on the tread was compared.
Equivalent). The larger the index, the better the wear resistance.
(C) Wet grip performance Measure the braking distance from the initial speed of 40, 60, 80 km / hr on the wet asphalt road surface. The index was calculated by the braking distance of Comparative Example 1 / the braking distance of the test tire × 100, and the index was expressed as an average of the three levels. Therefore, the larger the number, the better.

Synthesis Example 1 (Synthesis of organosilane compound a used in modification step)
In a nitrogen atmosphere, 36 g of 3-aminopropylmethyldiethoxysilane (manufactured by Gelest) was added as an aminosilane moiety to 400 ml of dichloromethane solvent in a glass flask equipped with a stirrer, and trimethylsilane chloride (Aldrich) was further added as a protective moiety. 48 ml and 53 ml of triethylamine were added to the solution and stirred at room temperature for 17 hours, after which the solvent was removed by applying the reaction solution to an evaporator to obtain a reaction mixture. The obtained reaction mixture was further reduced in pressure under the condition of 665 Pa. By distillation, 40 g of an organosilane compound e {N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane} was obtained as a fraction at 130 to 135 ° C.

Production Example 1 Production of Unmodified SBR-A In an 800 mL pressure-resistant glass container that was dried and purged with nitrogen, a cyclohexane solution of 1,3-butadiene and a cyclohexane solution of styrene were converted to 60 g of 1,3-butadiene and 15 g of styrene. In addition, 0.70 mmol of 2,2-ditetrahydrofurylpropane and 0.70 mmol of n-butyllithium (BuLi) were added, followed by carrying out a polymerization reaction in a hot water bath at 50 ° C. for 1.5 hours. The polymerization conversion rate at this time was almost 100%. Next, an isopropanol solution of 2,6-di-tert-butyl-p-cresol (BHT) was added to the polymerization reaction system to stop the polymerization reaction. Then, it vacuum-dried and obtained unmodified | denatured SBR-A.
Unmodified SBR-A had a bound styrene content of 20% by mass, a bound vinyl content of 56 mol%, and a weight average molecular weight of 186 × 10 ³ .

Production Example 2 Production of Modified SBR-B <Production of SBR with Active End>
To an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, a cyclohexane solution of 1,3-butadiene and a cyclohexane solution of styrene are added to 60 g of 1,3-butadiene and 15 g of styrene, and 2,2-ditetrahydrofuryl is added. After adding 0.70 mmol of propane and further adding 0.70 mmol of n-butyllithium (BuLi), a polymerization reaction was performed in a hot water bath at 50 ° C. for 1.5 hours. The polymerization conversion rate at this time was almost 100%.
<Modification reaction process>
Next, an amount of the organosilane compound a obtained in Synthesis Example 1 in an equimolar amount relative to lithium (Li) was added to the polymerization reaction system, and a modification reaction was further performed at 50 ° C. for 30 minutes.
<Hydrolysis step and subsequent steps>
Thereafter, 1.5 ml of dilute hydrochloric acid was added to the polymerization reaction system little by little, and then water was added in a molar amount three times that of lithium (Li), followed by stirring for 30 minutes. Next, an isopropanol solution of 2,6-di-tert-butyl-p-cresol (BHT) was added to the polymerization reaction system to stop the polymerization reaction. Thereafter, steam was blown to lower the solvent partial pressure (steam stripping) to remove the solvent, followed by vacuum drying to obtain modified SBR-B.
Modified SBR-B had a bound styrene content of 20% by mass, a vinyl bond content of 55 mol%, and a weight average molecular weight of 188 × 10 ³ .

Examples 1-6 and Comparative Examples 1-4
Using the unmodified SBR-A obtained in Production Example 1 and the modified SBR-B obtained in Production Example 2, 10 types of rubbers of Examples 1 to 6 and Comparative Examples 1 to 4 according to the composition shown in Table 1 A composition was prepared.
Next, 10 types of tires having a tire size of 195 / 65R15 were manufactured in accordance with a conventional method using these 10 types of rubber compositions in the tread, and their performance was evaluated. The results are shown in Table 1.

[note]
1) Oil-extended SBR: manufactured by JSR, trademark “SBR1712”, oil-extended rubber containing 37.5 parts by mass of aromatic oil per 100 parts by mass of rubber component 2) Unmodified SBR-A: obtained in Production Example 1 Things 3) Modified SBR-B: those obtained in Production Example 2 4) Aromatic oil: Trade name “Aromax # 3” manufactured by Fuji Kosan Co., Ltd.
5) Carbon black: Tokai Carbon Co., Ltd., trademark “SEAST 7HM”
6) Silica: Trademark “Nipsil AQ” manufactured by Tosoh Silica Co., Ltd.
7) Silane coupling agent a: bis (3-triethoxysilylpropyl) tetrasulfide, manufactured by Degussa, trademark “Si69”
8) Silane coupling agent b: manufactured by Motive Performance Materials, trademark “NXT Ultra LOW-V Silane”
9) Silane coupling agent c: trademark “NXT Z”, manufactured by Motive Performance Materials
10) Silane coupling agent d: Trademark “Si363” manufactured by Degussa
11) Silane coupling agent e: Chemical name Bis (triethoxylpropylthiodecyl) disulfide 12) Silane coupling agent f: Bis [3- (diethoxymethylsilyl) propyl] tetrasulfide 13) Anti-aging agent 6C: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, manufactured by Seiko Chemical Co., Ltd., trademark “Ozonon 6C”
14) Vulcanization accelerator DPG: Diphenylguanidine, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “Noxeller D”
15) Vulcanization accelerator CZ: N-cyclohexyl-2-benzothiazylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “Noxeller CZ”
16) Vulcanization accelerator DM: dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “Noxeller DM”
As can be seen from Table 1, the tires of the present invention (Examples 1 to 6) all have an index value of 100 or more for rolling resistance, wet grip performance and wear resistance, and are excellent in performance balance. In contrast, in the tires of Comparative Examples 2 to 4, at least one of rolling resistance, wet grip performance, and wear resistance index values is less than 100.

  The tire of the present invention uses, for a tread, a rubber composition containing a rubber component containing a specific modified conjugated diene polymer, a reinforcing filler containing at least silica, and a silane coupling agent having a specific structure. Thus, generation of a volatile organic compound (VOC) during work can be prevented, and both low heat build-up, wear resistance and wet grip performance can be satisfied.

Claims (12)

(A) Modification having a silanol group and a functional group in the vicinity of the silanol group, which promotes the reaction between the silanol group and the reinforcing filler, at the molecular end of the conjugated diene polymer. A rubber component containing 10% by mass or more of a conjugated diene polymer, (B) a reinforcing filler containing at least silica, and (A) 100 parts by mass of the rubber component, (C) a silane coupling agent 1 to 1 A tire using a rubber composition containing 25 parts by mass for a tread,
The (C) silane coupling agent is (c-1) a compound represented by the following general formula (1), (c-2) a compound represented by the following general formula (2), (c-3) A compound represented by the general formula (3), (c-4) a compound represented by the following general formula (4), and (c-5) a compound represented by the following general formula (5). A tire comprising at least one compound.

[Wherein R ¹⁵ represents —Cl, —Br, R ²⁰ O—, R ²⁰ C (═O) O—, R ²⁰ R ²¹ C═NO—, R ²⁰ R ²¹ N— or — (OSiR ²⁰ R ^{21 _{) m (OSiR 19 R 20 R}} 21) ( provided that, R ²¹ and R ²¹ are each independently a hydrogen atom or a C1-18 monovalent hydrocarbon group.), R ¹⁶ is R ^15, hydrogen An atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, R ¹⁷ is R ¹⁵ , R ¹⁶ or — [O (R ²² O) _a ] _0.5 — group (where R ²² is alkylene having 1 to 18 carbon atoms) Group, a is an integer of 1 to 4), R ¹⁸ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ¹⁹ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, x, y and z are numbers satisfying the relationship of x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, and 0 ≦ z ≦ 1. ]

[Wherein R ²³ is or straight chain having 1 to 20 carbon atoms, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a are each independently a group capable of binding with two silicon _{atoms, [- O-] 0.5, [} - O-G-] is a group selected from _0.5, or _{[-O-G-O-] 0.5} , Z ^b is a group that can independently bond to two silicon atoms, and is a functional group represented by [—O—G—O—] _0.5 ; Z ^c is independently —Cl, —Br , —OR ²⁴ , R ²⁴ C (═O) O—, R ²⁴ R ²⁵ C═NO—, R ²⁴ R ²⁵ N—, R ²⁴ —, HO—G—O—, R and G coincide with the above notation.
m, n, u, v, and w are independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, and 1 / 2u + v + 2w = 2 or 3.
When there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, Z ^a _u in the plurality of B parts , Z ^b _v and Z ^c _w may be the same or different. ]
R ^1a R ^2a R ^3a Si-R ^4a -SH (3)
[Wherein, R ^1a represents a methyl group or an ethyl group, R ^2a represents a methoxy group, an ethoxy group, or —O— (YO) _m —X, Y represents a divalent hydrocarbon group, and X represents a carbon number of 1 -15 alkyl groups, m is a number from 1-40. R ^3a represents a methyl group, an ethyl group or R ^2a , and R ^4a represents a divalent hydrocarbon group having 1 to 12 carbon atoms. ]
_{^{(R 31 O) 3-p}} (R 32) p Si-R 33 -S m -R 34 -S m -R 33 -Si (R 32) p (OR 31) 3-p ··· (4)
[R ³¹ and R ³² are each a hydrocarbon group having 1 to 4 carbon atoms, R ³³ is a divalent hydrocarbon group having 1 to 15 carbon atoms, p is an integer of 0 to 2, and m is an average value of 1 or more and less than 4 , R ³⁴ represents —S—R ³⁵ —S—, —R ³⁶ —S _x —R ³⁷ —, or —R ³⁸ —S _y —R ³⁹ —S _z —R ⁴⁰ — (R ^{35 to} R ⁴⁰ represent the number of carbon atoms. 1 to 20 divalent hydrocarbon groups or divalent organic groups containing a hetero element other than S and O, which may be the same or different, and x, y, and z are each an average value of 1 or more and 4 Is less than.]

[Wherein, R ⁴¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms, and R ⁴² and R ⁴³ each independently represents an alkyl group or phenyl group having 1 to 6 carbon atoms. Or one of them represents R ⁴¹ O, each R ⁴¹ O may be the same or different, and x is a number from 3 to 5. ]   (B) The tire according to claim 1, wherein the silica content in the reinforcing filler is 20% by mass or more.   (A) The tire according to claim 2, comprising 10 to 150 parts by mass of silica with respect to 100 parts by mass of the rubber component. The tire according to any one of claims 1 to 3, wherein the modified conjugated diene polymer has a structure represented by the following general formula (6) or (7).

[Wherein, R ¹ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms; R ² and R ³ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; A ³ Is a functional group that promotes the reaction between a single bond, a hydrocarbon group having 1 to 20 carbon atoms or a silanol group and the reinforcing filler, and m is an integer of 1 to 10.]

Wherein R ⁴ is a single bond or a hydrocarbon group having 1 to 20 carbon atoms; R ⁵ and R ⁶ are each independently a single bond, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; A ⁴ is a single bond , A functional group that promotes the reaction between the hydrocarbon group having 1 to 20 carbon atoms or the silanol group and the reinforcing filler; and B and D are each independently a functional group that promotes the reaction between the silanol group and the reinforcing filler. A group containing at least one; p and q are each independently an integer of 0 to 5, (p + q) is 1 or more, and n is an integer of 1 to 10] In the general formula (6) or the general formula (7), the functional groups A ³ and A ⁴ that promote the reaction between the silanol group and the reinforcing filler are each independently a (thio) ether bond or a (thio) urethane bond. A divalent functional group having at least one bond selected from an imino bond and an amide bond, and a nitrile group, pyridyl group, N-alkylpyrrolidonyl group, N-alkylimidazolyl group, N-alkylpyrazolyl group, Residue of (thio) ketone group, (thio) aldehyde group, isocyanuric acid triester residue, (thio) carboxylic acid hydrocarbyl ester residue having 1 to 20 carbon atoms, (thio) carboxylic acid metal salt having 1 to 20 carbon atoms Selected from a group, a carboxylic acid anhydride residue having 1 to 20 carbon atoms, a carboxylic acid halide residue having 1 to 20 carbon atoms, and a carbonic acid dihydrocarbyl ester residue. The tire according to claim 4, wherein the tire is at least one divalent functional group selected from the group consisting of divalent functional groups derived from functional groups. In the general formula (7), groups B and D containing at least one functional group that promotes the reaction between the silanol group and the reinforcing filler are independently protected with a primary amino group, a secondary amino group, and a protected group. Primary or secondary amino group, tertiary amino group, cyclic amino group, oxazolyl group, imidazolyl group, aziridinyl group, (thio) ketone group, (thio) aldehyde group and amide group, (thio) epoxy group, (thio) Isocyanate group, nitrile group, pyridyl group, N-alkylpyrrolidonyl group, N-alkylimidazolyl group, N-alkylpyrazolyl group, imino group, amide group, ketimine group, imine residue, isocyanuric acid triester residue, carbon 1 to 20 (thio) carboxylic acid hydrocarbyl ester residue, (thio) carboxylic acid metal salt residue having 1 to 20 carbon atoms, 1 to 2 carbon atoms At least one selected from the group consisting of a carboxylic acid anhydride residue, a carboxylic acid halide residue having 1 to 20 carbon atoms, a carbonic acid dihydrocarbyl ester residue and a functional group represented by the general formula -EFFG The tire according to claim 4 or 5, which is a functional group.
[In the formula, E is an imino group, a divalent imine residue, a divalent pyridine residue or a divalent amide residue, F is an alkylene group having 1 to 20 carbon atoms, a phenylene group, or 8 to 20 carbon atoms. Aralkylene group, G is primary amino group, secondary amino group, imidazolyl group, aziridinyl group, ketimine group, nitrile group, amide group, pyridine group or (thio) isocyanate group] The modified conjugated diene polymer is a modified product of polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer or styrene-isoprene-butadiene terpolymer. The tire according to any one of claims 1 to 6. The compound (c-1) represented by the general formula (1) is represented by the following formula (1-1)

The tire according to any one of claims 1 to 7, which is a silane coupling agent having a structure represented by: The compound (c-2) represented by the general formula (2) is represented by the following formula (2-1), formula (2-2) or formula (2-3).

[In formula, L shows a C1-C9 alkanediyl group or alkenediyl group each independently, x shows the number of 1-20, y shows the number of 0-20. ]
The tire according to any one of claims 1 to 7, which is a silane coupling agent having a structure represented by: (C) The silane coupling agent is represented by the compound (c-2) represented by the formula (2-2) and the formula (2-3), and the general formula (3), and R ^2a is —O ( YO) _m- X, wherein X is at least one selected from compounds (c-3) which is an alkyl group having 6 to 15 carbon atoms. Tires. The compound (c-3) represented by the general formula (3) is represented by the following formula (3-1)

The tire according to claim 10, having a structure represented by:   The tire according to claim 1, wherein the reinforcing filler contains carbon black together with silica.