JP2019001958A - Rubber composition and tire - Google Patents

Abstract

To provide a rubber composition capable of improving wear resistance while achieving both low rolling resistance and wet performance of a tire, and to provide a tire excellent in low rolling resistance, wet performance, and wear resistance.SOLUTION: The rubber composition contains a modified polybutadiene rubber (A), a natural rubber (B), and one or more thermoplastic resins (C) selected from the group consisting of Cresins, C-Cresins, Cresins, and dicyclopentadiene resins. The tire uses the rubber composition for a tread rubber.SELECTED DRAWING: None

Description

  The present invention relates to a rubber composition and a tire.

Conventionally, various studies have been made to improve braking performance on a wet road surface (hereinafter abbreviated as “wet performance”) from the viewpoint of improving vehicle safety. For example, in Patent Document 1 below, a rubber composition obtained by blending a rubber component containing 70% by mass or more of natural rubber with a thermoplastic resin and a filler containing silica is applied to a tire tread rubber. Thus, it is disclosed that the braking performance of the tire with respect to both the dry road surface and the wet road surface is improved.
On the other hand, demands for fuel efficiency reduction of automobiles are increasing in connection with the movement of global carbon dioxide emission regulations accompanying the recent increase in interest in environmental problems. In order to meet such demands, reduction of rolling resistance is also demanded for tire performance.
Further, from the viewpoint of tire economy, in developing a rubber composition for a tire tread, it is also required to improve wear resistance in addition to low rolling resistance and wet performance.

International Publication No. 2015/0797703

However, as a result of investigation by the present inventor, it has been found that although the wet performance of the tire can be improved according to the technique described in Patent Document 1, there is room for improvement in wear resistance.
Further, as a result of further investigation by the present inventor, in the technique described in Patent Document 1, the rubber component is a modified polybutadiene rubber, thereby reducing the rolling resistance of the tire and improving the wear resistance of the tire. However, it has been found that the wet performance of a tire to which such a rubber composition is applied is reduced.

Then, this invention solves the problem of the said prior art, and it aims at providing the rubber composition which can improve abrasion resistance, making low rolling resistance and wet performance of a tire compatible. To do.
Another object of the present invention is to provide a tire excellent in low rolling resistance, wet performance, and wear resistance.

  The gist configuration of the present invention for solving the above problems is as follows.

The rubber composition of the present invention, the selection and the modified polybutadiene rubber (A), natural rubber (B), C ₅ resins, C ₅ -C ₉ resins, from the group consisting of C ₉ resins and dicyclopentadiene resins And one or more thermoplastic resins (C).
By using such a rubber composition of the present invention for a tread rubber of a tire, it is possible to improve wear resistance while achieving both low rolling resistance and wet performance of the tire.

In the rubber composition of the present invention, the modified polybutadiene rubber (A) has the following general formula (I):
R ¹ _a -Si- (OR ² ) _4-a (I)
[Wherein, R ¹ and R ² each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; Is an integer of ˜2, and when there are a plurality of OR ² , each OR ² may be the same as or different from each other, and the molecule contains no active protons] It is preferable. In this case, the low rolling resistance and wear resistance of the tire can be further improved by using the tire tread rubber.

［式中、ｎ１＋ｎ２＋ｎ３＋ｎ４は４であり（但し、ｎ２は１〜４の整数であり、ｎ１、ｎ３及びｎ４は０〜３の整数である）、Ａ^１は、飽和環状３級アミン化合物残基、不飽和環状３級アミン化合物残基、ケチミン残基、ニトリル基、イソシアナート基、チオイソシアナート基、エポキシ基、チオエポキシ基、イソシアヌル酸トリヒドロカルビルエステル基、炭酸ジヒドロカルビルエステル基、ピリジン基、ケトン基、チオケトン基、アルデヒド基、チオアルデヒド基、アミド基、カルボン酸エステル基、チオカルボン酸エステル基、カルボン酸エステルの金属塩、チオカルボン酸エステルの金属塩、カルボン酸無水物残基、カルボン酸ハロゲン化合物残基、エポキシ、シラザン若しくはジスルフィドを有する一価の基、並びに加水分解性基を有する第一若しくは第二アミノ基又は加水分解性基を有するメルカプト基の中から選択される少なくとも１種の官能基であり、ｎ４が２以上の場合には同一でも異なっていてもよく、Ａ^１は、Ｓｉと結合して環状構造を形成する二価の基であってもよく、Ｒ^２１は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｎ１が２以上の場合には同一でも異なっていてもよく、Ｒ^２３は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基、炭素数６〜１８の一価の芳香族炭化水素基又はハロゲン原子であり、ｎ３が２以上の場合には同一でも異なっていてもよく、Ｒ^２２は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、いずれも窒素原子及び／又はケイ素原子を含有していてもよく、ｎ２が２以上の場合には、互いに同一若しくは異なっていてもよく、或いは、一緒になって環を形成していてもよく、Ｒ^２４は、炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、ｎ４が２以上の場合には同一でも異なっていてもよい］で表される化合物で変性されていることも好ましい。この場合、タイヤのトレッドゴムに用いることにより、タイヤの低転がり抵抗性、ウェット性能及び耐摩耗性を更に向上させることができる。 In the rubber composition of the present invention, the modified polybutadiene rubber (A) has the following general formula (II):

[Wherein n1 + n2 + n3 + n4 is 4 (where n2 is an integer of 1 to 4, n1, n3 and n4 are integers of 0 to 3), A ¹ is a saturated cyclic tertiary amine compound residue, Unsaturated cyclic tertiary amine compound residue, ketimine residue, nitrile group, isocyanate group, thioisocyanate group, epoxy group, thioepoxy group, isocyanuric acid trihydrocarbyl ester group, carbonic acid dihydrocarbyl ester group, pyridine group, ketone group Thioketone group, aldehyde group, thioaldehyde group, amide group, carboxylic acid ester group, thiocarboxylic acid ester group, metal salt of carboxylic acid ester, metal salt of thiocarboxylic acid ester, carboxylic acid anhydride residue, carboxylic acid halogen compound residue Group, monovalent group with epoxy, silazane or disulfide, and hydrolyzable At least one functional group selected from a primary or secondary amino group having a group or a mercapto group having a hydrolyzable group, and when n4 is 2 or more, they may be the same or different, A ¹ may be a divalent group that binds to Si to form a cyclic structure, and R ²¹ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or 6 carbon atoms. -18 monovalent aromatic hydrocarbon group, and when n1 is 2 or more, they may be the same or different, and R ²³ is a monovalent aliphatic or alicyclic carbon atom having 1 to 20 carbon atoms. A hydrogen group, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and when n3 is 2 or more, they may be the same or different, and R ²² is one having 1 to 20 carbon atoms. Valent aliphatic or alicyclic hydrocarbon group or monovalent aromatic having 6 to 18 carbon atoms It is a hydrocarbon group, both of which may contain a nitrogen atom and / or a silicon atom, and when n2 is 2 or more, they may be the same or different from each other, or together form a ring R ²⁴ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and n4 is 2 or more. In this case, it may be the same or different]. In this case, by using the tire tread rubber, the low rolling resistance, wet performance and wear resistance of the tire can be further improved.

［式中、Ｒ^１１及びＲ^１２は、それぞれ独立して炭素数１〜１２の、アルキル基、シクロアルキル基又はアラルキル基である］で表される置換アミノ基、又は下記式（ｉｉ）：

［式中、Ｒ^１３は、３〜１６のメチレン基を有する、アルキレン基、置換アルキレン基、オキシアルキレン基又はＮ−アルキルアミノ−アルキレン基を示す］で表される環状アミノ基を有することが好ましい。この場合、タイヤのトレッドゴムに用いることにより、タイヤの耐摩耗性を更に向上させることができる。 In the rubber composition of the present invention, the modified polybutadiene rubber (A) has the following formula (i):

[Wherein R ¹¹ and R ¹² are each independently an alkyl group, a cycloalkyl group, or an aralkyl group having 1 to 12 carbon atoms], or the following formula (ii):

[Wherein R ¹³ represents a cyclic amino group represented by the following formula: an alkylene group, a substituted alkylene group, an oxyalkylene group or an N-alkylamino-alkylene group having 3 to 16 methylene groups]. . In this case, the wear resistance of the tire can be further improved by using it for the tread rubber of the tire.

  The tire of the present invention is characterized by using the above rubber composition for a tread rubber. The tire of the present invention is excellent in low rolling resistance, wet performance, and wear resistance because the rubber composition is used for tread rubber.

ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which can improve abrasion resistance can be provided, making low rolling resistance and wet performance of a tire compatible.
Moreover, according to the present invention, a tire excellent in low rolling resistance, wet performance, and wear resistance can be provided.

  Below, the rubber composition of this invention and a tire are illustrated and demonstrated in detail based on the embodiment.

<Rubber composition>
The rubber composition of the present invention, the selection and the modified polybutadiene rubber (A), natural rubber (B), C ₅ resins, C ₅ -C ₉ resins, from the group consisting of C ₉ resins and dicyclopentadiene resins And one or more thermoplastic resins (C).

In the rubber composition of the present invention, by using the modified polybutadiene rubber (A) as the rubber component, the dispersibility of the filler generally used in the rubber composition is improved, and the wear resistance of the rubber composition is improved. improves.
Further, in the rubber composition of the present invention, by using the modified polybutadiene rubber (A), the tan δ (loss tangent) at 30 to 60 ° C. of the rubber composition is lowered, and the low heat build-up is improved.
Furthermore, in the rubber composition of the present invention, the modified polybutadiene rubber is used by combining the modified polybutadiene rubber (A) and the natural rubber (B) as the rubber component and further blending the thermoplastic resin (C). The thermoplastic resin (C) is dispersed in both (A) and natural rubber (B), and the amount of deformation of the rubber composition with respect to strain increases.
Therefore, by applying the rubber composition of the present invention to a tread rubber of a tire, the wear resistance of the tire is improved due to the excellent wear resistance of the rubber composition. Due to the excellent exothermic property, the rolling resistance of the tire is reduced (that is, the fuel efficiency performance of the tire is improved), and further, the amount of deformation with respect to the distortion of the rubber composition is large, so that the wetness of the tire is reduced. Performance is improved. Therefore, according to the rubber composition of the present invention, it is possible to improve the wear resistance while achieving both the low rolling resistance and the wet performance of the tire by using it for the tread rubber of the tire.

  In addition to the above-described effects, according to the rubber composition of the present invention, the distribution ratio of the filler to the modified polybutadiene rubber (A) generally having a low glass transition temperature (Tg) is increased. ) Temperature dependency can be reduced.

  The rubber composition of the present invention contains a modified polybutadiene rubber (A), and the content of the modified polybutadiene rubber (A) is preferably 30% by mass or more as the content of the rubber composition in the rubber component. Preferably it is 40 mass% or more, Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less. If the content of the modified polybutadiene rubber (A) in the rubber component is 30% by mass or more, the low rolling resistance and wear resistance of the tire can be further improved, and if it is 70% by mass or less, The content of the natural rubber (B) can be ensured and the decrease in wet performance can be sufficiently suppressed.

Examples of the modified functional group in the modified polybutadiene rubber (A) include a nitrogen-containing functional group, a silicon-containing functional group, and an oxygen-containing functional group.
As the modified polybutadiene rubber (A), 1,3-butadiene is used as a monomer, a polymer obtained by modifying the molecular terminal and / or main chain of the butadiene polymer with a modifier, A polymer obtained by polymerizing the butadiene using 3-butadiene and a polymerization initiator having a modified functional group, or a polymerization initiator having a modified functional group using 1,3-butadiene as a monomer It is possible to use a polymer obtained by further modifying the molecular terminal and / or main chain of a butadiene polymer obtained by polymerizing the butadiene with a modifier.

As the modifier, a hydrocarbyloxysilane compound is preferable.
Examples of the hydrocarbyloxysilane compound include the following general formula (I):
R ¹ _a -Si- (OR ² ) _4-a (I)
The compound represented by these is preferable.
In general formula (I), R ¹ and R ² each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, a is an integer of 0 to 2, and when there are a plurality of OR ² , each OR ² may be the same as or different from each other, and no active proton is contained in the molecule.

で表される化合物も好ましい。
一般式（ＩＩ）中、ｎ１＋ｎ２＋ｎ３＋ｎ４は４であり（但し、ｎ２は１〜４の整数であり、ｎ１、ｎ３及びｎ４は０〜３の整数である）、Ａ^１は、飽和環状３級アミン化合物残基、不飽和環状３級アミン化合物残基、ケチミン残基、ニトリル基、イソシアナート基、チオイソシアナート基、エポキシ基、チオエポキシ基、イソシアヌル酸トリヒドロカルビルエステル基、炭酸ジヒドロカルビルエステル基、ピリジン基、ケトン基、チオケトン基、アルデヒド基、チオアルデヒド基、アミド基、カルボン酸エステル基、チオカルボン酸エステル基、カルボン酸エステルの金属塩、チオカルボン酸エステルの金属塩、カルボン酸無水物残基、カルボン酸ハロゲン化合物残基、エポキシ、シラザン若しくはジスルフィドを有する一価の基、並びに加水分解性基を有する第一若しくは第二アミノ基又は加水分解性基を有するメルカプト基の中から選択される少なくとも１種の官能基であり、ｎ４が２以上の場合には同一でも異なっていてもよく、Ａ^１は、Ｓｉと結合して環状構造を形成する二価の基であってもよく、Ｒ^２１は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｎ１が２以上の場合には同一でも異なっていてもよく、Ｒ^２３は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基、炭素数６〜１８の一価の芳香族炭化水素基又はハロゲン原子であり、ｎ３が２以上の場合には同一でも異なっていてもよく、Ｒ^２２は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、いずれも窒素原子及び／又はケイ素原子を含有していてもよく、ｎ２が２以上の場合には、互いに同一若しくは異なっていてもよく、或いは、一緒になって環を形成してもよく、Ｒ^２４は、炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、ｎ４が２以上の場合には同一でも異なっていてもよい。
前記加水分解性基を有する第一若しくは第二アミノ基又は加水分解性基を有するメルカプト基における加水分解性基としては、トリメチルシリル基、ｔｅｒｔ−ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。
前記エポキシを有する一価の基を含む化合物としては、例えば、２−グリシドキシエチルトリメトキシシラン、２−グリシドキシエチルトリエトキシシラン、（２−グリシドキシエチル）メチルジメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、（３−グリシドキシプロピル）メチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチル（メチル）ジメトキシシラン等を挙げることができる。 Examples of the hydrocarbyloxysilane compound include the following general formula (II):

The compound represented by these is also preferable.
In the general formula (II), n1 + n2 + n3 + n4 is 4 (where n2 is an integer of 1 to 4, n1, n3 and n4 are integers of 0 to 3), and A ¹ is a saturated cyclic tertiary amine compound Residue, unsaturated cyclic tertiary amine compound residue, ketimine residue, nitrile group, isocyanate group, thioisocyanate group, epoxy group, thioepoxy group, isocyanuric acid trihydrocarbyl ester group, carbonic acid dihydrocarbyl ester group, pyridine group , Ketone group, thioketone group, aldehyde group, thioaldehyde group, amide group, carboxylic acid ester group, thiocarboxylic acid ester group, metal salt of carboxylic acid ester, metal salt of thiocarboxylic acid ester, carboxylic acid anhydride residue, carboxylic acid A monovalent group having a halogenated residue, epoxy, silazane or disulfide, and It is at least one functional group selected from a hydrolyzable primary or secondary amino group or a hydrolyzable mercapto group, and when n4 is 2 or more, they are the same or different. A ¹ may be a divalent group that forms a cyclic structure by bonding to Si, and R ²¹ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or A monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and may be the same or different when n1 is 2 or more, and R ²³ is a monovalent aliphatic or fatty acid having 1 to 20 carbon atoms. cyclic hydrocarbon group, an aromatic hydrocarbon group or a halogen atom monovalent C6-18, may be the same or different in the case of n3 is 2 or more, R ²² is 1 to carbon atoms 20 monovalent aliphatic or alicyclic hydrocarbon groups or one having 6 to 18 carbon atoms Each of which may contain a nitrogen atom and / or a silicon atom, and when n2 is 2 or more, they may be the same or different from each other, or together R ²⁴ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and n4 When is 2 or more, they may be the same or different.
The hydrolyzable group in the primary or secondary amino group having a hydrolyzable group or a mercapto group having a hydrolyzable group is preferably a trimethylsilyl group or a tert-butyldimethylsilyl group, and particularly preferably a trimethylsilyl group.
Examples of the compound containing a monovalent group having an epoxy include 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl) methyldimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, and the like.

で表される化合物が好ましい。
一般式（ＩＩＩ）中、ｐ１＋ｐ２＋ｐ３は２であり（但し、ｐ２は１〜２の整数であり、ｐ１及びｐ３は０〜１の整数である）、Ａ^２は、ＮＲａ（Ｒａは、一価の炭化水素基、加水分解性基又は含窒素有機基である）、或いは、硫黄であり、Ｒ^２５は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、Ｒ^２７は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基、炭素数６〜１８の一価の芳香族炭化水素基又はハロゲン原子であり、Ｒ^２６は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基、炭素数６〜１８の一価の芳香族炭化水素基又は含窒素有機基であり、いずれも窒素原子及び／又はケイ素原子を含有していてもよく、ｐ２が２の場合には、互いに同一でも異なっていてもよく、或いは、一緒になって環を形成してもよく、Ｒ^２８は、炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基である。
前記加水分解性基として、トリメチルシリル基、ｔｅｒｔ−ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。 Examples of the compound represented by the general formula (II) include the following general formula (III):

The compound represented by these is preferable.
In general formula (III), p1 + p2 + p3 is 2 (provided that p2 is an integer of 1 to 2 and p1 and p3 are integers of 0 to 1), A ² is NRa (Ra is a monovalent) A hydrocarbon group, a hydrolyzable group or a nitrogen-containing organic group), or sulfur, and R ²⁵ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or 6 to 6 carbon atoms. 18 monovalent aromatic hydrocarbon group, and R ²⁷ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Or a halogen atom, and R ²⁶ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a nitrogen-containing organic group. Any of them may contain nitrogen atoms and / or silicon atoms, and when p2 is 2, They may be the same or different, or may be combined to form a ring, and R ²⁸ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or 6 to 18 carbon atoms. These are divalent aromatic hydrocarbon groups.
As the hydrolyzable group, a trimethylsilyl group and a tert-butyldimethylsilyl group are preferable, and a trimethylsilyl group is particularly preferable.

で表される化合物も好ましい。
一般式（ＩＶ）中、ｑ１＋ｑ２は３であり（但し、ｑ１は０〜２の整数であり、ｑ２は１〜３の整数である）、Ｒ^３１は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ^３２及びＲ^３３はそれぞれ独立して加水分解性基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、Ｒ^３４は炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｑ１が２の場合には同一でも異なっていてもよく、Ｒ^３５は炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｑ２が２以上の場合には同一でも異なっていてもよい。
前記加水分解性基としては、トリメチルシリル基、ｔｅｒｔ−ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。 Examples of the compound represented by the general formula (II) include the following general formula (IV):

The compound represented by these is also preferable.
In general formula (IV), q1 + q2 is 3 (provided that q1 is an integer of 0 to 2 and q2 is an integer of 1 to 3), and R ³¹ is a divalent aliphatic having 1 to 20 carbon atoms. Or an alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein R ³² and R ³³ are each independently a hydrolyzable group, a monovalent fat having 1 to 20 carbon atoms. An aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³⁴ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a carbon number A monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, which may be the same or different when q1 is 2, and R ³⁵ is a monovalent aliphatic or alicyclic hydrocarbon having 1 to 20 carbon atoms Group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the same or different when q2 is 2 or more It can have.
As the hydrolyzable group, a trimethylsilyl group and a tert-butyldimethylsilyl group are preferable, and a trimethylsilyl group is particularly preferable.

で表される化合物も好ましい。
一般式（Ｖ）中、ｒ１＋ｒ２は３であり（但し、ｒ１は１〜３の整数であり、ｒ２は０〜２の整数である）、Ｒ^３６は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ^３７はジメチルアミノメチル基、ジメチルアミノエチル基、ジエチルアミノメチル基、ジエチルアミノエチル基、メチルシリル（メチル）アミノメチル基、メチルシリル（メチル）アミノエチル基、メチルシリル（エチル）アミノメチル基、メチルシリル（エチル）アミノエチル基、ジメチルシリルアミノメチル基、ジメチルシリルアミノエチル基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｒ１が２以上の場合には同一でも異なっていてもよく、Ｒ^３８は炭素数１〜２０のヒドロカルビルオキシ基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｒ２が２の場合には同一でも異なっていてもよい。 Examples of the compound represented by the general formula (II) include the following general formula (V):

The compound represented by these is also preferable.
In general formula (V), r1 + r2 is 3 (provided that r1 is an integer of 1 to 3, r2 is an integer of 0 to 2), and R ³⁶ is a divalent aliphatic having 1 to 20 carbon atoms. Or an alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³⁷ is a dimethylaminomethyl group, dimethylaminoethyl group, diethylaminomethyl group, diethylaminoethyl group, methylsilyl (methyl) Aminomethyl group, methylsilyl (methyl) aminoethyl group, methylsilyl (ethyl) aminomethyl group, methylsilyl (ethyl) aminoethyl group, dimethylsilylaminomethyl group, dimethylsilylaminoethyl group, monovalent fat having 1 to 20 carbon atoms An aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r1 is 2 or more, they are the same or different. At best, R ³⁸ is a hydrocarbyloxy group, an aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, monovalent C1-20 C20 And when r2 is 2, they may be the same or different.

で表される化合物も好ましい。
一般式（ＶＩ）中、Ｒ^４０はトリメチルシリル基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、Ｒ^４１は炭素数１〜２０のヒドロカルビルオキシ基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、Ｒ^４２は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基である。ここで、ＴＭＳは、トリメチルシリル基を示す（以下、同じ。）。 Examples of the compound represented by the general formula (II) include the following general formula (VI):

The compound represented by these is also preferable.
In the general formula (VI), R ⁴⁰ is a trimethylsilyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; ⁴¹ is a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ⁴² Is a C1-C20 divalent aliphatic or alicyclic hydrocarbon group or a C6-C18 divalent aromatic hydrocarbon group. Here, TMS represents a trimethylsilyl group (hereinafter the same).

で表される化合物も好ましい。
一般式（ＶＩＩ）中、Ｒ^４３及びＲ^４４はそれぞれ独立して炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ^４５は炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、各Ｒ^４５は、同一でも異なっていてもよい。 Examples of the compound represented by the general formula (II) include the following general formula (VII):

The compound represented by these is also preferable.
In general formula (VII), R ⁴³ and R ⁴⁴ are each independently a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R ⁴⁵ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and each R ⁴⁵ is the same or different. It may be.

で表される化合物も好ましい。
一般式（ＶＩＩＩ）中、ｓ１＋ｓ２は３であり（但し、ｓ１は０〜２の整数であり、ｓ２は１〜３の整数である）、Ｒ^４６は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ^４７およびＲ^４８はそれぞれ独立して炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基である。複数のＲ^４７又はＲ^４８は、同一でも異なっていてもよい。 Examples of the compound represented by the general formula (II) include the following general formula (VIII):

The compound represented by these is also preferable.
In general formula (VIII), s1 + s2 is 3 (provided that s1 is an integer of 0 to 2 and s2 is an integer of 1 to 3), and R ⁴⁶ is a divalent aliphatic having 1 to 20 carbon atoms. Or an alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ⁴⁷ and R ⁴⁸ are each independently a monovalent aliphatic or alicyclic group having 1 to 20 carbon atoms. It is a hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. A plurality of R ⁴⁷ or R ⁴⁸ may be the same or different.

で表される化合物も好ましい。
一般式（ＩＸ）中、Ｘはハロゲン原子であり、Ｒ^４９は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ^５０及びＲ^５１はそれぞれ独立して加水分解性基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であるか、或いは、Ｒ^５０及びＲ^５１は結合して二価の有機基を形成しており、Ｒ^５２及びＲ^５３はそれぞれ独立してハロゲン原子、ヒドロカルビルオキシ基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基である。
Ｒ^５０及びＲ^５１としては、加水分解性基であることが好ましく、加水分解性基として、トリメチルシリル基、ｔｅｒｔ−ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。 Examples of the compound represented by the general formula (II) include the following general formula (IX):

The compound represented by these is also preferable.
In the general formula (IX), X is a halogen atom, and R ⁴⁹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R ⁵⁰ and R ⁵¹ are each independently a hydrolyzable group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 18 carbon atoms. R ⁵⁰ and R ⁵¹ are bonded to form a divalent organic group, and R ⁵² and R ⁵³ are each independently a halogen atom, a hydrocarbyloxy group, or a C 1-20 group. A monovalent aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ⁵⁰ and R ⁵¹ are preferably hydrolyzable groups, and the hydrolyzable group is preferably a trimethylsilyl group or a tert-butyldimethylsilyl group, and particularly preferably a trimethylsilyl group.

で表される化合物も好ましい。
一般式（Ｘ）〜（ＸＩＩＩ）中、記号Ｕ、Ｖはそれぞれ０〜２且つＵ＋Ｖ＝２を満たす整数である。一般式（Ｘ）〜（ＸＩＩＩ）中のＲ^５４〜^９２は同一でも異なっていてもよく、炭素数１〜２０の一価若しくは二価の脂肪族又は脂環式炭化水素基、或いは、炭素数６〜１８の一価若しくは二価の芳香族炭化水素基である。なお、一般式（ＸＩＩＩ）中のα及びβは０〜５の整数である。 The hydrocarbyloxysilane compounds represented by the general formula (II) are represented by the following general formulas (X) to (XIII):

The compound represented by these is also preferable.
In general formulas (X) to (XIII), symbols U and V are integers satisfying 0 to 2 and U + V = 2, respectively. R ⁵⁴ to ⁹² in the general formulas (X) to (XIII) may be the same or different, and the monovalent or divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or the number of carbon atoms 6-18 monovalent or divalent aromatic hydrocarbon groups. In addition, (alpha) and (beta) in general formula (XIII) are the integers of 0-5.

  The polymerization initiator having the modified functional group is preferably a lithium amide compound. Examples of the lithium amide compound include lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethylamide, lithium diethylamide, lithium dibutylamide, lithium dipropylamide, Lithium diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiperazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide, lithium methyl Examples thereof include phenethylamide.

（式中、Ｒ^１１及びＲ^１２は、それぞれ独立して炭素数１〜１２のアルキル基、シクロアルキル基又はアラルキル基である）で表される置換アミノ基、又は下記式（ｉｉ）：

（式中、Ｒ^１３は、３〜１６のメチレン基を有する、アルキレン基、置換アルキレン基、オキシアルキレン基又はＮ−アルキルアミノ−アルキレン基を示す）で表される環状アミノ基である］で表されるリチウムアミド化合物を用いることで、式（ｉ）で表される置換アミノ基及び式（ｉｉ）で表される環状アミノ基からなる群から選択される少なくとも一種の窒素含有官能基が導入された変性ポリブタジエンゴム（Ａ）が得られる。 Moreover, as said lithium amide compound, Formula: Li-AM [In formula, AM is following formula (i):

(Wherein R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or an aralkyl group), or the following formula (ii):

Wherein R ¹³ is a cyclic amino group represented by an alkylene group, a substituted alkylene group, an oxyalkylene group or an N-alkylamino-alkylene group having 3 to 16 methylene groups. By using the lithium amide compound, at least one nitrogen-containing functional group selected from the group consisting of a substituted amino group represented by formula (i) and a cyclic amino group represented by formula (ii) is introduced. A modified polybutadiene rubber (A) is obtained.

In the above formula (i), R ¹¹ and R ¹² are an alkyl group, a cycloalkyl group or an aralkyl group having 1 to 12 carbon atoms, specifically, a methyl group, an ethyl group, a butyl group, an octyl group, Preferred examples include a cyclohexyl group, a 3-phenyl-1-propyl group, and an isobutyl group. R ¹¹ and R ¹² may be the same or different.
In the above formula (ii), R ¹³ is an alkylene group, a substituted alkylene group, an oxyalkylene group or an N-alkylamino-alkylene group having 3 to 16 methylene groups. Here, the substituted alkylene group includes a mono- to octa-substituted alkylene group, and examples of the substituent include a chain or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a bicycloalkyl group, An aryl group and an aralkyl group are mentioned. R ¹³ is specifically preferably a trimethylene group, a tetramethylene group, a hexamethylene group, an oxydiethylene group, an N-alkylazadiethylene group, a dodecamethylene group, a hexadecamethylene group, or the like.

The lithium amide compound may be preliminarily prepared from a secondary amine and a lithium compound and used for the polymerization reaction, but may be generated in a polymerization system.
Here, as the secondary amine, in addition to dimethylamine, diethylamine, dibutylamine, dioctylamine, dicyclohexylamine, diisobutylamine and the like, azacycloheptane (ie, hexamethyleneimine), 2- (2-ethylhexyl) pyrrolidine, 3 -(2-propyl) pyrrolidine, 3,5-bis (2-ethylhexyl) piperidine, 4-phenylpiperidine, 7-decyl-1-azacyclotridecane, 3,3-dimethyl-1-azacyclotetradecane, 4- Dodecyl-1-azacyclooctane, 4- (2-phenylbutyl) -1-azacyclooctane, 3-ethyl-5-cyclohexyl-1-azacycloheptane, 4-hexyl-1-azacycloheptane, 9-isoamyl -1-Azacycloheptadecane, 2-methyl-1-aza Chloheptade-9-ene, 3-isobutyl-1-azacyclododecane, 2-methyl-7-tert-butyl-1-azacyclododecane, 5-nonyl-1-azacyclododecane, 8- (4′-methylphenyl) ) -5-pentyl-3-azabicyclo [5.4.0] undecane, 1-butyl-6-azabicyclo [3.2.1] octane, 8-ethyl-3-azabicyclo [3.2.1] octane, 1-propyl-3-azabicyclo [3.2.2] nonane, 3- (tert-butyl) -7-azabicyclo [4.3.0] nonane, 1,5,5-trimethyl-3-azabicyclo [4. 4.0] cyclic amines such as decane.
Examples of the lithium compound include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl- Hydrocarbyl lithium such as phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, a reaction product of diisopropenylbenzene and butyl lithium, and the like can be used.

In the polymerization of 1,3-butadiene for producing the modified polybutadiene rubber (A), the above-described polymerization initiator having a modified functional group or the lithium compound (that is, a polymerization initiator having no modified functional group). However, the polymerization reaction of 1,3-butadiene is not limited to this, and for example, coordination polymerization may be used.
Here, when 1,3-butadiene is polymerized by coordination polymerization, a rare earth metal compound is preferably used as the polymerization initiator, and the following components (a), (b), and (c) are combined. More preferably, it is used.

The component (a) used for the coordination polymerization is selected from a rare earth metal compound, a complex compound of a rare earth metal compound and a Lewis base, and the like. Here, examples of rare earth metal compounds include rare earth element carboxylates, alkoxides, β-diketone complexes, phosphates and phosphites, and Lewis bases include acetylacetone, tetrahydrofuran, pyridine, N, N. -Dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, monovalent or divalent alcohol, etc. are mentioned. As the rare earth element of the rare earth metal compound, lanthanum, neodymium, praseodymium, samarium and gadolinium are preferable, and among these, neodymium is particularly preferable.
Specific examples of the component (a) include neodymium tri-2-ethylhexanoate, a complex compound thereof with acetylacetone, neodymium trineodecanoate, a complex compound thereof with acetylacetone, neodymium tri-n-butoxide, and the like. It is done.

  The component (b) used for the coordination polymerization is selected from organoaluminum compounds. Specific examples of the organoaluminum compound include a trihydrocarbyl aluminum compound, a hydrocarbyl aluminum hydride, and a hydrocarbyl aluminoxane compound having a hydrocarbon group having 1 to 30 carbon atoms. Specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, and alkylaluminoxane. In addition, as (b) component, it is preferable to use aluminoxane and another organoaluminum compound together.

  The component (c) used in the coordination polymerization is a compound having a hydrolyzable halogen or a complex compound thereof with a Lewis base; an organic halide having a tertiary alkyl halide, benzyl halide or allyl halide; a non-coordinating anion And an ionic compound comprising a counter cation. Specific examples of the component (c) include alkylaluminum dichloride, dialkylaluminum chloride, silicon tetrachloride, tin tetrachloride, complexes of zinc chloride with Lewis bases such as alcohol, magnesium chloride and Lewis such as alcohol. Examples include complexes with bases, benzyl chloride, t-butyl chloride, benzyl bromide, t-butyl bromide, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like.

In addition, the modified polybutadiene rubber (A) is reacted with a modifying agent such as a hydrocarbyloxysilane compound and then at least one selected from the group consisting of a condensation accelerator containing a metal element, an inorganic acid and a metal halide. You may make it react.
A modified polybutadiene rubber (A) having a high Mooney viscosity and excellent shape stability by reacting with a condensation accelerator containing the metal element or at least one selected from the group consisting of the inorganic acid and metal halide. Can be manufactured.

As the condensation accelerator containing the metal element, it is preferable to use a metal compound containing at least one metal among the metals included in Groups 2 to 15 of the periodic table. Specific examples of the metal element include titanium, zirconium, aluminum, bismuth, and tin. Moreover, as a condensation accelerator containing the said metal element, the above-mentioned metal alkoxide, carboxylate, or acetylacetonate complex salt is preferable.
Specifically, as the condensation accelerator, tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-ethylhexyloxy) titanium, tetra (octanediolate) titanium, tris (2-ethyl) Hexanoate) bismuth, tetra n-propoxyzirconium, tetra n-butoxyzirconium, bis (2-ethylhexanoate) zirconium oxide, bis (oleate) zirconium oxide, tri-i-propoxyaluminum, trisec-butoxyaluminum, tris (2-ethylhexanoate) aluminum, tris (stearate) aluminum, zirconium tetrakis (acetylacetonate), aluminum tris (acetylacetonate), bis (2-ethylhexanoate) tin Di -n- octyl tin bis (2-ethylhexyl maleate) and the like are preferable.

On the other hand, examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid.
Further, as the metal halide, a metal halide containing at least one metal among the metals included in Group 2 to Group 15 of the periodic table can be suitably used. For example, silicon, tin, More preferably, a halide containing at least one metal atom selected from the group consisting of aluminum, zinc, titanium, and zirconium is used.
Specifically, as the metal halide, trimethylsilyl chloride, dimethyldichlorosilane, methyltrichlorosilane, silicon tetrachloride, methyldichlorosilane, tin tetrachloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, zinc chloride. Titanium tetrachloride, titanocene dichloride, zirconium tetrachloride, zirconocene dichloride and the like are preferable.
The reaction with the inorganic acid or metal halide is preferably performed in the presence of water. The water may be used in the form of a simple substance, a solution of alcohol or the like, or a dispersed micelle in a hydrocarbon solvent.

The modified polybutadiene rubber (A) may be stabilized by reacting with a carboxylic acid partial ester of a polyhydric alcohol after reacting with a modifying agent such as a hydrocarbyloxysilane compound.
Here, the carboxylic acid partial ester of the polyhydric alcohol is an ester of a polyhydric alcohol and a carboxylic acid and means a partial ester having one or more hydroxyl groups. Specifically, an ester of a saccharide having 4 or more carbon atoms or a modified saccharide and a fatty acid is preferably used. This ester is more preferably (1) a fatty acid partial ester of a polyhydric alcohol, particularly a partial ester of a saturated higher fatty acid or unsaturated higher fatty acid having 10 to 20 carbon atoms and a polyhydric alcohol (monoester, diester, triester). And (2) an ester compound in which 1 to 3 partial esters of a polycarboxylic acid and a higher alcohol are bonded to the polyhydric alcohol.
The polyhydric alcohol used as the raw material of the partial ester is preferably a saccharide having 5 or 6 carbon atoms having at least three hydroxyl groups (which may be hydrogenated or not hydrogenated), glycol or poly Hydroxy compounds and the like are used. The raw fatty acid is preferably a saturated or unsaturated fatty acid having 10 to 20 carbon atoms, and for example, stearic acid, lauric acid, and palmitic acid are used.
Among the fatty acid partial esters of the polyhydric alcohols, sorbitan fatty acid esters are preferable. Specifically, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate Examples thereof include esters and sorbitan trioleate.

The rubber composition of the present invention contains natural rubber (B). The natural rubber (B) has a glass transition temperature (Tg) of preferably −50 ° C. or lower, more preferably −55 ° C. or lower, still more preferably −60 ° C. or lower, and preferably −120 ° C. As mentioned above, More preferably, it is -100 degreeC or more. The natural rubber (B) having a glass transition temperature (Tg) of −50 ° C. or less has a great effect of improving the dispersibility of the filler in the rubber composition.
Here, in the present invention, the glass transition temperature (Tg) of a rubber component such as natural rubber (B) can be measured by a temperature dispersion curve of tan δ, for example, a differential scanning calorimeter manufactured by TA Instruments. Can be measured under conditions of a sweep rate of 5 to 10 ° C./min.

  The content of the natural rubber (B) is preferably 30% by mass or more, more preferably 40% by mass or more, and preferably 70% by mass or less, as the content in the rubber component of the rubber composition. More preferably, it is 60 mass% or less. If the content of the natural rubber (B) in the rubber component is 30% by mass or more, the deterioration of the wet performance of the tire can be sufficiently suppressed, and if it is 70% by mass or less, the modified polybutadiene rubber (A) The content can be ensured to further improve the low rolling resistance and wear resistance of the tire.

  The rubber composition of the present invention may contain a rubber component other than the modified polybutadiene rubber (A) and the natural rubber (B). Examples of the rubber component include a modified synthetic isoprene rubber (IR), a modified styrene-butadiene copolymer. Examples thereof include modified diene-based synthetic rubbers such as rubber (SBR) and modified styrene-isoprene copolymer rubber (SIR), and unmodified synthetic rubber. The content of the rubber component other than these modified polybutadiene rubber (A) and natural rubber (B) is preferably 20% by mass or less, more preferably 10% by mass or less as the content of the rubber composition in the rubber component. Yes, and particularly preferably 0% by mass.

The rubber composition of the present invention include C ₅ resins, C ₅ -C ₉ resins, at least one thermoplastic resin selected from the group consisting of C ₉ resins and dicyclopentadiene resin (C). By blending the thermoplastic resin (C) in the rubber composition, it is possible to reduce the elastic modulus in the high strain region while suppressing the decrease in the elastic modulus in the low strain region. While increasing the deformation volume of the tread rubber in the vicinity of the ground contact surface with the large road surface, it is possible to ensure the rigidity of the tread rubber in a portion far from the ground contact surface with the road surface having a small distortion during traveling. Here, since the coefficient of friction (μ) on the wet road surface is proportional to the product of the rigidity of the entire tread rubber, the deformation amount of the tread rubber, and tan δ (loss tangent), the thermoplastic resin (C) is blended. By increasing the amount of deformation of the tread rubber while ensuring the rigidity of the entire tread rubber, the coefficient of friction (μ) on the wet road surface can be sufficiently improved, and the coefficient of friction on the wet road surface (μ) Increases the wettability. Therefore, the wet performance of the tire can be improved by applying the rubber composition containing the thermoplastic resin (C) to the tire tread.

  The blending amount of the thermoplastic resin (C) is preferably in the range of 5 to 40 parts by mass, more preferably 8 to 30 parts by mass, and even more preferably 10 to 20 parts per 100 parts by mass of the rubber component of the rubber composition. Part by mass. When the blending amount of the thermoplastic resin (C) is 5 parts by mass or more with respect to 100 parts by mass of the rubber component, the elastic modulus in the high strain region of the rubber composition can be sufficiently reduced, and 40 masses. If it is less than or equal to a part, a decrease in elastic modulus in the low strain region of the rubber composition can be sufficiently suppressed.

Wherein A _{C 5} resins, refers to _{C 5} type synthetic petroleum resins, examples of the _{C 5} resin, for example, a _{C 5} fraction obtained by thermal cracking of petroleum chemical industry naphtha, AlCl _3, BF _3, etc. And aliphatic petroleum resins obtained by polymerization using a Friedel-Crafts type catalyst. Wherein the _{C 5} fraction, typically 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-olefin hydrocarbons butene, 2-methyl Diolefin hydrocarbons such as -1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, 3-methyl-1,2-butadiene and the like are included. Incidentally, examples of the C ₅ resin may be commercially available products, for example, an ExxonMobil Chemical Co. aliphatic petroleum resin "Escorez (registered trademark) 1000 Series", Nippon Zeon Co., Ltd. aliphatic "A100, B170, M100, R100", "T-REZ RA100" manufactured by Tonen Chemical Co., Ltd., among the "Quinton (registered trademark) 100 series" which are petroleum-based petroleum resins.

Wherein A _C 5 -C _{9 resins,} refers to C 5 -C ₉ based synthetic petroleum resins, examples of the _C 5 -C ₉ resins, for example, a _{C 5} fraction derived from petroleum and _{C 9} fraction Solid polymers obtained by polymerization using Friedel-Crafts type catalysts such as AlCl ₃ and BF _3. More specifically, styrene, vinyltoluene, α-methylstyrene, indene and the like are the main components. And the like. As the C ₅ -C ₉ resins, less resin of C ₉ or more components is preferable from the viewpoint of compatibility with the rubber component. Here, “there is little component of C ₉ or more” means that the component of C ₉ or more in the total amount of the resin is less than 50% by mass, preferably 40% by mass or less. Commercially available products can be used as the C ₅ -C ₉ resin, for example, trade name “Quinton (registered trademark) G100B” (manufactured by Nippon Zeon Co., Ltd.), trade name “ECR213” (ExxonMobil Chemical Co., Ltd.) Product name) and trade name “T-REZ RD104” (manufactured by Tonen Chemical Co., Ltd.).

The C ₉ resin is, for example, vinyl toluene, alkyl styrene, and indene, which are C ₉ fractions by-produced together with petrochemical basic raw materials such as ethylene and propylene by thermal decomposition of naphtha of petrochemical industry. It is resin which polymerized the C9 aromatic. Here, specific examples of the C ₉ fraction obtained by thermal decomposition of naphtha, vinyl toluene, alpha-methyl styrene, beta-methyl styrene, .gamma.-methyl styrene, o- methyl styrene, p- methyl styrene, indene and the like Is mentioned. The C ₉ resin includes C ₉ fraction, C ₈ fraction styrene, etc., C ₁₀ fraction methyl indene, 1,3-dimethyl styrene, etc., as well as naphthalene, vinyl naphthalene, vinyl anthracene, p used as the raw material also -tert- butyl styrene, leave these C ₈ -C ₁₀ fraction or the like mixtures, for example can be obtained by copolymerizing a Friedel-Crafts catalyst. Also, the C ₉ resin, a compound having a hydroxy group may be a modified modified petroleum resin with an unsaturated carboxylic acid compound or the like. Incidentally, examples of the C ₉ resins, can be utilized commercially, for example, the unmodified C ₉ petroleum resin, trade name "Nisseki Neo Polymer (registered trademark) L-90", "Nisseki Neopolymer (registered trademark) 120 "," Nisseki Neopolymer (registered trademark) 130 "," Nisseki Neopolymer (registered trademark) 140 "(manufactured by JX Nippon Mining & Energy Corporation) and the like.

  The dicyclopentadiene resin is a petroleum resin produced from dicyclopentadiene obtained by dimerizing cyclopentadiene as a main raw material. Commercially available products can be used as the dicyclopentadiene resin. For example, “1105, 1325,” of the trade name “Quinton (registered trademark) 1000 series”, which is an alicyclic petroleum resin manufactured by ZEON CORPORATION. 1340 "and the like.

  The rubber composition of the present invention preferably contains a filler. The rubber composition of the present invention preferably contains silica as the filler, and the ratio of silica in the filler is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably. It is 90 mass% or more, and the total amount of the filler may be silica. When silica is included as a filler, the tan δ of the rubber composition is lowered, the low rolling resistance of the tire to which the rubber composition is applied is further improved, and the fuel consumption performance of the tire is further improved. Moreover, if the ratio of the silica in a filler is 70 mass% or more, tan-delta of a rubber composition will fall and the low rolling resistance of the tire to which this rubber composition is applied will improve further.

  There is no restriction | limiting in particular as said silica, For example, wet silica (hydrous silicic acid), dry-type silica (anhydrous silicic acid), calcium silicate, aluminum silicate etc. are mentioned, Among these, wet silica is preferable. These silicas may be used alone or in combination of two or more.

  The amount of silica is preferably in the range of 40 to 70 parts by mass, more preferably 45 to 60 parts by mass with respect to 100 parts by mass of the rubber component of the rubber composition. When the compounding amount of silica is 40 parts by mass or more with respect to 100 parts by mass of the rubber component, the tan δ of the rubber composition is lowered, and the low rolling resistance of the tire to which the rubber composition is applied is further improved. When the amount is 70 parts by mass or less, the flexibility of the rubber composition is high. By applying the rubber composition to the tread rubber of the tire, the deformation volume of the tread rubber is increased, and the wet performance of the tire is further improved. Can be made.

  In the rubber composition of the present invention, it is preferable to further contain carbon black as a filler, and the blending amount of the carbon black is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the rubber component. The range of 3 to 8 parts by mass is more preferable. By adding 1 part by mass or more of carbon black, the rigidity of the rubber composition is improved, and if the amount of carbon black is 10 parts by mass or less, an increase in tan δ can be suppressed. By applying to tire tread rubber, both low rolling resistance and wet performance can be achieved at a high level.

  The carbon black is not particularly limited, and examples thereof include GPF, FEF, HAF, ISAF, and SAF grade carbon black. Among these, from the viewpoint of improving the wet performance of the tire, ISAF and SAF grade carbon black is preferable. These carbon blacks may be used alone or in combination of two or more.

  The filler may contain aluminum hydroxide, alumina, clay, calcium carbonate, etc. in addition to the silica and carbon black described above.

  In the rubber composition of the present invention, the amount of the filler is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and preferably 100 parts by mass or less with respect to 100 parts by mass of the rubber component. More preferably, it is 80 mass parts or less, More preferably, it is 65 mass parts or less. When the blending amount of the filler in the rubber composition is within the above range, the low rolling resistance and wet performance of the tire can be further improved by applying the rubber composition to the tire tread rubber.

In order to improve the compounding effect of the silica, the rubber composition of the present invention preferably further contains a silane coupling agent. The silane coupling agent is not particularly limited, and examples thereof include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, and bis (3-triethoxysilylpropyl). ) Disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercapto Propyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpro Ru-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothia Zolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl -N, N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide and the like can be mentioned. These silane coupling agents may be used alone or in combination of two or more.
Moreover, the range of 2-20 mass parts is preferable with respect to 100 mass parts of said silica, and, as for the compounding quantity of the said silane coupling agent, the range of 5-15 mass parts is still more preferable. When the compounding amount of the silane coupling agent is 2 parts by mass or more with respect to 100 parts by mass of silica, the compounding effect of silica is sufficiently improved, and the compounding amount of the silane coupling agent is with respect to 100 parts by mass of silica. If it is 20 parts by mass or less, the possibility of gelation of the rubber component is low.

The rubber composition of the present invention may further contain a softening agent from the viewpoint of processability and workability. The blending amount of the softening agent is preferably in the range of 1 to 5 parts by mass, more preferably in the range of 1.5 to 3 parts by mass with respect to 100 parts by mass of the rubber component. By blending 1 part by mass or more of the softening agent, kneading of the rubber composition is facilitated, and by blending 5 parts by mass or less of the softening agent, it is possible to suppress a decrease in rigidity of the rubber composition.
Here, examples of the softening agent include mineral-derived mineral oil, petroleum-derived aromatic oil, paraffin oil, naphthene oil, natural-derived palm oil, and the like. Among these, improvement of tire wet performance From this point of view, mineral-derived softeners and petroleum-derived softeners are preferred.

The rubber composition of the present invention may further contain a fatty acid metal salt. Examples of the metal used in the fatty acid metal salt include Zn, K, Ca, Na, Mg, Co, Ni, Ba, Fe, Al, Cu, and Mn, and Zn is preferable. On the other hand, the fatty acid used in the fatty acid metal salt includes a fatty acid having a saturated or unsaturated linear, branched or cyclic structure having 4 to 30 carbon atoms, or a mixture thereof. ~ 22 saturated or unsaturated linear fatty acids are preferred. Examples of the saturated linear fatty acid having 10 to 22 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid and the like, and examples of the unsaturated linear fatty acid having 10 to 22 carbon atoms include oleic acid and linoleic acid. Linolenic acid, arachidonic acid and the like. The said fatty acid metal salt may be used individually by 1 type, and may be used in combination of 2 or more type.
The compounding amount of the fatty acid metal salt is preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component of the rubber composition.

  The rubber composition of the present invention includes modified polybutadiene rubber (A), natural rubber (B), thermoplastic resin (C), filler, silane coupling agent, softener, fatty acid metal salt, as well as in the rubber industry. Commonly used compounding agents, for example, stearic acid, anti-aging agent, zinc oxide (zinc white), vulcanization accelerator, vulcanizing agent, etc. are appropriately selected and blended within the range not impairing the object of the present invention. May be. As these compounding agents, commercially available products can be suitably used.

  The rubber composition of the present invention can be used for various rubber products including tires. In particular, the rubber composition of the present invention is suitable as a tread rubber for tires.

<Tire>
The tire of the present invention is characterized by using the above-described rubber composition for a tread rubber. The tire of the present invention is excellent in low rolling resistance, wet performance, and wear resistance because the rubber composition is used for tread rubber. The tire of the present invention can be used as a tire for various vehicles, but is preferable as a tire for passenger cars.

  The tire of the present invention may be obtained by vulcanization after molding using an unvulcanized rubber composition depending on the type of tire to be applied, or by using a semi-vulcanized rubber that has undergone a preliminary vulcanization step or the like After molding, it may be obtained by further vulcanization. The tire of the present invention is preferably a pneumatic tire, and as a gas filled in the pneumatic tire, an inert gas such as nitrogen, argon, helium, or the like other than normal or oxygen partial pressure adjusted air is used. Can be used.

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

<Preparation and evaluation of rubber composition>
In addition to the formulation shown in Table 1, the following components were also added, and a rubber composition was produced using a normal Banbury mixer.
Petroleum oil [made by Japan Energy, trade name “Process X-140”]: 3 parts by mass Antiaging agent [N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, Ouchi Shinsei Chemical Co., Ltd., trade name "NOCRACK 6C"]: 1 part by mass-Stearic acid: 1 part by mass-Zinc flower: 2.5 parts by mass-Vulcanization accelerator A [1,3-diphenylguanidine, Product name “Soccinol (registered trademark) DG” manufactured by Sumitomo Chemical Co., Ltd .: 0.8 part by mass ・ Vulcanization accelerator B [dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., product name “Noxeller ( (Registered Trademark) DM-P ": 1.1 parts by mass-Vulcanization accelerator C [N-cyclohexyl-2-benzothiazylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name" Noxeller (registered trademark) " C Z-G ": 1 part by mass-Sulfur: 1.9 parts by mass

  The resulting rubber composition was evaluated for wet performance, low rolling resistance, wear resistance, fracture resistance, and temperature dependence of tan δ by the following methods. The results are shown in Table 1.

(1) Wet performance A pneumatic radial tire for a passenger car having a size of 195 / 65R15 was produced using the rubber composition obtained as described above as a tread rubber. The prepared test tire was mounted on a test vehicle, and in an actual vehicle test on a wet road surface, steering stability was represented by a driver's feeling score, and the tire feeling score of Comparative Example 4 was indicated as an index. It shows that it is excellent in wet performance, so that an index value is large.

(2) Low rolling resistance With respect to the vulcanized rubber obtained by vulcanizing the rubber composition at 145 ° C. for 33 minutes, an initial load of 160 mg, dynamic strain of 1%, Under the condition of a frequency of 52 Hz, tan δ (loss tangent) at 60 ° C. was measured. The reciprocal of the obtained tan δ value was calculated, and the value of Comparative Example 4 was taken as 100, and displayed as an index. The larger the index value, the smaller the tan δ, and the lower the rolling resistance.

(3) Abrasion resistance After the obtained rubber composition was vulcanized at 145 ° C. for 33 minutes, the amount of wear was measured at 23 ° C. using a Lambone abrasion tester in accordance with JIS K 6264-2: 2005. The reciprocal of the amount of wear in Comparative Example 4 was taken as 100, and each index was displayed. The larger the index value, the smaller the amount of wear and the better the wear resistance performance.

(4) Fracture resistance Rubber obtained by performing a tensile test at room temperature in accordance with JIS K 6251 using a vulcanized rubber obtained by vulcanizing the obtained rubber composition at 145 ° C. for 33 minutes. The tensile strength of the composition was measured. The evaluation results are shown as an index with the value of Comparative Example 4 being 100. The larger the value, the better the fracture resistance.

(5) Temperature dependence of tan δ With respect to a vulcanized rubber obtained by vulcanizing a rubber composition at 145 ° C. for 33 minutes, an initial load of 160 mg and a dynamic strain of 1% using a spectrometer manufactured by Ueshima Seisakusho Co., Ltd. , Tan δ (loss tangent) at 30 ° C. and 60 ° C. was measured under a frequency of 52 Hz, and tan δ at 30 ° C. minus tan δ at 60 ° C. [(tan δ at 30 ° C.) − (Tan δ at 60 ° C.) ] Was calculated. The value [(tan δ at 30 ° C.) − (Tan δ at 60 ° C.)] obtained by subtracting tan δ at 60 ° C. from the tan δ at 30 ° C. of the rubber composition of Comparative Example 4 was expressed as an index. The smaller the index value, the smaller the temperature dependency of tan δ.

* 1 Natural rubber: RSS # 3, glass transition temperature (Tg) = − 73 ° C.
* 2 Modified styrene-butadiene copolymer rubber: Modified styrene-butadiene copolymer rubber synthesized by the following method, glass transition temperature (Tg) = − 70 ° C.
* 3 Unmodified styrene-butadiene copolymer rubber: manufactured by JSR Corporation, trade name “# 1500”, glass transition temperature (Tg) = − 70 ° C.
* 4 Modified polybutadiene rubber A: Modified polybutadiene rubber synthesized by the following method * 5 Modified polybutadiene rubber B: Modified polybutadiene rubber synthesized by the following method * 6 Modified polybutadiene rubber C: Modified polybutadiene rubber synthesized by the following method * 7 Unmodified polybutadiene rubber: Product name “BR01” manufactured by JSR Corporation
* 8 _{C 9} resins: JX Nippon Oil & Energy Co., Ltd., trade name "Oil Neo polymer (registered trademark) 140"
* 9 Dicyclopentadiene resin: Product name “Quinton (registered trademark) 1105” manufactured by Zeon Corporation
* 10 _C 5 -C ₉ resin: Nippon Zeon Co., Ltd., trade name "Quinton (registered trademark) G100B"
* 11 Silica: Tosoh Silica Industry Co., Ltd., trade name “Nipsil AQ”
* 12 Carbon black: N234 (ISAF), manufactured by Asahi Carbon Co., Ltd., trade name “# 78”
* 13 Silane coupling agent: bis (3-triethoxysilylpropyl) disulfide (average sulfur chain length: 2.35), manufactured by Evonik, trade name “Si75” (registered trademark)

<Synthesis of Modified Styrene-Butadiene Copolymer Rubber>
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 67.5 g of 1,3-butadiene and 7.5 g of styrene, and 2,2 -Ditetrahydrofurylpropane 0.6 mmol was added, 0.8 mmol of n-butyllithium was added, and then polymerization was performed at 50 ° C for 1.5 hours. In this case, 0.72 mmol of N, N-bis (trimethylsilyl) -3- [diethoxy (methyl) silyl] propylamine was added as a modifier to the polymerization reaction system in which the polymerization conversion rate was almost 100%, and 50% A denaturation reaction was performed at 30 ° C. for 30 minutes. Thereafter, 2 mL of a 2,6-di-t-butyl-p-cresol (BHT) isopropanol 5 mass% solution was added to stop the reaction, followed by drying according to a conventional method to obtain a modified styrene-butadiene copolymer rubber. It was.

<Synthesis of modified polybutadiene rubber A>
(1) Production of unmodified polybutadiene Into a nitrogen-substituted 5 L autoclave, 1.4 kg of cyclohexane, 250 g of 1,3-butadiene, and 2,2-ditetrahydrofurylpropane (0.285 mmol) were injected as a cyclohexane solution under nitrogen. Then, 2.85 mmol of n-butyllithium (BuLi) was added thereto, followed by polymerization in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The reaction conversion of 1,3-butadiene was almost 100%. A part of this polymer solution was drawn into a methanol solution containing 1.3 g of 2,6-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping, and a roll at 110 ° C. To obtain polybutadiene before modification.
(2) Production of primary amine-modified polybutadiene The polymer solution obtained in (1) above is maintained at a temperature of 50 ° C. without deactivating the polymerization catalyst, and N, wherein the primary amino group is protected. 1129 mg (3.364 mmol) of N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane [corresponding to the compound of general formula (IV)] was added, and the modification reaction was carried out for 15 minutes.
Thereafter, 8.111 g of tetrakis (2-ethyl-1,3-hexanediolato) titanium, which is a condensation accelerator, was added and further stirred for 15 minutes.
Finally, 242 mg of silicon tetrachloride as a metal halide was added to the polymer solution after the reaction, and 2,6-di-tert-butyl-p-cresol was added. Next, deprotection of the primary amino group which has been desolvated and protected by steam stripping is performed, and the rubber is dried by a ripening roll adjusted to 110 ° C., and primary amine-modified polybutadiene (modified polybutadiene rubber A) Got.

<Synthesis of modified polybutadiene rubber B>
(1) Preparation of catalyst In a glass bottle with a volume of 100 mL with a rubber jar, dried and nitrogen-substituted, in the following order, 7.11 g of cyclohexane solution of butadiene (15.2% by mass), cyclohexane of neodymium neodecanoate Solution (0.56 mol / L) 0.59 mL, methylaluminoxane MAO (PMAO manufactured by Tosoh Akzo) in toluene solution (aluminum concentration 3.23 mol / L) 10.32 mL, hexane solution of diisobutylaluminum hydride (manufactured by Kanto Chemical) (0.90 mol / L) 7.77 mL was added, and after aging at room temperature for 2 minutes, 1.45 mL of a hexane solution (0.95 mol / L) of chlorinated diethylaluminum (manufactured by Kanto Chemical) was added and occasionally at room temperature. The mixture was aged for 15 minutes with stirring. The neodymium concentration in the catalyst solution thus obtained was 0.011 mol / L.
(2) Production of intermediate polymer A glass bottle with a rubber cap of 900 mL capacity was dried and purged with nitrogen, and a dry-purified cyclohexane solution of butadiene and dry cyclohexane were added to each, and 400 g of a cyclohexane solution containing 12.5% by mass of butadiene was added. It was in the state of being thrown in. Next, 2.28 mL (0.025 mmol in terms of neodymium) of the catalyst solution prepared in the above (1) was added, and polymerization was performed in a 50 ° C. warm water bath for 1.0 hour to produce an intermediate polymer.
(3) Modification treatment A hexane solution having a concentration of 3-glycidoxypropyltrimethoxysilane [corresponding to the compound of general formula (II)] of 1.0 mol / L, and 3-glycidoxypropyltrimethoxysilane converted to neodymium On the other hand, the polymerization solution obtained in the above (2) was added so as to be 23.5 molar equivalents and treated at 50 ° C. for 60 minutes.
Next, 1.2 mL of sorbitan trioleate (manufactured by Kanto Chemical Co., Inc.) was added, and after a further denaturation reaction at 50 ° C. for 1 hour, the anti-aging agent 2,2′-methylene-bis (4- Ethyl-6-t-butylphenol) (NS-5) 2 mL of isopropanol 5% by mass was added to stop the reaction, and a trace amount of 2,2′-methylene-bis (4-ethyl-6-t-butylphenol) was added. ) Reprecipitation was carried out in isopropanol containing (NS-5), and drum drying was performed to obtain a modified polybutadiene rubber B.

<Synthesis of modified polybutadiene rubber C>
In a pressure-resistant glass container having an internal volume of about 900 mL that has been dried and purged with nitrogen, 283 g of cyclohexane, 50 g of 1,3-butadiene monomer, 0.0057 mmol of 2,2-ditetrahydrofurylpropane, and 0.513 mmol of hexamethyleneimine are added to the cyclohexane solution. And 0.57 mmol of n-butyllithium (BuLi) was added thereto, followed by polymerization in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The polymerization conversion was almost 100%. To this polymerization system, 0.100 mmol of tin tetrachloride was added as a cyclohexane solution and stirred at 50 ° C. for 30 minutes. Thereafter, 0.5 mL of a 5% solution of 2,6-di-t-butylparacresol (BHT) in isopropanol was added to stop the reaction, followed by drying according to a conventional method to obtain a modified polybutadiene rubber C.

  It can be seen from Table 1 that the rubber compositions of the examples according to the present invention can improve the wear resistance while achieving both the low rolling resistance and the wet performance of the tire when applied to the tire.

The rubber composition of the present invention can be used for tire tread rubber.
The tire of the present invention can be used as a tire for various vehicles.

Claims (4)

Modified polybutadiene rubber (A);
Natural rubber (B),
C ₅ resins, C ₅ -C ₉ resins, and one or more thermoplastic resin selected from the group consisting of C ₉ resins and dicyclopentadiene resin (C),
A rubber composition comprising: The modified polybutadiene rubber (A) has the following general formula (II):

[Wherein n1 + n2 + n3 + n4 is 4 (where n2 is an integer of 1 to 4, n1, n3 and n4 are integers of 0 to 3), A ¹ is a saturated cyclic tertiary amine compound residue, Unsaturated cyclic tertiary amine compound residue, ketimine residue, nitrile group, isocyanate group, thioisocyanate group, epoxy group, thioepoxy group, isocyanuric acid trihydrocarbyl ester group, carbonic acid dihydrocarbyl ester group, pyridine group, ketone group Thioketone group, aldehyde group, thioaldehyde group, amide group, carboxylic acid ester group, thiocarboxylic acid ester group, metal salt of carboxylic acid ester, metal salt of thiocarboxylic acid ester, carboxylic acid anhydride residue, carboxylic acid halogen compound residue Group, monovalent group with epoxy, silazane or disulfide, and hydrolyzable At least one functional group selected from a primary or secondary amino group having a group or a mercapto group having a hydrolyzable group, and when n4 is 2 or more, they may be the same or different, A ¹ may be a divalent group that binds to Si to form a cyclic structure, and R ²¹ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or 6 carbon atoms. -18 monovalent aromatic hydrocarbon group, and when n1 is 2 or more, they may be the same or different, and R ²³ is a monovalent aliphatic or alicyclic carbon atom having 1 to 20 carbon atoms. A hydrogen group, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and when n3 is 2 or more, they may be the same or different, and R ²² is one having 1 to 20 carbon atoms. Valent aliphatic or alicyclic hydrocarbon group or monovalent aromatic having 6 to 18 carbon atoms It is a hydrocarbon group, both of which may contain a nitrogen atom and / or a silicon atom, and when n2 is 2 or more, they may be the same or different from each other, or together form a ring R ²⁴ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and n4 is 2 or more. The rubber composition according to claim 1, wherein the rubber composition is modified with a compound represented by the formula: The modified polybutadiene rubber (A) has the following formula (i):

[Wherein R ¹¹ and R ¹² are each independently an alkyl group, a cycloalkyl group, or an aralkyl group having 1 to 12 carbon atoms], or the following formula (ii):

[Wherein R ¹³ represents a cyclic amino group represented by the following formula: R ¹³ represents an alkylene group, a substituted alkylene group, an oxyalkylene group or an N-alkylamino-alkylene group having 3 to 16 methylene groups] 2. The rubber composition according to 1.   A tire comprising the rubber composition according to any one of claims 1 to 3 as a tread rubber.