JP5529930B2 - Rubber composition for tread and pneumatic tire - Google Patents

Description

The present invention relates to a rubber composition for a tread and a pneumatic tire produced using the rubber composition.

As a rubber composition for an automobile tire, a rubber composition containing a conjugated diene polymer such as polybutadiene or butadiene-styrene copolymer and a filler such as carbon black or silica is used. In recent years, due to increasing interest in environmental issues, there has been a strong demand for lower fuel consumption for automobiles, and rubber compositions used for automobile tires are also required to have excellent fuel efficiency. .

As a method for improving fuel economy, for example, Patent Document 1 proposes a method using a diene rubber (modified rubber) modified with an organosilicon compound containing an amino group and an alkoxy group. However, in recent years, further improvement in fuel economy has been demanded due to an increase in interest in environmental problems. In addition, the performance required for rubber compositions for automobile tires includes wet grip performance and wear resistance, but these performances are generally in contradiction to low fuel consumption. It was difficult to obtain a high dimension and good balance.

JP 2000-344955 A

An object of the present invention is to solve the above problems and provide a rubber composition for a tread that can improve fuel economy, wet grip performance, and wear resistance in a well-balanced manner, and a pneumatic tire using the same.

（式中、Ｒ^１１は水素原子又はヒドロカルビル基を表し、ｍは０又は１であり、Ｒ^１２はヒドロカルビレン基を表し、Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立に、置換アミノ基、又は、置換基を有していてもよいヒドロカルビル基を表し、Ｘ^１、Ｘ^２及びＸ^３の少なくとも１つが置換アミノ基である。）

（式中、Ｒ^２１は水素原子又はヒドロカルビル基を表し、ｎは０又は１であり、Ｒ^２２はヒドロカルビレン基を表し、Ａは置換アミノ基、又は、含窒素複素環基を表す。） The present invention contains a rubber component, silica, and a silane coupling agent having a mercapto group, and is a monomer unit based on a conjugated diene represented by the following formula (1) in 100% by mass of the rubber component. The content of the conjugated diene polymer having a monomer unit based on the compound and a monomer unit based on the compound represented by the following formula (2) is 5% by mass or more, and 100 parts by mass of the rubber component It is related with the rubber composition for treads whose content of the said silica with respect to 5-150 mass parts.

Wherein R ¹¹ represents a hydrogen atom or a hydrocarbyl group, m is 0 or 1, R ¹² represents a hydrocarbylene group, and X ¹ , X ² and X ³ are each independently a substituted amino group Or a hydrocarbyl group which may have a substituent, and at least one of X ¹ , X ² and X ³ is a substituted amino group.)

(In the formula, R ²¹ represents a hydrogen atom or a hydrocarbyl group, n is 0 or 1, R ²² represents a hydrocarbylene group, and A represents a substituted amino group or a nitrogen-containing heterocyclic group.)

In formula (1), R ¹¹ is preferably a hydrogen atom, and m is preferably 0.

（式中、ｒは０〜５の整数を表し、ｒが１から５の整数である場合、（ＣＨ_２）_ｒはベンゼン環上の置換基であり、（ＣＨ_２）_ｒがＡと結合し、ｒが０である場合、（ＣＨ_２）_ｒはベンゼン環とＡとの結合を表す。） In formula (2), R ²¹ is preferably a hydrogen atom, n is 1, R ²² is a group represented by the following formula (2-Y), and A is preferably a substituted amino group.

(In the formula, r represents an integer of 0 to 5, and when r is an integer of 1 to 5, (CH ₂ ) _r is a substituent on the benzene ring, and (CH ₂ ) _r is bonded to A. , R is 0, (CH ₂ ) _r represents a bond between the benzene ring and A.)

The vinyl bond content of the conjugated diene polymer is preferably 20 mol% or more and 70 mol% or less, with the content of the structural unit based on the conjugated diene being 100 mol%.

（式中、Ｒ^１０１〜Ｒ^１０３は、分岐若しくは非分岐の炭素数１〜１２のアルキル基、分岐若しくは非分岐の炭素数１〜１２のアルコキシ基、又は−Ｏ−（Ｒ^１１１−Ｏ）_ｂ−Ｒ^１１２（ｂ個のＲ^１１１は、分岐若しくは非分岐の炭素数１〜３０の２価の炭化水素基を表す。ｂ個のＲ^１１１はそれぞれ同一でも異なっていてもよい。Ｒ^１１２は、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、炭素数６〜３０のアリール基、又は炭素数７〜３０のアラルキル基を表す。ｂは１〜３０の整数を表す。）で表される基を表す。Ｒ^１０１〜Ｒ^１０３はそれぞれ同一でも異なっていてもよい。Ｒ^１０４は、分岐若しくは非分岐の炭素数１〜６のアルキレン基を表す。）

（式中、Ｒ^２０１は水素、ハロゲン、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、分岐若しくは非分岐の炭素数２〜３０のアルキニル基、又は該アルキル基の末端の水素が水酸基若しくはカルボキシル基で置換されたものを表す。Ｒ^２０２は分岐若しくは非分岐の炭素数１〜３０のアルキレン基、分岐若しくは非分岐の炭素数２〜３０のアルケニレン基、又は分岐若しくは非分岐の炭素数２〜３０のアルキニレン基を表す。Ｒ^２０１とＲ^２０２とで環構造を形成してもよい。） The silane coupling agent includes a silane coupling agent represented by the following formula (I) and / or a binding unit B represented by the following formula (II) and a binding unit A represented by the following formula (III). A silane coupling agent is preferred.

(Wherein R ^{101 to} R ¹⁰³ are branched or unbranched alkyl groups having 1 to 12 carbon atoms, branched or unbranched alkoxy groups having 1 to 12 carbon atoms, or —O— (R ¹¹¹ —O) _b. -R ¹¹² (b pieces ^{by R 111} are .b pieces ^{by R 111} are optionally each be the same or different ^{.R 112} representing a divalent hydrocarbon group of branched or unbranched C1-30 is A branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms; Represents an integer of 1 to 30.) R ^{101 to} R ¹⁰³ may be the same or different, and R ¹⁰⁴ is a branched or unbranched alkylene group having 1 to 6 carbon atoms. Represents.)

Wherein R ²⁰¹ is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, branched or unbranched alkenyl group having 2 to 30 carbon atoms, branched or unbranched carbon group having 2 to 30 carbon atoms. An alkynyl group or a group in which the hydrogen at the terminal of the alkyl group is substituted with a hydroxyl group or a carboxyl group, R ²⁰² represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched carbon number of 2 30 represents an alkenylene group or a branched or unbranched alkynylene group having 2 to 30 carbon atoms, and R ²⁰¹ and R ²⁰² may form a ring structure.)

The present invention also relates to a pneumatic tire produced using the rubber composition.

According to the present invention, since it is a rubber composition in which a conjugated diene polymer having a specific monomer unit, silica, and a silane coupling agent having a mercapto group are blended, low fuel consumption, wet grip performance And a pneumatic tire with improved wear resistance in a well-balanced manner.

（式中、Ｒ^１１は水素原子又はヒドロカルビル基を表し、ｍは０又は１であり、Ｒ^１２はヒドロカルビレン基を表し、Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立に、置換アミノ基、又は、置換基を有していてもよいヒドロカルビル基を表し、Ｘ^１、Ｘ^２及びＸ^３の少なくとも１つが置換アミノ基である。）

（式中、Ｒ^２１は水素原子又はヒドロカルビル基を表し、ｎは０又は１であり、Ｒ^２２はヒドロカルビレン基を表し、Ａは置換アミノ基、又は、含窒素複素環基を表す。） The conjugated diene polymer according to the present invention is based on a monomer unit based on a conjugated diene, a monomer unit based on a compound represented by the following formula (1), and a compound represented by the following formula (2). Monomer units.

Wherein R ¹¹ represents a hydrogen atom or a hydrocarbyl group, m is 0 or 1, R ¹² represents a hydrocarbylene group, and X ¹ , X ² and X ³ are each independently a substituted amino group Or a hydrocarbyl group which may have a substituent, and at least one of X ¹ , X ² and X ³ is a substituted amino group.)

(In the formula, R ²¹ represents a hydrogen atom or a hydrocarbyl group, n is 0 or 1, R ²² represents a hydrocarbylene group, and A represents a substituted amino group or a nitrogen-containing heterocyclic group.)

As used herein, a hydrocarbyl group represents a hydrocarbon residue. The hydrocarbylene group represents a divalent hydrocarbon residue. The nitrogen-containing heterocyclic group represents a group obtained by removing one hydrogen atom from the carbon atom of a heterocyclic ring of a compound having a nitrogen-containing heterocyclic ring. The nitrogen-containing heterocyclic ring is a heterocyclic group having a nitrogen atom as a hetero atom constituting the ring. Represents a ring.

Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene and the like, and one or more of these are used. . The conjugated diene is preferably 1,3-butadiene or isoprene.

R ^{11 in the} formula (1) represents a hydrogen atom or a hydrocarbyl group.

Examples of the hydrocarbyl group for R ¹¹ include an alkyl group and an alkenyl group.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group is preferable. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group, and a vinyl group is preferable.

R ¹¹ is preferably a hydrogen atom, a methyl group, or a vinyl group.

Examples of the hydrocarbylene group for R ¹² include an alkylene group, an arylene group, and a group in which an arylene group and an alkylene group are bonded.

Examples of the alkylene group include a methylene group, an ethylene group, and a trimethylene group. Preferably, it is a methylene group or an ethylene group.

Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. A phenylene group is preferred.

Examples of the group in which an arylene group and an alkylene group are bonded include a group in which a phenylene group and an alkylene group are bonded, a group in which a naphthylene group and an alkylene group are bonded, and a group in which a biphenylene group and an alkylene group are bonded. .

In the group in which the arylene group and the alkylene group are bonded, it is preferable that the carbon atom of the alkylene group is bonded to the silicon atom of the formula (1).

（式中、ｑは、１〜１０の整数を表す。） In a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), depending on the position of the carbon atom on the benzene ring from which a hydrogen atom is removed and the phenylene group to which the alkylene group is bonded, a para-phenylene-alkylene group ( For example, a group represented by the following formula (1a)), a meta-phenylene-alkylene group (for example, a group represented by the following formula (1b)), an ortho-phenylene-alkylene group (for example, the following formula (1c )))).

(In the formula, q represents an integer of 1 to 10.)

The group in which an arylene group and an alkylene group are bonded is preferably a group in which a phenylene group and an alkylene group are bonded, and more preferably a group represented by the above formula (1a) or a group represented by the above formula (1b). And more preferably a para-phenylene-methylene group (a group represented by the formula (1a) where q = 1) and a meta-phenylene-methylene group (a formula (1b) where q = 1). Group, a para-phenylene-ethylene group (a group represented by formula (1a) where q = 2), a meta-phenylene-ethylene group (a formula (1b) where q = 2). Group).

When R ¹¹ is a hydrogen atom or a methyl group, and m is 1, R ¹² is preferably a group in which an arylene group and an alkylene group are bonded or an arylene group, more preferably a phenylene group and an alkylene group. And a phenylene group, more preferably a phenylene group.

When R ¹¹ is a vinyl group and m is 1, R ¹² is preferably an alkylene group, more preferably a methylene group or an ethylene group.

In the formula (1), R ¹¹ is preferably a hydrogen atom and m is 0.

The hydrocarbyl group optionally having a substituent of X ¹ , X ² and X ³ is a hydrocarbyl group optionally having at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom Can give.

Examples of the hydrocarbyl group of X ¹ , X ² and X ³ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group and an aralkyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group. Examples of the alkynyl group include an ethynyl group and a propargyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group. The hydrocarbyl group is preferably an alkyl group.

Examples of the hydrocarbyl group having an oxygen atom of X ¹ , X ² and X ³ include alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, ethoxymethyl group and ethoxyethyl group.

Examples of the hydrocarbyl group having nitrogen atoms of X ¹ , X ² and X ³ include dialkylaminoalkyl groups such as dimethylaminomethyl group, dimethylaminoethyl group, diethylaminomethyl group and diethylaminoethyl group.

Examples of the hydrocarbyl group having silicon atoms of X ¹ , X ² and X ³ include trialkylsilylalkyl groups such as trimethylsilylmethyl group, trimethylsilylethyl group, triethylsilylmethyl group and triethylsilylethyl group.

The number of carbon atoms of the hydrocarbyl group which may have a substituent of X ¹ , X ² and X ³ is preferably 1 to 10, more preferably 1 to 4.

The hydrocarbyl group which may have a substituent of X ¹ , X ² and X ³ is preferably an alkyl group or an alkoxyalkyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 4 carbon atoms.

（式中、Ｒ^１３及びＲ^１４は、それぞれ、ヒドロカルビル基、又は、トリヒドロカルビルシリル基、あるいは、Ｒ^１３とＲ^１４とが結合して、窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基、又は、Ｒ^１３とＲ^１４は１つの基であって、窒素原子に二重結合で結合する基を表す。） The substituted amino group for X ¹ , X ² and X ³ is preferably a group represented by the following formula (1-X).

(In the formula, each of R ¹³ and R ¹⁴ has a hydrocarbyl group, a trihydrocarbyl silyl group, or R ¹³ and R ¹⁴ bonded to each other, and has a nitrogen atom and / or an oxygen atom as a hetero atom. The hydrocarbylene group which may be substituted, or R ¹³ and R ¹⁴ are one group and represent a group bonded to the nitrogen atom with a double bond.)

Examples of the hydrocarbyl group of R ¹³ and R ¹⁴ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group. Examples of the alkynyl group include an ethynyl group and a propargyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group.

The number of carbon atoms of the hydrocarbyl group of R ¹³ and R ¹⁴ is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.

The hydrocarbyl group of R ¹³ and R ¹⁴ is preferably an alkyl group, more preferably a linear alkyl group.

Examples of the trihydrocarbylsilyl group of R ¹³ and R ¹⁴ include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group.

The trihydrocarbylsilyl group of R ¹³ and R ¹⁴ is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably an alkyl group bonded to a silicon atom having 1 to 3 carbon atoms. A trialkylsilyl group which is an alkyl group, and more preferably a trimethylsilyl group.

The hydrocarbylene group optionally having a nitrogen atom and / or an oxygen atom to which R ¹³ and R ¹⁴ are bonded as a hetero atom includes a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and an oxygen atom. And hydrocarbylene groups. Examples of the hydrocarbylene group include an alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. As the hydrocarbylene group having a nitrogen atom, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH—N A group represented by ═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified. Examples of the hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom to which R ¹³ and R ¹⁴ are bonded as a hetero atom is preferably 2 to 20, more preferably 2 to 7. Yes, more preferably 4-6.

The hydrocarbylene group which may have a nitrogen atom and / or oxygen atom to which R ¹³ and R ¹⁴ are bonded as a hetero atom is preferably a hydrocarbylene group, more preferably an alkylene group, A polymethylene group is preferred.

Examples of one group in which R ¹³ and R ¹⁴ are bonded to the nitrogen atom with a double bond include ethylidene group, propylidene group, butylidene group, 1-methylethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene And hydrocarbylidene groups such as groups.

The number of carbon atoms of one group in which R ¹³ and R ¹⁴ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 6.

R ¹³ and R ¹⁴ are preferably an alkyl group, a trialkylsilyl group, an alkylene group in which R ¹³ and R ¹⁴ are bonded, and more preferably an alkyl group.

Examples of the group represented by the formula (1-X) include an acyclic amino group and a cyclic amino group.

Examples of the acyclic amino group include a dialkylamino group and a bis (trialkylsilyl) amino group. Dialkylamino groups include dimethylamino, diethylamino, di (n-propyl) amino, di (isopropyl) amino, di (n-butyl) amino, di (sec-butyl) amino, di (tert -Butyl) amino group and ethylmethylamino group can be mentioned. Examples of the bis (trialkylsilyl) amino group include a bis (trimethylsilyl) amino group and a bis (t-butyldimethylsilyl) amino group.

Examples of the acyclic amino group include an ethylideneamino group, a 1-methylpropylideneamino group, a 1,3-dimethylbutylideneamino group, a 1-methylethylideneamino group, and a 4-N, N-dimethylaminobenzylideneamino group. Can do.

Examples of the cyclic amino group include 1-aziridinyl group, 1-azetidinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-decamidine group. Examples thereof include 1-polymethyleneimino groups such as a methyleneimino group and 1-dodecamethyleneimino group. Moreover, 1-pyrrolyl group, 1-pyrazolidinyl group, 1-imidazolidinyl group, 1-pyrazolyl group, 1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1-piperazinyl group and morpholino group are exemplified.

The group represented by the formula (1-X) is preferably an acyclic amino group, and more preferably a dialkylamino group. The dialkylamino group is preferably a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, or a di (n-butyl) amino group, and more preferably a dimethylamino group or a diethylamino group.

At least one of X ¹ , X ² and X ^{3 in} the formula (1) is a substituted amino group, preferably two or more of X ¹ , X ² and X ³ are substituted amino groups, more preferably, ^{Two of} X ¹ , X ² and X ³ are substituted amino groups.

Examples of the compound represented by formula (1) include the following compounds as compounds in which R ¹¹ is a hydrogen atom and one of X ¹ , X ² and X ³ is a dialkylamino group.

Compound in which m is 0:
(Dimethylamino) dimethylvinylsilane,
(Diethylamino) dimethylvinylsilane,
(Di-n-propylamino) dimethylvinylsilane,
(Di-n-butylamino) dimethylvinylsilane,
(Dimethylamino) diethylvinylsilane,
(Diethylamino) diethylvinylsilane,
(Di-n-propylamino) diethylvinylsilane,
(Di-n-butylamino) diethylvinylsilane.

Compound in which m is 1:
(Dimethylamino) dimethyl-4-vinylphenylsilane,
(Dimethylamino) dimethyl-3-vinylphenylsilane,
(Diethylamino) dimethyl-4-vinylphenylsilane,
(Diethylamino) dimethyl-3-vinylphenylsilane,
(Di-n-propylamino) dimethyl-4-vinylphenylsilane,
(Di-n-propylamino) dimethyl-3-vinylphenylsilane,
(Di-n-butylamino) dimethyl-4-vinylphenylsilane,
(Di-n-butylamino) dimethyl-3-vinylphenylsilane,
(Dimethylamino) diethyl-4-vinylphenylsilane,
(Dimethylamino) diethyl-3-vinylphenylsilane,
(Diethylamino) diethyl-4-vinylphenylsilane,
(Diethylamino) diethyl-3-vinylphenylsilane,
(Di-n-propylamino) diethyl-4-vinylphenylsilane,
(Di-n-propylamino) diethyl-3-vinylphenylsilane,
(Di-n-butylamino) diethyl-4-vinylphenylsilane,
(Di-n-butylamino) diethyl-3-vinylphenylsilane.

Examples of the compound represented by formula (1) include the following compounds as compounds in which R ¹¹ is a hydrogen atom and ^{two of} X ¹ , X ² and X ³ are dialkylamino groups.

Compound in which m is 0:
Bis (dimethylamino) methylvinylsilane,
Bis (diethylamino) methylvinylsilane,
Bis (di-n-propylamino) methylvinylsilane,
Bis (di-n-butylamino) methylvinylsilane,
Bis (dimethylamino) ethylvinylsilane,
Bis (diethylamino) ethylvinylsilane,
Bis (di-n-propylamino) ethylvinylsilane,
Bis (di-n-butylamino) ethylvinylsilane.

Compound in which m is 1:
Bis (dimethylamino) methyl-4-vinylphenylsilane,
Bis (dimethylamino) methyl-3-vinylphenylsilane,
Bis (diethylamino) methyl-4-vinylphenylsilane,
Bis (diethylamino) methyl-3-vinylphenylsilane,
Bis (di-n-propylamino) methyl-4-vinylphenylsilane,
Bis (di-n-propylamino) methyl-3-vinylphenylsilane,
Bis (di-n-butylamino) methyl-4-vinylphenylsilane,
Bis (di-n-butylamino) methyl-3-vinylphenylsilane,
Bis (dimethylamino) ethyl-4-vinylphenylsilane,
Bis (dimethylamino) ethyl-3-vinylphenylsilane,
Bis (diethylamino) ethyl-4-vinylphenylsilane,
Bis (diethylamino) ethyl-3-vinylphenylsilane,
Bis (di-n-propylamino) ethyl-4-vinylphenylsilane,
Bis (di-n-propylamino) ethyl-3-vinylphenylsilane,
Bis (di-n-butylamino) ethyl-4-vinylphenylsilane,
Bis (di-n-butylamino) ethyl-3-vinylphenylsilane.

Examples of the compound represented by formula (1) include the following compounds as compounds in which R ¹¹ is a methyl group and ^{two of} X ¹ , X ² and X ³ are dialkylamino groups.

Compound in which m is 1:
Bis (dimethylamino) methyl-4-isopropenylphenylsilane,
Bis (dimethylamino) methyl-3-isopropenylphenylsilane,
Bis (diethylamino) methyl-4-isopropenylphenylsilane,
Bis (diethylamino) methyl-3-isopropenylphenylsilane,
Bis (di-n-propylamino) methyl-4-isopropenylphenylsilane,
Bis (di-n-propylamino) methyl-3-isopropenylphenylsilane,
Bis (di-n-butylamino) methyl-4-isopropenylphenylsilane,
Bis (di-n-butylamino) methyl-3-isopropenylphenylsilane,
Bis (dimethylamino) ethyl-4-isopropenylphenylsilane,
Bis (dimethylamino) ethyl-3-isopropenylphenylsilane,
Bis (diethylamino) ethyl-4-isopropenylphenylsilane,
Bis (diethylamino) ethyl-3-isopropenylphenylsilane,
Bis (di-n-propylamino) ethyl-4-isopropenylphenylsilane,
Bis (di-n-propylamino) ethyl-3-isopropenylphenylsilane,
Bis (di-n-butylamino) ethyl-4-isopropenylphenylsilane,
Bis (di-n-butylamino) ethyl-3-isopropenylphenylsilane.

Examples of the compound represented by formula (1) include the following compounds as compounds in which R ¹¹ is a vinyl group and ^{two of} X ¹ , X ² and X ³ are dialkylamino groups.

Compound in which m is 0:
Bis (dimethylamino) methyl (1-methylene-2-propenyl) silane,
Bis (diethylamino) methyl (1-methylene-2-propenyl) silane,
Bis (di-n-propylamino) methyl (1-methylene-2-propenyl) silane,
Bis (di-n-butylamino) methyl (1-methylene-2-propenyl) silane,
Bis (dimethylamino) ethyl (1-methylene-2-propenyl) silane,
Bis (diethylamino) ethyl (1-methylene-2-propenyl) silane,
Bis (di-n-propylamino) ethyl (1-methylene-2-propenyl) silane,
Bis (di-n-butylamino) ethyl (1-methylene-2-propenyl) silane.

Examples of the compound represented by the formula (1) include the following compounds as compounds in which R ¹¹ is a hydrogen atom and ^three of X ¹ , X ² and X ³ are dialkylamino groups.

Compound in which m is 0:
Tris (dimethylamino) vinylsilane,
Tris (diethylamino) vinylsilane,
Tris (di-n-propylamino) vinylsilane,
Tris (di-n-butylamino) vinylsilane.

Compound in which m is 1:
Tris (dimethylamino) -4-vinylphenylsilane,
Tris (dimethylamino) -3-vinylphenylsilane,
Tris (diethylamino) -4-vinylphenylsilane,
Tris (diethylamino) -3-vinylphenylsilane,
Tris (di-n-propylamino) -4-vinylphenylsilane,
Tris (di-n-propylamino) -3-vinylphenylsilane,
Tris (di-n-butylamino) -4-vinylphenylsilane,
Tris (di-n-butylamino) -3-vinylphenylsilane.

Examples of the compound represented by the formula (1) include the following compounds as compounds in which R ¹¹ is a methyl group and ^three of X ¹ , X ² and X ³ are dialkylamino groups.

Compound in which m is 1:
Tris (dimethylamino) -4-isopropenylphenylsilane,
Tris (dimethylamino) -3-isopropenylphenylsilane,
Tris (diethylamino) -4-isopropenylphenylsilane,
Tris (diethylamino) -3-isopropenylphenylsilane,
Tris (di-n-propylamino) -4-isopropenylphenylsilane,
Tris (di-n-propylamino) -3-isopropenylphenylsilane,
Tris (di-n-butylamino) -4-isopropenylphenylsilane,
Tris (di-n-butylamino) -3-isopropenylphenylsilane.

Examples of the compound represented by formula (1) include the following compounds as compounds in which R ¹¹ is a vinyl group and ^three of X ¹ , X ² and X ³ are dialkylamino groups.

Compound in which m is 0:
Tris (dimethylamino) (1-methylene-2-propenyl) silane,
Tris (diethylamino) (1-methylene-2-propenyl) silane,
Tris (di-n-propylamino) (1-methylene-2-propenyl) silane,
Tris (di-n-butylamino) (1-methylene-2-propenyl) silane.

The compound represented by the formula (1) is preferably a compound in which ^{two of} X ¹ , X ² and X ³ are dialkylamino groups, more preferably R ¹¹ is a hydrogen atom, and m = A compound that is zero. More preferably, it is a compound in which the remaining ^one of X ¹ , X ² and X ³ is an alkyl group or an alkoxyalkyl group. Particularly preferably,
Bis (dimethylamino) methylvinylsilane,
Bis (diethylamino) methylvinylsilane,
Bis (di-n-propylamino) methylvinylsilane,
Bis (di-n-butylamino) methylvinylsilane,
Bis (dimethylamino) ethylvinylsilane,
Bis (diethylamino) ethylvinylsilane,
Bis (di-n-propylamino) ethylvinylsilane,
Bis (di-n-butylamino) ethylvinylsilane.

R ^{21 in the} above formula (2) represents a hydrogen atom or a hydrocarbyl group.

Examples of the hydrocarbyl group for R ²¹ include an alkyl group and an alkenyl group.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group is preferable. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group, and a vinyl group is preferable.

R ²¹ is preferably a hydrogen atom, a methyl group, or a vinyl group.

Examples of the hydrocarbylene group for R ²² include an alkylene group, an arylene group, and a group in which an arylene group and an alkylene group are bonded.

Examples of the alkylene group include a methylene group, an ethylene group, and a trimethylene group. Preferably, it is a methylene group or an ethylene group.

Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. A phenylene group is preferred.

Examples of the group in which an arylene group and an alkylene group are bonded include a group in which a phenylene group and an alkylene group are bonded, a group in which a naphthylene group and an alkylene group are bonded, and a group in which a biphenylene group and an alkylene group are bonded. A group in which a phenylene group and an alkylene group are bonded is preferable.

In the group in which the arylene group and the alkylene group are bonded, the carbon atom of the arylene group is preferably bonded to the carbon atom to which R ^{21 in} the formula (2) is bonded.

（式中、ｓは１〜１０の整数を表す。） In a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), depending on the position of the carbon atom on the benzene ring from which a hydrogen atom is removed and the phenylene group to which the alkylene group is bonded, a para-phenylene-alkylene group ( For example, a group represented by the following formula (2a)), a meta-phenylene-alkylene group (for example, a group represented by the following formula (2b)), an ortho-phenylene-alkylene group (for example, the following formula (2c) )))).

(In the formula, s represents an integer of 1 to 10.)

The group in which an arylene group and an alkylene group are bonded is preferably a group in which a phenylene group and an alkylene group are bonded, and more preferably a group represented by the above formula (2a) or a group represented by the above formula (2b). More preferably a para-phenylene-methylene group (a group represented by the formula (2a) where s = 1), a meta-phenylene-methylene group (a formula (2b) where s = 1). A group represented by formula (2a) in which s = 2, a meta-phenylene-ethylene group (in formula (2b) in which s = 2). Group).

（式中、ｒは０〜５の整数を表し、ｒが１から５の整数である場合、（ＣＨ_２）_ｒはベンゼン環上の置換基であり、（ＣＨ_２）_ｒがＡと結合し、ｒが０である場合、（ＣＨ_２）_ｒはベンゼン環とＡとの結合を表す。）

（式中、ｒは０〜５の整数を表し、ｒが１から５の整数である場合、（ＣＨ_２）_ｒがＡと結合し、ｒが０である場合、（ＣＨ_２）_ｒはベンゼン環とＡとの結合を表す。） When R ²¹ is a hydrogen atom or a methyl group and n is 1, R ²² is preferably a group in which an arylene group and an alkylene group are bonded or an arylene group, more preferably a phenylene group and an alkylene group. And a phenylene group, more preferably a group represented by the following formula (2-Y), particularly preferably a group represented by the following formula (2-Ya) or the following formula ( 2-Yb). Moreover, r is 0-5 in a formula, Preferably it is 0-2.

(In the formula, r represents an integer of 0 to 5, and when r is an integer of 1 to 5, (CH ₂ ) _r is a substituent on the benzene ring, and (CH ₂ ) _r is bonded to A. , R is 0, (CH ₂ ) _r represents a bond between the benzene ring and A.)

(In the formula, r represents an integer of 0 to 5, and when r is an integer of 1 to 5, (CH ₂ ) when _r is bonded to A and r is 0, (CH ₂ ) _r is benzene. Represents the bond between the ring and A.)

When R ²¹ is a vinyl group and n is 1, R ²² is preferably an alkylene group, more preferably a methylene group or an ethylene group.

A represents a substituted amino group or a nitrogen-containing heterocyclic group.

（式中、Ｒ^２３及びＲ^２４は、それぞれ、ヒドロカルビル基、又は、トリヒドロカルビルシリル基、あるいは、Ｒ^２３とＲ^２４とが結合して、窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基、又は、Ｒ^２３とＲ^２４は１つの基であって、窒素原子に二重結合で結合する基を表す。） The substituted amino group for A is preferably a group represented by the following formula (2-X).

(Wherein R ²³ and R ²⁴ each have a hydrocarbyl group, a trihydrocarbyl silyl group, or R ²³ and R ²⁴ bonded to each other and have a nitrogen atom and / or an oxygen atom as a hetero atom. Hydrocarbylene group which may be substituted, or R ²³ and R ²⁴ are one group and represent a group bonded to a nitrogen atom by a double bond.)

Examples of the hydrocarbyl group of R ²³ and R ²⁴ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group. Examples of the alkynyl group include an ethynyl group and a propargyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group.

The number of carbon atoms of the hydrocarbyl group of R ²³ and R ²⁴ is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.

The hydrocarbyl group for R ²³ and R ²⁴ is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and still more preferably a linear alkyl group.

The trihydrocarbyl silyl group R ²³ and R ^24, may be mentioned trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, a trialkylsilyl group such as tert- butyldimethylsilyl group.

The trihydrocarbylsilyl group of R ²³ and R ²⁴ is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably an alkyl group bonded to a silicon atom having 1 to 4 carbon atoms. A trialkylsilyl group which is an alkyl group, and more preferably a trimethylsilyl group.

The hydrocarbylene group optionally having a nitrogen atom and / or oxygen atom to which R ²³ and R ²⁴ are bonded as a hetero atom includes a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and an oxygen atom. And hydrocarbylene groups. Examples of the hydrocarbylene group include an alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. As the hydrocarbylene group having a nitrogen atom, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH—N A group represented by ═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified. Examples of the hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the hydrocarbylene group which may have a nitrogen atom and / or oxygen atom to which R ²³ and R ²⁴ are bonded as a hetero atom is preferably 2 to 20, more preferably 2 to 7. Yes, more preferably 4-6.

The hydrocarbylene group which may have a nitrogen atom and / or oxygen atom to which R ²³ and R ²⁴ are bonded as a hetero atom is preferably a hydrocarbylene group, more preferably an alkylene group, A polymethylene group is preferred.

Examples of one group in which R ²³ and R ²⁴ are bonded to the nitrogen atom with a double bond include ethylidene group, propylidene group, butylidene group, 1-methylethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene And hydrocarbylidene groups such as groups.

The number of carbon atoms of one group in which R ²³ and R ²⁴ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 6.

R ²³ and R ²⁴ are preferably a hydrocarbyl group, a trihydrocarbyl silyl group, or a hydrocarbylene group in which R ²³ and R ²⁴ are bonded.

Examples of the group represented by the formula (2-X) include an acyclic amino group and a cyclic amino group.

Examples of the acyclic amino group include a dialkylamino group and a bis (trialkylsilyl) amino group. Dialkylamino groups include dimethylamino, diethylamino, di (n-propyl) amino, di (isopropyl) amino, di (n-butyl) amino, di (sec-butyl) amino, di (tert -Butyl) amino group and ethylmethylamino group can be mentioned. Examples of the bis (trialkylsilyl) amino group include a bis (trimethylsilyl) amino group and a bis (tert-butyldimethylsilyl) amino group.

The acyclic amino group further includes an ethylideneamino group, a 1-methylpropylideneamino group, a 1,3-dimethylbutylideneamino group, a 1-methylethylideneamino group, and a 4-N, N-dimethylaminobenzylideneamino group. You can also give it.

Examples of the cyclic amino group include 1-aziridinyl group, 1-azetidinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexamethyleneimino group, 1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1 Examples include -pyrrolyl group, 1-pyrazolyl group, 1-imidazolidinyl group, 1-piperazinyl group, and morpholino group.

The group represented by the formula (2-X) is preferably a group in which R ²³ and R ²⁴ are hydrocarbyl groups, a group in which R ²³ and R ²⁴ are trihydrocarbylsilyl groups, and R ²³ and R ²⁴ are bonded. Group which is a hydrocarbylene group. More preferably, R ²³ and R ²⁴ are a group that is a linear alkyl group, R ²³ and R ²⁴ are a group that is a trialkylsilyl group, and a group that is a polymethylene group to which R ²³ and R ²⁴ are bonded.

The group represented by the formula (2-X) is more preferably a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, a di (n-butyl) amino group, a bis (trimethylsilyl) amino group, A bis (tert-butyldimethylsilyl) amino group, a 1-pyrrolidinyl group, a 1-piperidinyl group, and a 1-hexamethyleneimino group, particularly preferably a 1-pyrrolidinyl group.

Examples of the nitrogen-containing heterocyclic group of A include a nitrogen-containing aliphatic heterocyclic group and a nitrogen-containing aromatic heterocyclic group. In the present specification, a nitrogen-containing aliphatic heterocyclic group represents a group obtained by removing one hydrogen atom from a carbon atom of a heterocyclic ring of a compound having a nitrogen-containing aliphatic heterocyclic ring. Represents an aliphatic heterocycle having a nitrogen atom as a heteroatom. The nitrogen-containing aromatic heterocyclic group represents a group obtained by removing one hydrogen atom from a carbon atom of a heterocyclic ring of a compound having a nitrogen-containing aromatic heterocyclic ring, and the nitrogen-containing aromatic heterocyclic ring constitutes a ring. An aromatic heterocyclic ring having a nitrogen atom as a hetero atom is represented.

The nitrogen-containing aliphatic heterocyclic group of A includes a group having only a nitrogen atom as a hetero atom constituting the ring, a group having a nitrogen atom and an oxygen atom as a hetero atom constituting the ring, and nitrogen as a hetero atom constituting the ring. Examples thereof include a group having an atom and a sulfur atom.

The nitrogen-containing aliphatic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring includes a group having an aziridine ring, a group having an azetidine ring, a group having a pyrrolidine ring, a group having a piperidine ring, a hexamethyleneimine ring , A group having an imidazolidine ring, a group having a piperazine ring, a group having a pyrazolidine ring, and the like.

Examples of the group having an aziridine ring include an N-alkyl-2-aziridinyl group.
Examples of the group having an azetidine ring include an N-alkyl-2-azetidinyl group and an N-alkyl-3-azetidinyl group.
Examples of the group having a pyrrolidine ring include an N-alkyl-2-pyrrolidinyl group and an N-alkyl-3-pyrrolidinyl group.
Examples of the group having a piperidine ring include an N-alkyl-2-piperidinyl group, an N-alkyl-3-piperidinyl group, and an N-alkyl-4-piperidinyl group.
Examples of the group having a hexamethyleneimine ring include an N-alkyl-2-hexamethyleneimino group, an N-alkyl-3-hexamethyleneimino group, and an N-alkyl-4-hexamethyleneimino group.
Examples of the group having an imidazolidine ring include a 1,3-dialkyl-2-imidazolidyl group and a 1,3-dialkyl-4-imidazolidyl group.
Examples of the group having a piperazine ring include a 1,4-dialkyl-2-piperazinyl group.
Examples of the group having a pyrazolidine ring include a 1,2-dialkyl-3-pyrazolidyl group and a 1,2-dialkyl-4-pyrazolidyl group.

Examples of the nitrogen-containing aliphatic heterocyclic group having a nitrogen atom and an oxygen atom as a hetero atom constituting the ring include a group having a morpholine ring and a group having an isoxazolidine ring.

Examples of the group having a morpholine ring include an N-alkyl-2-morpholino group and an N-alkyl-3-morpholino group.
Examples of the group having an isoxazolidine ring include an N-alkyl-3-isoxazolidinyl group, an N-alkyl-4-isoxazolidinyl group, and an N-alkyl-5-isoxazolidinyl group. Can do.

Examples of the nitrogen-containing aliphatic heterocyclic group having a nitrogen atom and a sulfur atom as hetero atoms constituting the ring include a group having a thiomorpholine ring and a group having an isothiazolidine ring.

Examples of the group having a thiomorpholine ring include an N-alkyl-2-thiomorpholino group and an N-alkyl-3-thiomorpholino group.
Examples of the group having an isothiazolidine ring include an N-alkyl-3-isothiazolidinyl group, an N-alkyl-4-isothiazolidinyl group, and an N-alkyl-5-isothiazolidinyl group.

The nitrogen-containing aliphatic heterocyclic group for A is preferably a group having only a nitrogen atom as a hetero atom constituting the ring. The number of carbon atoms in the nitrogen-containing aliphatic heterocyclic group is preferably 4-10.

The nitrogen-containing aromatic heterocyclic group of A includes a group having only a nitrogen atom as a hetero atom constituting the ring, a group having a nitrogen atom and an oxygen atom as a hetero atom constituting the ring, and nitrogen as a hetero atom constituting the ring. Examples thereof include a group having an atom and a sulfur atom.

The nitrogen-containing aromatic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring includes a group having a pyrrole ring, a group having an imidazole ring, a group having a pyrazole ring, a group having a pyridine ring, and a pyridazine ring. A group having a pyrimidine ring, a group having a pyrazine ring, a group having a quinoline ring, a group having an isoquinoline ring, a group having a cinnoline ring, a group having a quinazoline ring, a group having a phthalazine ring, and the like.

Examples of the group having a pyrrole ring include a 2-pyrrolyl group, a 3-pyrrolyl group, a 2- (N-methylpyrrolyl) group, and a 3- (N-methylpyrrolyl) group.
Examples of the group having an imidazole ring include 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 2- (N-methylimidazolyl) group, 4- (N-methylimidazolyl) group, and 5- (N-methylimidazolyl). ) Group.
Examples of the group having a pyrazole ring include 3-pyrazolyl group, 4-pyrazolyl group, 5-pyrazolyl group, 3- (N-methylpyrazolyl) group, 4- (N-methylpyrazolyl) group, and 5- (N-methylpyrazolyl). ) Group.
Examples of the group having a pyridine ring include a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group.
Examples of the group having a pyridazine ring include a 3-pyridazyl group and a 4-pyridazyl group.
Examples of the group having a pyrimidine ring include a 2-pyrimidyl group, a 4-pyrimidyl group, and a 5-pyrimidyl group.
Examples of the group having a pyrazine ring include a 2-pyrazyl group.
Examples of the group having a quinoline ring include a 2-quinolyl group, a 3-quinolyl group, a 4-quinolyl group, a 5-quinolyl group, a 6-quinolyl group, a 7-quinolyl group, and an 8-quinolyl group.
Examples of the group having an isoquinoline ring include a 1-isoquinolyl group, a 3-isoquinolyl group, a 4-isoquinolyl group, a 5-isoquinolyl group, a 6-isoquinolyl group, a 7-isoquinolyl group, and an 8-isoquinolyl group.
Examples of the group having a cinnoline ring include a 3-cinnolinyl group, a 4-cinnolinyl group, a 5-cinnolinyl group, a 6-cinnolinyl group, a 7-cinnolinyl group, and an 8-cinnolinyl group.
Examples of the group having a quinazoline ring include a 2-quinazolinyl group, a 4-quinazolinyl group, a 5-quinazolinyl group, a 6-quinazolinyl group, a 7-quinazolinyl group, and an 8-quinazolinyl group.
Examples of the group having a phthalazine ring include a 1-phthalazinyl group, a 5-phthalazinyl group, and a 6-phthalazinyl group.
The nitrogen-containing aromatic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring is preferably a group having an imidazole ring, a group having a pyridine ring, or a group having a quinoline ring.

Examples of the nitrogen-containing aromatic heterocyclic group having a nitrogen atom and an oxygen atom as hetero atoms constituting the ring include a group having an oxazole ring and a group having an isoxazole ring.

Examples of the group having an oxazole ring include a 2-oxazolyl group, a 4-oxazolyl group, and a 5-oxazolyl group.
Examples of the group having an isoxazole ring include a 3-isoxazolyl group, a 4-isoxazolyl group, and a 5-isoxazolyl group.
The nitrogen-containing aromatic heterocyclic group having a nitrogen atom and an oxygen atom as hetero atoms constituting the ring is preferably a group having an oxazole ring.

Examples of the nitrogen-containing aromatic heterocyclic group having a nitrogen atom and a sulfur atom as the hetero atoms constituting the ring include a group having a thiazole ring, a group having an isothiazole ring, and the like.

Examples of the group having a thiazole ring include a 2-thiazolyl group, a 4-thiazolyl group, and a 5-thiazolyl group.
Examples of the group having an isothiazole ring include a 3-isothiazolyl group, a 4-isothiazolyl group, and a 5-isothiazolyl group.
The nitrogen-containing aromatic heterocyclic group having a nitrogen atom and a sulfur atom as a hetero atom constituting the ring is preferably a group having a thiazole ring.

The nitrogen-containing heterocyclic group for A is preferably a nitrogen-containing aromatic heterocyclic group, more preferably a nitrogen-containing aromatic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring, A group having an imidazole ring, a group having a pyridine ring, and a group having a quinoline ring are preferable, and a group having a pyridine ring is particularly preferable.

Examples of the compound represented by formula (2) include the following compounds as compounds in which R ²¹ is a hydrogen atom, n is 0, and A is a substituted amino group.

1-vinylpyrrolidine,
1-vinyl piperidine,
1-vinylhexamethyleneimine,
1-vinyl piperazine,
1-vinyl pyrrole,
1-vinylimidazole,
1-vinylpyrazole,
Vinyl quinoline.

As a compound represented by the formula (2), R ²¹ is a hydrogen atom, n is 1, R ²² is a group represented by the formula (2-Y), and A is a substituted amino group. Examples of the compound include the following compounds.

Compound in which r in formula (2-Y) is 0:
4-N, N-dimethylaminostyrene,
3-N, N-dimethylaminostyrene,
4-N, N-diethylaminostyrene,
3-N, N-diethylaminostyrene,
4-N, N-di-n-propylaminostyrene,
3-N, N-di-n-propylaminostyrene,
4-N, N-di-n-butylaminostyrene,
3-N, N-di-n-butylaminostyrene,
4-N, N-diallylaminostyrene,
3-N, N-diallylaminostyrene,
4-N, N-bis (trimethylsilyl) aminostyrene,
3-N, N-bis (trimethylsilyl) aminostyrene,
4-N, N-bis (tert-butyldimethylsilyl) aminostyrene,
3-N, N-bis (tert-butyldimethylsilyl) aminostyrene,
4- (1-aziridinyl) styrene,
3- (1-aziridinyl) styrene,
4- (1-pyrrolidinyl) styrene,
3- (1-pyrrolidinyl) styrene,
4- (1-piperidinyl) styrene,
3- (1-piperidinyl) styrene,
4- (1-hexamethyleneimino) styrene,
3- (1-Hexamethyleneimino) styrene.

Compound in which r in formula (2-Y) is 1:
4-N, N-dimethylaminomethylstyrene,
3-N, N-dimethylaminomethylstyrene,
4-N, N-diethylaminomethylstyrene,
3-N, N-diethylaminomethylstyrene,
4-N, N-di-n-propylaminomethylstyrene,
3-N, N-di-n-propylaminomethylstyrene,
4-N, N-di-n-butylaminomethylstyrene,
3-N, N-di-n-butylaminomethylstyrene,
4-N, N-diallylaminomethylstyrene,
3-N, N-diallylaminomethylstyrene,
4-N, N-bis (trimethylsilyl) aminomethylstyrene,
3-N, N-bis (trimethylsilyl) aminomethylstyrene,
4-N, N-bis (tert-butyldimethylsilyl) aminomethylstyrene,
3-N, N-bis (tert-butyldimethylsilyl) aminomethylstyrene,
4- (1-aziridinyl) methylstyrene,
3- (1-aziridinyl) methylstyrene,
4- (1-pyrrolidinyl) methylstyrene,
3- (1-pyrrolidinyl) methylstyrene,
4- (1-piperidinyl) methylstyrene,
3- (1-piperidinyl) methylstyrene,
4- (1-hexamethyleneimino) methylstyrene,
3- (1-Hexamethyleneimino) methylstyrene.

Compound in which r in formula (2-Y) is 2:
4-N, N-dimethylaminoethylstyrene,
3-N, N-dimethylaminoethylstyrene,
4-N, N-diethylaminoethylstyrene,
3-N, N-diethylaminoethylstyrene,
4-N, N-di-n-propylaminoethylstyrene,
3-N, N-di-n-propylaminoethylstyrene,
4-N, N-di-n-butylaminoethylstyrene,
3-N, N-di-n-butylaminoethylstyrene,
4-N, N-diallylaminoethylstyrene,
3-N, N-diallylaminoethylstyrene,
4-N, N-bis (trimethylsilyl) aminoethylstyrene,
3-N, N-bis (trimethylsilyl) aminoethylstyrene,
4-N, N-bis (tert-butyldimethylsilyl) aminoethylstyrene,
3-N, N-bis (tert-butyldimethylsilyl) aminoethylstyrene,
4- (1-aziridinyl) ethylstyrene,
3- (1-aziridinyl) ethylstyrene,
4- (1-pyrrolidinyl) ethylstyrene,
3- (1-pyrrolidinyl) ethylstyrene,
4- (1-piperidinyl) ethylstyrene,
3- (1-piperidinyl) ethylstyrene,
4- (1-hexamethyleneimino) ethylstyrene,
3- (1-Hexamethyleneimino) ethylstyrene.

Examples of the compound represented by formula (2) include the following compounds as compounds in which R ²¹ is a methyl group, n is 0, and A is a substituted amino group.

1-isopropenylpyrrolidine,
1-isopropenyl piperidine,
1-isopropenyl hexamethyleneimine,
1-isopropenyl piperazine,
1-isopropenyl pyrrole,
1-isopropenylimidazole,
1-isopropenylpyrazole,
Isopropenyl quinoline.

As a compound represented by the formula (2), R ²¹ is a methyl group, n is 1, R ²² is a group represented by the formula (2-Y), and A is a substituted amino group. Examples of the compound include the following compounds.

Compound in which r in formula (2-Y) is 0:
4-N, N-dimethylaminoisopropenylbenzene,
3-N, N-dimethylaminoisopropenylbenzene,
4-N, N-diethylaminoisopropenylbenzene,
3-N, N-diethylaminoisopropenylbenzene,
4-N, N-di-n-propylaminoisopropenylbenzene,
3-N, N-di-n-propylaminoisopropenylbenzene,
4-N, N-di-n-butylaminoisopropenylbenzene,
3-N, N-di-n-butylaminoisopropenylbenzene,
4-N, N-diallylaminoisopropenylbenzene,
3-N, N-diallylaminoisopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminoisopropenylbenzene,
3-N, N-bis (trimethylsilyl) aminoisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminoisopropenylbenzene, 3-N, N-bis (tert-butyldimethylsilyl) aminoisopropenylbenzene, 4- (1-aziridinyl) isopropenylbenzene,
3- (1-aziridinyl) isopropenylbenzene,
4- (1-pyrrolidinyl) isopropenylbenzene,
3- (1-pyrrolidinyl) isopropenylbenzene,
4- (1-piperidinyl) isopropenylbenzene,
3- (1-piperidinyl) isopropenylbenzene,
4- (1-hexamethyleneimino) isopropenylbenzene,
3- (1-Hexamethyleneimino) isopropenylbenzene.

Compound in which r in formula (2-Y) is 1:
4-N, N-dimethylaminomethylisopropenylbenzene,
3-N, N-dimethylaminomethylisopropenylbenzene,
4-N, N-diethylaminomethylisopropenylbenzene,
3-N, N-diethylaminomethylisopropenylbenzene,
4-N, N-di-n-propylaminomethylisopropenylbenzene,
3-N, N-di-n-propylaminomethylisopropenylbenzene,
4-N, N-di-n-butylaminomethylisopropenylbenzene,
3-N, N-di-n-butylaminomethylisopropenylbenzene,
4-N, N-diallylaminomethylisopropenylbenzene,
3-N, N-diallylaminomethylisopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminomethylisopropenylbenzene,
3-N, N-bis (trimethylsilyl) aminomethylisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminomethylisopropenylbenzene,
3-N, N-bis (tert-butyldimethylsilyl) aminomethylisopropenylbenzene,
4- (1-aziridinyl) methylisopropenylbenzene,
3- (1-aziridinyl) methyl isopropenylbenzene,
4- (1-pyrrolidinyl) methylisopropenylbenzene,
3- (1-pyrrolidinyl) methylisopropenylbenzene,
4- (1-piperidinyl) methyl isopropenylbenzene,
3- (1-piperidinyl) methylisopropenylbenzene,
4- (1-hexamethyleneimino) methylisopropenylbenzene,
3- (1-Hexamethyleneimino) methylisopropenylbenzene.

Compound in which r in formula (2-Y) is 2:
4-N, N-dimethylaminoethylisopropenylbenzene,
3-N, N-dimethylaminoethylisopropenylbenzene,
4-N, N-diethylaminoethylisopropenylbenzene,
3-N, N-diethylaminoethylisopropenylbenzene,
4-N, N-di-n-propylaminoethylisopropenylbenzene,
3-N, N-di-n-propylaminoethylisopropenylbenzene,
4-N, N-di-n-butylaminoethylisopropenylbenzene,
3-N, N-di-n-butylaminoethyl isopropenylbenzene,
4-N, N-diallylaminoethyl isopropenylbenzene,
3-N, N-diallylaminoethylisopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminoethylisopropenylbenzene,
3-N, N-bis (trimethylsilyl) aminoethylisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminoethylisopropenylbenzene,
3-N, N-bis (tert-butyldimethylsilyl) aminoethylisopropenylbenzene,
4- (1-aziridinyl) ethyl isopropenylbenzene,
3- (1-aziridinyl) ethyl isopropenylbenzene,
4- (1-pyrrolidinyl) ethyl isopropenylbenzene,
3- (1-pyrrolidinyl) ethyl isopropenylbenzene,
4- (1-piperidinyl) ethyl isopropenylbenzene,
3- (1-piperidinyl) ethyl isopropenylbenzene,
4- (1-hexamethyleneimino) ethyl isopropenylbenzene,
3- (1-Hexamethyleneimino) ethyl isopropenylbenzene.

Examples of the compound represented by formula (2) include the following compounds as compounds in which R ²¹ is a vinyl group, n is 0, and A is a substituted amino group.

2-N, N-dimethylamino-1,3-butadiene,
2-N, N-diethylamino-1,3-butadiene,
2-N, N-di-n-propylamino-1,3-butadiene,
2-N, N-di-n-butylamino-1,3-butadiene,
2-N, N-diallylamino-1,3-butadiene,
2-N, N-bis (trimethylsilyl) amino-1,3-butadiene,
2-N, N-bis (tert-butyldimethylsilyl) amino-1,3-butadiene,
2- (1-aziridinyl) -1,3-butadiene,
2- (1-pyrrolidinyl) -1,3-butadiene,
2- (1-piperidinyl) -1,3-butadiene,
2- (1-hexamethyleneimino) -1,3-butadiene,
2- (1-pyrrolyl) -1,3-butadiene,
2- (1-imidazolyl) -1,3-butadiene,
2- (1-Pyrazolyl) -1,3-butadiene.

Examples of the compound represented by the formula (2) include the following compounds as compounds in which R ²¹ is a vinyl group, n is 1, R ²² is an alkylene group, and A is a substituted amino group. Can do.

Compound in which R ²² is a methylene group:
2-N, N-dimethylaminomethyl-1,3-butadiene,
2-N, N-diethylaminomethyl-1,3-butadiene,
2-N, N-di-n-propylaminomethyl-1,3-butadiene,
2-N, N-di-n-butylaminomethyl-1,3-butadiene,
2-N, N-diallylaminomethyl-1,3-butadiene,
2-N, N-bis (trimethylsilyl) aminomethyl-1,3-butadiene,
2-N, N-bis (tert-butyldimethylsilyl) aminomethyl-1,3-butadiene,
2- (1-aziridinyl) methyl-1,3-butadiene,
2- (1-pyrrolidinyl) methyl-1,3-butadiene,
2- (1-piperidinyl) methyl-1,3-butadiene,
2- (1-hexamethyleneimino) methyl-1,3-butadiene,
1- (2-methylene-3-butenyl) pyrrole,
1- (2-methylene-3-butenyl) imidazole,
1- (2-Methylene-3-butenyl) pyrazole.

Compound in which R ²² is an ethylene group:
5-N, N-dimethylamino-3-methylene-1-pentene,
5-N, N-diethylamino-3-methylene-1-pentene,
5-N, N-di-n-propylamino-3-methylene-1-pentene,
5-N, N-di-n-butylamino-3-methylene-1-pentene,
5-N, N-diallylamino-3-methylene-1-pentene,
5-N, N-bis (trimethylsilyl) amino-3-methylene-1-pentene,
5-N, N-bis (tert-butyldimethylsilyl) amino-3-methylene-1-pentene,
5- (1-aziridinyl) -3-methylene-1-pentene,
5- (1-pyrrolidinyl) -3-methylene-1-pentene,
5- (1-piperidinyl) -3-methylene-1-pentene,
5- (1-hexamethyleneimino) -3-methylene-1-pentene,
1- (3-methylene-4-pentenyl) pyrrole,
1- (3-methylene-4-pentenyl) imidazole,
1- (3-methylene-4-pentenyl) pyrazole.

As the compound represented by the formula (2), R ²¹ is a hydrogen atom, n is 1, R ²² is a group represented by the formula (2-Y), and A is a nitrogen-containing aliphatic complex. Examples of the compound that is a cyclic group include the following compounds.

Compound in which r in formula (2-Y) is 0:
4-N-methyl-2-aziridinylstyrene,
4-N-methyl-2-pyrrolidinylstyrene,
4-N-methyl-3-pyrrolidinylstyrene,
4-N-methyl-2-hexamethyleneiminostyrene,
4-N-methyl-3-hexamethyleneiminostyrene,
4-N-methyl-4-hexamethyleneiminostyrene.

Compound in which r in formula (2-Y) is 1:
4-N-methyl-2-aziridinylmethylstyrene,
4-N-methyl-2-pyrrolidinylmethylstyrene,
4-N-methyl-3-pyrrolidinylmethylstyrene,
4-N-methyl-2-hexamethyleneiminomethylstyrene,
4-N-methyl-3-hexamethyleneiminomethylstyrene,
4-N-methyl-4-hexamethyleneiminomethylstyrene.

Compound in which r in formula (2-Y) is 2:
4-N-methyl-2-aziridinylethylstyrene,
4-N-methyl-2-pyrrolidinylethylstyrene,
4-N-methyl-3-pyrrolidinylethylstyrene,
4-N-methyl-2-hexamethyleneiminoethylstyrene,
4-N-methyl-3-hexamethyleneiminoethylstyrene,
4-N-methyl-4-hexamethyleneiminoethylstyrene.

As the compound represented by the formula (2), R ²¹ is a methyl group, n is 1, R ²² is a group represented by the formula (2-Y), and A is a nitrogen-containing aliphatic complex. Examples of the compound that is a cyclic group include the following compounds.

Compound in which r in formula (2-Y) is 0:
4-N-methyl-2-aziridinylisopropenylbenzene,
4-N-methyl-2-pyrrolidinylisopropenylbenzene,
4-N-methyl-3-pyrrolidinylisopropenylbenzene,
4-N-methyl-2-hexamethyleneiminoisopropenylbenzene,
4-N-methyl-3-hexamethyleneiminoisopropenylbenzene,
4-N-methyl-4-hexamethyleneiminoisopropenylbenzene.

Compound in which r in formula (2-Y) is 1:
4-N-methyl-2-aziridinylmethyl isopropenylbenzene,
4-N-methyl-2-pyrrolidinylmethylisopropenylbenzene,
4-N-methyl-3-pyrrolidinylmethylisopropenylbenzene,
4-N-methyl-2-hexamethyleneiminomethylisopropenylbenzene,
4-N-methyl-3-hexamethyleneiminomethylisopropenylbenzene,
4-N-methyl-4-hexamethyleneiminomethylisopropenylbenzene.

Compound in which r in formula (2-Y) is 2:
4-N-methyl-2-aziridinylethyl isopropenylbenzene,
4-N-methyl-2-pyrrolidinylethyl isopropenylbenzene,
4-N-methyl-3-pyrrolidinylethyl isopropenylbenzene,
4-N-methyl-2-hexamethyleneiminoethylisopropenylbenzene,
4-N-methyl-3-hexamethyleneiminoethyl isopropenylbenzene,
4-N-methyl-4-hexamethyleneiminoethylisopropenylbenzene.

Examples of the compound represented by formula (2) include the following compounds as compounds in which R ²¹ is a vinyl group, n is 0, and A is a nitrogen-containing aliphatic heterocyclic group.

N-methyl-2- (1-methylene-2-propenyl) aziridine,
N-methyl-2- (1-methylene-2-propenyl) pyrrolidine,
N-methyl-3- (1-methylene-2-propenyl) pyrrolidine,
N-methyl-2- (1-methylene-2-propenyl) hexamethyleneimine,
N-methyl-3- (1-methylene-2-propenyl) hexamethyleneimine,
N-methyl-4- (1-methylene-2-propenyl) hexamethyleneimine.

As the compound represented by the formula (2), R ²¹ is a vinyl group, n is 1, R ²² is an alkylene group, and A is a nitrogen-containing aliphatic heterocyclic group. Compounds can be mentioned.

Compound in which R ²² is a methylene group:
N-methyl-2- (2-methylene-3-butenyl) aziridine,
N-methyl-2- (2-methylene-3-butenyl) pyrrolidine,
N-methyl-3- (2-methylene-3-butenyl) pyrrolidine,
N-methyl-2- (2-methylene-3-butenyl) hexamethyleneimine,
N-methyl-3- (2-methylene-3-butenyl) hexamethyleneimine,
N-methyl-4- (2-methylene-3-butenyl) hexamethyleneimine.

Compound in which R ²² is an ethylene group:
N-methyl-2- (3-methylene-4-pentenyl) aziridine,
N-methyl-2- (3-methylene-4-pentenyl) pyrrolidine,
N-methyl-3- (3-methylene-4-pentenyl) pyrrolidine,
N-methyl-2- (3-methylene-4-pentenyl) hexamethyleneimine,
N-methyl-3- (3-methylene-4-pentenyl) hexamethyleneimine,
N-methyl-4- (3-methylene-4-pentenyl) hexamethyleneimine.

Examples of the compound represented by formula (2) include the following compounds as compounds in which R ²¹ is a hydrogen atom, n is 0, and A is a nitrogen-containing aromatic heterocyclic group.

N-methyl-2-vinylimidazole,
N-methyl-4-vinylimidazole,
N-methyl-5-vinylimidazole,
2-vinylpyridine,
3-vinylpyridine,
4-vinylpyridine,
2-vinylquinoline,
3-vinyl quinoline,
4-Vinylquinoline.

Examples of the compound represented by formula (2) include the following compounds as compounds in which R ²¹ is a methyl group, n is 0, and A is a nitrogen-containing aromatic heterocyclic group.

N-methyl-2-isopropenylimidazole,
N-methyl-4-isopropenylimidazole,
N-methyl-5-isopropenylimidazole,
2-isopropenyl pyridine,
3-isopropenyl pyridine,
4-isopropenyl pyridine,
2-isopropenyl quinoline,
3-isopropenyl quinoline,
4-Isopropenylquinoline.

Examples of the compound represented by formula (2) include the following compounds as compounds in which R ²¹ is a vinyl group, n is 0, and A is a nitrogen-containing aromatic heterocyclic group.

N-methyl-2- (1-methylene-2-propenyl) imidazole,
N-methyl-4- (1-methylene-2-propenyl) imidazole,
N-methyl-5- (1-methylene-2-propenyl) imidazole,
2- (1-methylene-2-propenyl) pyridine,
3- (1-methylene-2-propenyl) pyridine,
4- (1-methylene-2-propenyl) pyridine,
2- (1-methylene-2-propenyl) quinoline,
3- (1-methylene-2-propenyl) quinoline,
4- (1-methylene-2-propenyl) quinoline.

As the compound represented by the formula (2), R ²¹ is a vinyl group, n is 1, R ²² is an alkylene group, and A is a nitrogen-containing aromatic heterocyclic group. Compounds can be mentioned.

Compound in which R ²² is a methylene group:
N-methyl-2- (2-methylene-3-butenyl) imidazole,
N-methyl-4- (2-methylene-3-butenyl) imidazole,
N-methyl-5- (2-methylene-3-butenyl) imidazole,
2- (2-methylene-3-butenyl) pyridine,
3- (2-methylene-3-butenyl) pyridine,
4- (2-methylene-3-butenyl) pyridine,
2- (2-methylene-3-butenyl) quinoline,
3- (2-methylene-3-butenyl) quinoline,
4- (2-Methylene-3-butenyl) quinoline.

Compound in which R ²² is an ethylene group:
N-methyl-2- (3-methylene-4-pentenyl) imidazole,
N-methyl-4- (3-methylene-4-pentenyl) imidazole,
N-methyl-5- (3-methylene-4-pentenyl) imidazole,
2- (3-methylene-4-pentenyl) pyridine,
3- (3-methylene-4-pentenyl) pyridine,
4- (3-methylene-4-pentenyl) pyridine,
2- (3-methylene-4-pentenyl) quinoline,
3- (3-methylene-4-pentenyl) quinoline,
4- (3-Methylene-4-pentenyl) quinoline.

As the compound represented by the formula (2), preferably, R ²¹ is a hydrogen atom, n is 1, R ²² is a group represented by the formula (2-Y), and A is a substituted amino group. It is a compound that is a group. More preferably, R ²¹ is a hydrogen atom, n is 1, R ²² is a group represented by the formula (2-Y), and A is a group represented by the formula (2-X). A compound. More preferably, the compound ^{R 23} and ^{R 24} is a straight-chain alkyl group having a carbon number of 1-2 of the formula (2-X), the compound ^{R 23} and ^{R 24} is a trimethylsilyl group of the formula (2-X) And R ²³ and R ²⁴ in the formula (2-X) are bonded to each other, and the group is a polymethylene group having 4 to 6 carbon atoms.

As the compound represented by the formula (2), particularly preferably,
4-N, N-bis (trimethylsilyl) aminostyrene,
3-N, N-bis (trimethylsilyl) aminostyrene,
4-N, N-dimethylaminomethylstyrene,
3-N, N-dimethylaminomethylstyrene,
4- (1-pyrrolidinyl) ethylstyrene,
3- (1-pyrrolidinyl) ethylstyrene.

The content of the monomer unit based on the compound represented by the formula (1) is preferably 0.01% by mass or more per 100% by mass of the conjugated diene polymer in order to improve fuel efficiency. Preferably it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve economy and wear resistance, the content is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

In the monomer unit based on the compound represented by the formula (1), the groups represented by X ¹ , X ² and X ³ may be a hydroxyl group by hydrolysis or the like.

The content of the monomer unit based on the compound represented by the formula (2) is preferably 0.01% by mass or more per 100% by mass of the conjugated diene polymer in order to improve fuel economy and wear resistance. More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve economy and wear resistance, the content is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

The conjugated diene polymer according to the present invention may have a structural unit (vinyl aromatic hydrocarbon unit) based on a vinyl aromatic hydrocarbon in order to improve wear resistance. Examples of the vinyl aromatic hydrocarbon include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene. Styrene is preferable.

The content of the vinyl aromatic hydrocarbon unit is 0% by mass or more (the content of the conjugated diene unit is 100% by mass or less), where the total amount of the conjugated diene unit and the vinyl aromatic hydrocarbon unit is 100% by mass. The content is preferably 10% by mass or more (the content of the conjugated diene unit is 90% by mass or less), and more preferably 15% by mass or more (the content of the conjugated diene unit is 85% by mass or less). In order to improve fuel economy, the content of vinyl aromatic hydrocarbon units is preferably 50% by mass or less (the content of conjugated diene units is 50% by mass or more), more preferably 45% by mass or less. (The content of the conjugated diene unit is 55% by mass or more).

The Mooney viscosity (ML _{1 + 4} ) of the conjugated diene polymer is preferably 10 or more, more preferably 20 or more, in order to increase the wear resistance. Moreover, in order to improve workability, Preferably it is 200 or less, More preferably, it is 150 or less. The Mooney viscosity (ML _{1 + 4} ) is measured at 100 ° C. according to JIS K 6300 (1994).

The vinyl bond content of the conjugated diene polymer is preferably 80 mol% or less, and more preferably 70 mol% or less in order to improve the fuel efficiency by setting the content of the conjugated diene unit to 100 mol%. Moreover, in order to improve wet grip property, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more, Most preferably, it is 40 mol% or more. The vinyl bond amount is determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

The molecular weight distribution of the conjugated diene polymer is preferably 1 to 5 and more preferably 1 to 2 in order to improve fuel efficiency. The molecular weight distribution is obtained by measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) method and dividing Mw by Mn.

As a preferred method for producing a conjugated diene polymer, a conjugated diene, a monomer represented by the above formula (1), and a single compound represented by the above formula (2) are prepared in a hydrocarbon solvent with an alkali metal catalyst. The method of polymerizing the monomer component containing a monomer can be mentioned.

Examples of the alkali metal catalyst include alkali metals, organic alkali metal compounds, complexes of alkali metals and polar compounds, oligomers having alkali metals, and the like. Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium and the like. Examples of the organic alkali metal compound include ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, t-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2 -Butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, 4-cyclopentyllithium, dimethylaminopropyllithium, diethylaminopropyllithium, t-butyldimethylsiloxypropyllithium, N-morpholinopropyllithium, lithium hexamethyleneimide, lithium pyrrole Zido, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, 1,4-dilithio-2-butene, sodium naphthalenide, sodium Bifenirido, such as potassium napthalenide can be mentioned. Examples of the complex of alkali metal and polar compound include potassium-tetrahydrofuran complex and potassium-diethoxyethane complex. Examples of the oligomer having alkali metal include sodium salt of α-methylstyrene tetramer. Can do. An organic lithium compound or an organic sodium compound is preferable, and an organic lithium compound having 2 to 20 carbon atoms or an organic sodium compound having 2 to 20 carbon atoms is more preferable.

The hydrocarbon solvent is a solvent that does not deactivate the organic alkali metal compound catalyst, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.
Examples of the aliphatic hydrocarbon include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2- Examples include butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and the like. In addition, examples of the aromatic hydrocarbon include benzene, toluene, xylene, and ethylbenzene. Examples of the alicyclic hydrocarbon include cyclopentane and cyclohexane. One or more of these may be used, and the hydrocarbon solvent may be a mixture of various components such as industrial hexane. Preferably, it is a hydrocarbon having 2 to 12 carbon atoms.

A monomer component containing a conjugated diene, a compound represented by the above formula (1) and a compound represented by the above formula (2) is polymerized with an alkali metal catalyst in a hydrocarbon solvent, and the monomer based on the conjugated diene is used. A polymer having a monomer unit, a monomer unit based on the compound represented by the above formula (1), and a monomer unit based on the compound represented by the above formula (2) is produced. Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. One or more of these are used. 1,3-butadiene and isoprene are preferred.

The amount of the compound represented by the formula (1) is preferably 0.01% by mass or more in order to improve the fuel efficiency by setting the total amount of the monomer components used in the polymerization to 100% by mass. More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve economic efficiency and wear resistance, it is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. is there.

The amount of the compound represented by the formula (2) is preferably 0.01% by mass in order to increase the fuel efficiency and wear resistance, with the total amount of the monomer components used in the polymerization being 100% by mass. % Or more, more preferably 0.02 mass% or more, still more preferably 0.05 mass% or more. In order to improve economic efficiency and wear resistance, it is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. is there.

Polymerization may be carried out by combining a conjugated diene, a compound represented by the formula (1) and a compound represented by the formula (2) with a vinyl aromatic hydrocarbon. Examples of the vinyl aromatic hydrocarbon include styrene, α -Methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and the like can be mentioned. Styrene is preferable.

The amount of vinyl aromatic hydrocarbon used is preferably 10% by mass or more (the amount of conjugated diene used) in order to increase the strength with the total amount of conjugated diene and vinyl aromatic hydrocarbon being 100% by mass. Is 90% by mass or less), more preferably 15% by mass or more (the amount of conjugated diene used is 85% by mass or less). In order to improve fuel efficiency, the amount of vinyl aromatic hydrocarbon used is preferably 50% by mass or less (the amount of conjugated diene used is 50% by mass or more), more preferably 45% by mass or less (conjugated). The amount of diene used is 55% by mass or more).

In the polymerization reaction, the total amount of the conjugated diene, the compound represented by the formula (1), the compound represented by the formula (2) and the vinyl aromatic hydrocarbon is 100. In order to increase the strength, it is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and still more preferably 100% by mass.

Polymerization reaction is an agent that adjusts the amount of vinyl bonds of conjugated diene units, an agent that adjusts the distribution of monomer units based on monomers other than conjugated diene units and conjugated dienes in the conjugated diene polymer chain , And collectively referred to as “regulators”). Examples of such agents include ether compounds, tertiary amines, and phosphine compounds. Examples of the ether compound include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and diethylene glycol diethyl ether. And aliphatic diethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, quinoline and the like. Examples of the phosphine compound include trimethylphosphine, triethylphosphine, triphenylphosphine, and the like. One or more of these are used.

The polymerization temperature is usually 25 to 100 ° C, preferably 35 to 90 ° C.
More preferably, it is 50-80 degreeC. The polymerization time is usually 10 minutes to 5 hours.

In the above method for producing a conjugated diene polymer, a coupling agent is added to the hydrocarbon solution of the conjugated diene polymer from the start of polymerization of the monomer using an alkali metal catalyst to the termination of polymerization as necessary. Also good. An example of the coupling agent is a compound represented by the following formula (3).

R ³¹ _a ML _4-a (3)
(In the formula, R ³¹ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aryl group, M represents a silicon atom or a tin atom, L represents a halogen atom or a hydrocarbyloxy group, and a represents an integer of 0 to 2. Represents.)

As the coupling agent represented by the above formula (3), silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxysilane, Examples thereof include methyltrimethoxysilane, dimethoxydimethylsilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, and diethoxydiethylsilane.

The addition amount of the coupling agent is preferably 0.03 mol or more, more preferably 0.05 mol or more, per 1 mol of alkali metal derived from the alkali metal catalyst in order to improve the processability of the conjugated diene polymer. It is. Moreover, in order to improve low-fuel-consumption property, Preferably it is 0.4 mol or less, More preferably, it is 0.3 mol or less.

The conjugated diene polymer can be obtained by a known recovery method, for example, (1) a method of adding a coagulant to a hydrocarbon solution of the conjugated diene polymer, and (2) steam is added to the hydrocarbon solution of the conjugated diene polymer. Depending on the method of addition, it can be recovered from the hydrocarbon solution of the conjugated diene polymer. The recovered conjugated diene polymer may be dried by a known dryer such as a band dryer or an extrusion dryer.

The conjugated diene polymer can be used as a rubber component, and the rubber composition of the present invention can be obtained by blending other rubber components and additives such as silica.

The content of the conjugated diene polymer in 100% by mass of the rubber component is 5% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more. If the amount is less than 5% by mass, the effect of improving fuel economy tends to be difficult to obtain. Further, the content of the conjugated diene polymer is preferably 90% by mass or less, more preferably 80% by mass or less. When it exceeds 90% by mass, the wear resistance is lowered and the cost tends to be high.

The rubber component that can be used in addition to the conjugated diene polymer is not limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR). ), Chloroprene rubber (CR), butyl rubber (IIR) and the like. These rubber components may be used alone or in combination of two or more. Of these, NR and BR are preferred because they exhibit a good balance between low fuel consumption, wet grip performance and wear resistance.
These rubber components are not particularly limited, and those generally used in the tire industry can be used.

The content of NR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 15% by mass or more. If the amount is less than 5% by mass, sufficient fuel economy tends not to be obtained. The NR content is preferably 60% by mass or less, more preferably 40% by mass or less. When it exceeds 60 mass%, workability tends to deteriorate.

The content of BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 15% by mass or more. When it is less than 5% by mass, sufficient wear resistance tends to be not obtained. Further, the BR content is preferably 60% by mass or less, more preferably 40% by mass or less. When it exceeds 60% by mass, fuel efficiency tends to deteriorate.

The rubber composition of the present invention uses silica as a reinforcing agent. Examples of the silica include dry silica (anhydrous silicic acid), wet silica (hydrous silicic acid), colloidal silica, precipitated silica, calcium silicate, and aluminum silicate. One or more of these can be used. The BET specific surface area of silica is preferably 50 to 250 m ² / g. The BET specific surface area is measured according to ASTM D1993-03. As a commercial product of silica, the product name Ultrasil VN3-G manufactured by Degussa, the product name VN3, AQ, ER, RS-150 manufactured by Tosoh Silica Co., Ltd., and the product names Zeosil 1115MP, 1165MP manufactured by Rhodia can be used. .

The content of silica is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component. The content is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, in order to improve fuel efficiency. Moreover, in order to improve abrasion resistance and intensity | strength, Preferably it is 120 mass parts or less, More preferably, it is 100 mass parts or less.

The rubber composition of the present invention uses a silane coupling agent having a mercapto group as the silane coupling agent. By blending a silane coupling agent having a mercapto group with the conjugated diene polymer and silica, the silica can be dispersed well, and the fuel economy, wet grip performance and wear resistance can be significantly improved.

（式中、Ｒ^１０１〜Ｒ^１０３は、分岐若しくは非分岐の炭素数１〜１２のアルキル基、分岐若しくは非分岐の炭素数１〜１２のアルコキシ基、又は−Ｏ−（Ｒ^１１１−Ｏ）_ｂ−Ｒ^１１２（ｂ個のＲ^１１１は、分岐若しくは非分岐の炭素数１〜３０の２価の炭化水素基を表す。ｂ個のＲ^１１１はそれぞれ同一でも異なっていてもよい。Ｒ^１１２は、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、炭素数６〜３０のアリール基、又は炭素数７〜３０のアラルキル基を表す。ｂは１〜３０の整数を表す。）で表される基を表す。Ｒ^１０１〜Ｒ^１０３はそれぞれ同一でも異なっていてもよい。Ｒ^１０４は、分岐若しくは非分岐の炭素数１〜６のアルキレン基を表す。）

（式中、Ｒ^２０１は水素、ハロゲン、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、分岐若しくは非分岐の炭素数２〜３０のアルキニル基、又は該アルキル基の末端の水素が水酸基若しくはカルボキシル基で置換されたものを表す。Ｒ^２０２は分岐若しくは非分岐の炭素数１〜３０のアルキレン基、分岐若しくは非分岐の炭素数２〜３０のアルケニレン基、又は分岐若しくは非分岐の炭素数２〜３０のアルキニレン基を表す。Ｒ^２０１とＲ^２０２とで環構造を形成してもよい。） Examples of the silane coupling agent having a mercapto group include a silane coupling agent represented by the following formula (I) and / or a binding unit A represented by the following formula (II) and a coupling unit represented by the following formula (III). A silane coupling agent containing B can be preferably used.

(Wherein R ^{101 to} R ¹⁰³ are branched or unbranched alkyl groups having 1 to 12 carbon atoms, branched or unbranched alkoxy groups having 1 to 12 carbon atoms, or —O— (R ¹¹¹ —O) _b. -R ¹¹² (b pieces ^{by R 111} are .b pieces ^{by R 111} are optionally each be the same or different ^{.R 112} representing a divalent hydrocarbon group of branched or unbranched C1-30 is A branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms; Represents an integer of 1 to 30.) R ^{101 to} R ¹⁰³ may be the same or different, and R ¹⁰⁴ is a branched or unbranched alkylene group having 1 to 6 carbon atoms. Represents.)

Wherein R ²⁰¹ is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, branched or unbranched alkenyl group having 2 to 30 carbon atoms, branched or unbranched carbon group having 2 to 30 carbon atoms. An alkynyl group or a group in which the hydrogen at the terminal of the alkyl group is substituted with a hydroxyl group or a carboxyl group, R ²⁰² represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched carbon number of 2 30 represents an alkenylene group or a branched or unbranched alkynylene group having 2 to 30 carbon atoms, and R ²⁰¹ and R ²⁰² may form a ring structure.)

Hereinafter, the silane coupling agent represented by the formula (I) will be described.

R ^{101 to} R ¹⁰³ are each a branched or unbranched alkyl group having 1 to 12 carbon atoms, a branched or unbranched alkoxy group having 1 to 12 carbon atoms, or —O— (R ¹¹¹ —O) _z —R ¹¹² . Represents the group represented. From the viewpoint that the effect of the present invention can be obtained satisfactorily, at least one of R ^{101 to} R ¹⁰³ is preferably a group represented by —O— (R ¹¹¹ —O) _z —R ¹¹² , and two of them are — More preferably, it is a group represented by O— (R ¹¹¹ —O) _z —R ¹¹² , and one is a branched or unbranched C 1-12 alkoxy group.

Examples of the branched or unbranched alkyl group having 1 to 12 carbon atoms (preferably 1 to 5 carbon atoms) represented by R ^{101 to} R ¹⁰³ include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group and the like.

Examples of the branched or unbranched alkoxy group having 1 to 12 carbon atoms (preferably 1 to 5 carbon atoms) of R ^{101 to} R ¹⁰³ include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, n- Examples include butoxy, iso-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy and the like.

In —O— (R ¹¹¹ —O) _z —R ¹¹² of R ^{101 to} R ¹⁰³ , R ¹¹¹ represents a branched or unbranched carbon number of 1 to 30 (preferably having 1 to 15 carbon atoms, more preferably 1 carbon number). To 3) a divalent hydrocarbon group.
Examples of the hydrocarbon group include a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenylene group having 2 to 30 carbon atoms, and a branched or unbranched alkynylene group having 2 to 30 carbon atoms. And an arylene group having 6 to 30 carbon atoms. Of these, a branched or unbranched alkylene group having 1 to 30 carbon atoms is preferable.

Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms (preferably 1 to 15 carbon atoms, more preferably 1 to 3 carbon atoms) of R ¹¹¹ include, for example, a methylene group, an ethylene group, a propylene group, and a butylene group. Pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like.

Examples of the branched or unbranched carbon atoms 2-30 alkenylene group (preferably 2 to 15 carbon atoms, more preferably 2 to 3 carbon atoms) of R ^111, for example, vinylene group, propenylene group, 2-propenylene Group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group, 1-hexenylene group, 2-hexenylene group, 1-octenylene group and the like.

Examples of the branched or unbranched carbon atoms 2-30 alkynylene group (preferably 2 to 15 carbon atoms, more preferably 2 to 3 carbon atoms) of R ^111, for example, ethynylene group, propynylene group, butynylene group, pentynylene group Hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecynylene group, dodecynylene group and the like.

Examples of the arylene group having 6 to 30 carbon atoms (preferably 6 to 15 carbon atoms) of R ¹¹¹ include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.

z represents an integer of 1 to 30 (preferably 2 to 20, more preferably 3 to 7, still more preferably 5 to 6).

R ¹¹² represents a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. Represent. Of these, a branched or unbranched alkyl group having 1 to 30 carbon atoms is preferable.

Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms (preferably 3 to 25 carbon atoms, more preferably 10 to 15 carbon atoms) of R ¹¹² include, for example, a methyl group, an ethyl group, an n-propyl group, Isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group and the like.

Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms (preferably 3 to 25 carbon atoms, more preferably 10 to 15 carbon atoms) for R ¹¹² include, for example, a vinyl group, a 1-propenyl group, and 2-propenyl. Group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group Group, pentadecenyl group, octadecenyl group and the like.

Examples of the aryl group having 6 to 30 carbon atoms (preferably 10 to 20 carbon atoms) of R ¹¹² include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms (preferably 10 to 20 carbon atoms) of R ¹¹² include a benzyl group and a phenethyl group.

Specific examples of the group represented by —O— (R ¹¹¹ —O) _z —R ¹¹² include, for example, —O— (C ₂ H ₄ —O) ₅ —C ₁₁ H ₂₃ , —O— (C _{2 H 4 -O) 5 -C 12 H} 25, -O- (C 2 H 4 -O) 5 -C 13 H 27, -O- (C 2 H 4 -O) 5 -C 14 H 29, -O _{- (C 2 H 4 -O)} 5 -C 15 H 31, -O- (C 2 H 4 -O) 3 -C 13 H 27, -O- (C 2 H 4 -O) 4 -C 13 H _{27, -O- (C 2 H 4} -O) 6 -C 13 H 27, such as _{-O- (C 2 H 4 -O)} 7 -C 13 H 27 and the like. Among _{these, -O- (C 2 H 4 -O} ) 5 -C 11 H 23, -O- (C 2 H 4 -O) 5 -C 13 H 27, -O- (C 2 H 4 -O) 5 _{-C 15 H 31, -O- (C} 2 H 4 -O) 6 -C 13 H 27 are preferable.

Examples of the branched or unbranched alkylene group having 1 to 6 carbon atoms (preferably 1 to 5 carbon atoms) of R ¹⁰⁴ include the same groups as the branched or unbranched alkylene group having 1 to 30 carbon atoms of R ^111. Can give.

Examples of the silane coupling agent represented by the formula (I) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, A compound represented by the following formula (Si363 manufactured by Degussa) and the like can be mentioned, and a compound represented by the following formula can be preferably used. These may be used alone or in combination of two or more.

Next, the silane coupling agent containing the coupling unit A represented by the formula (II) and the coupling unit B represented by the formula (III) will be described.

A silane coupling agent containing a bond unit A represented by the formula (II) and a bond unit B represented by the formula (III) is processed as compared with a polysulfide silane such as bis- (3-triethoxysilylpropyl) tetrasulfide. Increase in viscosity is suppressed. This is presumably because the increase in Mooney viscosity is small because the sulfide portion of the bond unit A is a C—S—C bond and is thermally stable compared to tetrasulfide and disulfide.

Moreover, the shortening of the scorch time is suppressed as compared with mercaptosilane such as 3-mercaptopropyltrimethoxysilane. This is because the bonding unit B has a structure of mercaptosilane, but the —C ₇ H ₁₅ part of the bonding unit A covers the —SH group of the bonding unit B, so that it does not easily react with the polymer and scorch is less likely to occur. This is probably because of this.

In the silane coupling agent having the above structure, the content of the bond unit A is preferably 30 from the viewpoint that the effect of suppressing the increase in viscosity during processing and the effect of suppressing the shortening of the scorch time can be enhanced. It is at least mol%, more preferably at least 50 mol%, preferably at most 99 mol%, more preferably at most 90 mol%. Further, the content of the binding unit B is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, preferably 70 mol% or less, more preferably 65 mol% or less, More preferably, it is 55 mol% or less. Further, the total content of the binding units A and B is preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.
The content of the bond units A and B is an amount including the case where the bond units A and B are located at the terminal of the silane coupling agent. The form in the case where the bonding units A and B are located at the end of the silane coupling agent is not particularly limited as long as the units corresponding to the formulas (II) and (III) showing the bonding units A and B are formed. .

Examples of the halogen for R ²⁰¹ include chlorine, bromine, and fluorine.

^Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms of R ²⁰¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert- Examples thereof include a butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, and a decyl group. The number of carbon atoms of the alkyl group is preferably 1-12.

^Examples of the branched or unbranched C 2-30 alkenyl group of R ²⁰¹ include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, and 2-pentenyl. Group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group and the like. The alkenyl group preferably has 2 to 12 carbon atoms.

^Examples of the branched or unbranched alkynyl group having 2 to 30 carbon atoms of R ²⁰¹ include ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, And dodecynyl group. The alkynyl group preferably has 2 to 12 carbon atoms.

Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms of R ²⁰² include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, Examples include dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like. The alkylene group preferably has 1 to 12 carbon atoms.

^Examples of the branched or unbranched C2-C30 alkenylene group of R202 include vinylene group, 1-propenylene group, 2-propenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group and 2-pentenylene. Group, 1-hexenylene group, 2-hexenylene group, 1-octenylene group and the like. The alkenylene group preferably has 2 to 12 carbon atoms.

Examples of the branched or unbranched alkynylene group having 2 to 30 carbon atoms of R ²⁰² include ethynylene group, propynylene group, butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecynylene group, And dodecynylene group. The alkynylene group preferably has 2 to 12 carbon atoms.

In the silane coupling agent containing the bonding unit A represented by the formula (II) and the coupling unit B represented by the formula (III), the number of repetitions of the bonding unit A (x) and the number of repetitions of the bonding unit B (y) The total number of repetitions (x + y) is preferably in the range of 3 to 300. Within this range, since the mercaptosilane of the bond unit B is covered by —C ₇ H ₁₅ of the bond unit A, it is possible to suppress the scorch time from being shortened and to have good reactivity with silica and rubber components. Can be secured.

Examples of the silane coupling agent containing the binding unit A represented by the formula (II) and the coupling unit B represented by the formula (III) include NXT-Z30, NXT-Z45, NXT-Z60 manufactured by Momentive. Can be used. These may be used alone or in combination of two or more.

The content of the silane coupling agent having a mercapto group is preferably 0.5 parts by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2.5 parts by mass or more with respect to 100 parts by mass of silica. is there. If it is less than 0.5 part by mass, it may be difficult to sufficiently disperse silica. Moreover, content of the silane coupling agent which has a mercapto group becomes like this. Preferably it is 20 mass parts or less, More preferably, it is 15 mass parts or less, More preferably, it is 10 mass parts or less. When it exceeds 20 parts by mass, there is a tendency that an effect commensurate with the increase in cost cannot be obtained.

The rubber composition of the present invention may contain additives other than the above-mentioned chemicals. Known additives can be used, such as sulfur vulcanizing agents; thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, guanidine vulcanization accelerators. Vulcanization accelerators such as stearic acid and zinc oxide; organic peroxides such as dicumyl peroxide and ditertiary butyl peroxide; reinforcing agents such as carbon black; calcium carbonate, talc and alumina And fillers such as clay, aluminum hydroxide and mica; extension oils; processing aids; anti-aging agents; and lubricants.

Examples of the sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. The content of sulfur is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. It is.

Examples of the vulcanization accelerator include 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and thiazole vulcanization accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethylthiuram. Thiuram vulcanization accelerators such as disulfides; N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N -Sulfenamide vulcanization accelerators such as oxyethylene-2-benzothiazole sulfenamide and N, N'-diisopropyl-2-benzothiazole sulfenamide; diphenylguanidine, diortolylguanidine, orthotolylbiguanidine What guanidine-based vulcanization accelerator and the like. The content of the vulcanization accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the rubber component.

Examples of the carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. Carbon blacks include channel carbon blacks such as EPC, MPC and CC; furnace carbon blacks such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF; FT and MT Thermal carbon black such as acetylene carbon black is exemplified. One or more of these can be used.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 5 to 200 m ² / g, and the dibutyl phthalate (DBP) absorption amount of carbon black is preferably 5 to 300 ml / 100 g. . The nitrogen adsorption specific surface area is measured according to ASTM D4820-93, and the DBP absorption is measured according to ASTM D2414-93. As a commercial item, Mitsubishi Chemical Corporation trade name Dia Black N339, Tokai Carbon Co., Ltd. trade name Seast 6, Seast 7HM, Seast KH, Degussa Corporation trade name CK 3, Special Black 4A, etc. can be used.

The content of carbon black is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the rubber component. Further, the content is more preferably 3 parts by mass or more, and still more preferably 4 parts by mass or more, in order to increase wear resistance and strength. Moreover, in order to improve low fuel consumption, More preferably, it is 30 mass parts or less, More preferably, it is 10 mass parts or less.

The content of the reinforcing agent is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the rubber component. Further, the content is more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, in order to increase wear resistance and strength. Moreover, in order to improve low fuel consumption, More preferably, it is 120 mass parts or less, More preferably, it is 100 mass parts or less.

The mass ratio of the silica content and the carbon black content used as the reinforcing agent (silica content: carbon black content) is preferably 2: 1 to 50: 1. The mass ratio is more preferably 5: 1 to 20: 1 in order to increase fuel efficiency and enhance reinforcement.

Examples of the extending oil include aromatic mineral oil (viscosity specific gravity constant (VGC value) 0.900 to 1.049), naphthenic mineral oil (VGC value 0.850 to 0.899), paraffinic mineral oil (VGC value 0.790 to 0.849), and the like. The polycyclic aromatic content of the extender oil is preferably less than 3% by mass, more preferably less than 1% by mass. The polycyclic aromatic content is measured according to the British Petroleum Institute 346/92 method. Moreover, the aromatic compound content (CA) of the extending oil is preferably 20% by mass or more. One or more of these extending oils are used.

As a method for producing the rubber composition of the present invention, a known method, for example, a method of kneading each component with a known mixer such as a roll or Banbury can be used.

As kneading conditions, when additives other than the vulcanizing agent and the vulcanization accelerator are blended, the kneading temperature is usually 50 to 200 ° C., preferably 80 to 190 ° C., and the kneading time is usually 30 seconds. -30 minutes, preferably 1-30 minutes. When blending a vulcanizing agent and a vulcanization accelerator, the kneading temperature is usually 100 ° C. or lower, preferably room temperature to 80 ° C. A composition containing a vulcanizing agent and a vulcanization accelerator is usually used after vulcanization treatment such as press vulcanization. The vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.

The rubber composition of the present invention has a high level of good balance between low fuel consumption, wet grip performance and wear resistance.

The rubber composition of the present invention is used for tire treads (cap treads).

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, a rubber composition containing various additives as necessary is extruded in accordance with the shape of the tread of the tire at an unvulcanized stage, molded by a normal method on a tire molding machine, etc. The tire members are bonded together to form an unvulcanized tire. This unvulcanized tire can be heated and pressurized in a vulcanizer to produce the pneumatic tire of the present invention.

The pneumatic tire of the present invention can be suitably used as a tire for passenger cars.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

<Preparation of copolymer 1>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 137 g of 1,3-butadiene, 43 g of styrene, a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene. 53 g, 1.52 ml of tetrahydrofuran, and 1.18 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, 0.64 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 3.98 mmol) were charged into the polymerization reactor to initiate the polymerization reaction. .

1,3-butadiene, styrene, bis (diethylamino) methylvinylsilane while stirring rate is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. Copolymerization reaction of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene was performed for 2 hours. The supply amount of 1,3-butadiene was 205 g, and the supply amount of styrene was 65 g. Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of the mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene was 0.12% by mass, bis (diethylamino) methyl The amount of vinylsilane charged was 0.14% by mass.

10 ml of hexane solution containing 0.5 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 1 was added to the polymer solution. 0.8 g, 0.9 g of pentaerythrityltetrakis (3-laurylthiopropionate) (trade name: Sumilizer TP-D, manufactured by Sumitomo Chemical Co., Ltd.) was added, and then the polymer solution was evaporated at room temperature for 24 hours. And dried under reduced pressure at 55 ° C. for 12 hours to obtain a copolymer 1.

<Creation of copolymer 2>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 137 g of 1,3-butadiene, 43 g of styrene, 0.43 g of 4-N, N-dimethylaminomethylstyrene, 1.52 ml of tetrahydrofuran, ethylene glycol diethyl ether 1.18 ml was charged into the polymerization reactor. Next, 0.64 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 3.59 mmol) were charged into the polymerization reactor to initiate the polymerization reaction. .

1,3-butadiene, styrene, bis (diethylamino) methylvinylsilane while stirring rate is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. And 4-N, N-dimethylaminomethylstyrene was copolymerized for 2 hours. The supply amount of 1,3-butadiene was 205 g, and the supply amount of styrene was 65 g. Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of 4-N, N-dimethylaminomethylstyrene charged was 0.10% by mass, and the amount of bis (diethylamino) methylvinylsilane charged was 0.14% by mass. there were.

10 ml of hexane solution containing 0.5 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 1 was added to the polymer solution. 0.8 g, 0.9 g of pentaerythrityltetrakis (3-laurylthiopropionate) (trade name: Sumilizer TP-D, manufactured by Sumitomo Chemical Co., Ltd.) was added, and then the polymer solution was evaporated at room temperature for 24 hours. And dried under reduced pressure at 55 ° C. for 12 hours to obtain a copolymer 2.

<Creation of copolymer 3>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 1,3-butadiene 137 g, styrene 43 g, tetrahydrofuran 1.52 ml, ethylene glycol diethyl ether 1.18 ml, 4-N, N-bis (trimethylsilyl) Aminostyrene 0.70 g was charged into the polymerization reactor. Next, 3.81 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

While stirring speed is 130 rpm, polymerization reactor internal temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor, 1,3-butadiene, styrene, and 4-N, The copolymerization reaction of N-bis (trimethylsilyl) aminostyrene was performed for 2 hours. The supply amount of 1,3-butadiene was 205 g, and the supply amount of styrene was 65 g. The total amount of 4-N, N-bis (trimethylsilyl) aminostyrene charged in the total amount of monomers charged and supplied to the polymerization reactor was 0.16% by mass.

10 ml of hexane solution containing 0.5 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 1 was added to the polymer solution. 0.8 g, 0.9 g of pentaerythrityltetrakis (3-laurylthiopropionate) (trade name: Sumilizer TP-D, manufactured by Sumitomo Chemical Co., Ltd.) was added, and then the polymer solution was evaporated at room temperature for 24 hours. And dried under reduced pressure at 55 ° C. for 12 hours to obtain a copolymer 3.

The obtained copolymers 1 to 3 were analyzed by the following method. The results are shown in Table 1.

<Mooney viscosity (ML _{1 + 4} )>
The Mooney viscosity of the copolymer was measured at 100 ° C. according to JIS K6300 (1994).

<Amount of vinyl (unit: mol%)>
The amount of vinyl in the copolymer was determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

<Styrene amount (unit: mass%)>
According to JIS K6383 (1995), the styrene content of the copolymer was determined from the refractive index.

<Molecular weight distribution (Mw / Mn)>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC) method under the following conditions (1) to (8), and the molecular weight distribution (Mw) of the copolymer is measured. / Mn).
(1) Apparatus: HLC-8220 manufactured by Tosoh Corporation
(2) Separation column: Tosoh HM-H (two in series)
(3) Measurement temperature: 40 ° C
(4) Carrier: Tetrahydrofuran (5) Flow rate: 0.6 mL / min (6) Injection volume: 5 μL
(7) Detector: Differential refraction (8) Molecular weight standard: Standard polystyrene

シランカップリング剤３：デグッサ社製のＳｉ６９（ビス（３−トリエトキシシリルプロピル）テトラスルフィド）
カーボンブラック：三菱化学（株）製のダイアブラックＮ２２０（Ｎ_２ＳＡ：１１１ｍ^２／ｇ、ＤＢＰ吸収量：１１５ｍｌ／１００ｇ）
オイル：（株）ジャパンエナジー製のＸ−１４０
老化防止剤：住友化学（株）製のアンチゲン３Ｃ
ステアリン酸：日油（株）製のビーズステアリン酸つばき
酸化亜鉛：三井金属鉱業（株）製の亜鉛華１号
ワックス：大内新興化学工業（株）製のサンノックＮ
硫黄：鶴見化学工業（株）製の粉末硫黄
加硫促進剤ＣＺ：住友化学（株）製のソクシノールＣＺ
加硫促進剤Ｄ：住友化学（株）製のソクシノールＤ Below, various chemical | medical agents used by the Example and the comparative example are demonstrated.
NR: RSS # 3
BR: Ubepol BR150B manufactured by Ube Industries, Ltd.
Copolymers 1-3: synthesized by the above method Silica: Ultrasil VN3 manufactured by Degussa (N ₂ SA: 175 m ² / g)
Silane coupling agent 1: NXT-Z45 manufactured by Momentive (copolymer of bonding unit A and bonding unit B (bonding unit A: 55 mol%, bonding unit B: 45 mol%))
Silane coupling agent 2: Si363 manufactured by Degussa (compound represented by the following formula, content of mercapto group: 3.3%)

Silane coupling agent 3: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa
Carbon black: Diablack N220 manufactured by Mitsubishi Chemical Corporation (N ₂ SA: 111 m ² / g, DBP absorption: 115 ml / 100 g)
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Anti-aging agent: Antigen 3C manufactured by Sumitomo Chemical Co., Ltd.
Stearic acid: Beads manufactured by NOF Corporation Zinc stearate Zinc oxide: Zinc flower No. 1 manufactured by Mitsui Kinzoku Mining Co., Ltd. Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator CZ manufactured by Tsurumi Chemical Co., Ltd. CZ: Soxinol CZ manufactured by Sumitomo Chemical Co., Ltd.
Vulcanization accelerator D: Soxinol D manufactured by Sumitomo Chemical Co., Ltd.

(Examples and Comparative Examples)
According to the blending content shown in Table 2, materials other than sulfur and vulcanization accelerator were kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer manufactured by Kobe Steel Co., Ltd. Obtained. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes under the condition of 80 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized with a 0.5 mm thick mold at 170 ° C. for 20 minutes to obtain a vulcanized rubber composition. Further, the obtained unvulcanized rubber composition is molded into a tread shape and bonded together with other tire members on a tire molding machine to form an unvulcanized tire, which is vulcanized at 170 ° C. for 12 minutes, and tested. Tires (size: 195 / 65R15) were manufactured.

The following evaluation was performed about the obtained vulcanized rubber composition and the tire for a test. The results are shown in Table 2.

<Evaluation items and test methods>
<Rolling resistance>
Using a rolling resistance tester, the rolling resistance when a test tire is run at a rim (15 × 6JJ), internal pressure (230 kPa), load (3.43 kN), speed (80 km / h) is measured and compared. The results are shown as an index when Example 3 is taken as 100. Larger values indicate lower rolling resistance and better fuel efficiency.

<Wet grip performance>
Each test tire was mounted on all wheels of a vehicle (domestic FF2000cc), and a braking distance from an initial speed of 100 km / h was determined on a wet asphalt road surface. The result is expressed as an index. The larger the value, the better the wet skid performance (wet grip performance). The index was calculated by the following formula.
(Wet grip performance index) = (Brake distance of Comparative Example 3) / (Brake distance of each formulation) × 100

<Abrasion resistance>
Using a LAT tester (Laboratory Abbreviation and Skid Tester), the volume loss of each vulcanized rubber composition was measured under the conditions of a load of 50 N, a speed of 20 km / h, and a slip angle of 5 °. The numerical values (wear resistance index) in Table 2 are relative values when the volume loss amount of Comparative Example 3 is 100. The larger the value, the better the wear resistance.

As shown in Table 2, a conjugated diene polymer (copolymers 1 and 2) having a specific monomer unit and having a terminal modified with a specific compound, silica, and a silane having a mercapto group The examples blended with the coupling agents (silane coupling agents 1 and 2) are synergistically improved in fuel efficiency, wet grip performance and wear resistance compared to the rubber compositions of the comparative examples. The performance was obtained in a high-order and well-balanced manner.

Claims (8)

Containing a rubber component, silica, and a silane coupling agent having a mercapto group,
In 100% by mass of the rubber component, a monomer unit based on a conjugated diene, a monomer unit based on a compound represented by the following formula (1), and a single amount based on a compound represented by the following formula (2) The content of the conjugated diene polymer having a body unit is 5% by mass or more,
The rubber composition for treads whose content of the said silica with respect to 100 mass parts of said rubber components is 5-150 mass parts.

Wherein R ¹¹ represents a hydrogen atom or a hydrocarbyl group, m is 0 or 1, R ¹² represents a hydrocarbylene group, and X ¹ , X ² and X ³ are each independently a substituted amino group Or a hydrocarbyl group which may have a substituent, and at least one of X ¹ , X ² and X ³ is a substituted amino group.)

(In the formula, R ²¹ represents a hydrogen atom or a hydrocarbyl group, n is 0 or 1, R ²² represents a hydrocarbylene group, and A represents a substituted amino group or a nitrogen-containing heterocyclic group.) The rubber composition for a tread according to claim 1, wherein R ^{11 in the} formula (1) is a hydrogen atom, and m is 0. R ^{21 in the} formula (2) is a hydrogen atom, n is 1, R ²² is a group represented by the following formula (2-Y), and A is a substituted amino group. The rubber composition for a tread as described.

(In the formula, r represents an integer of 0 to 5, and when r is an integer of 1 to 5, (CH ₂ ) _r is a substituent on the benzene ring, and (CH ₂ ) _r is bonded to A. , R is 0, (CH ₂ ) _r represents a bond between the benzene ring and A.) The tread according to any one of claims 1 to 3, wherein the vinyl bond content of the conjugated diene polymer is 20 mol% or more and 70 mol% or less, where the content of the constituent unit based on the conjugated diene is 100 mol%. Rubber composition. The silane coupling agent includes a silane coupling agent represented by the following formula (I) and / or a binding unit B represented by the following formula (II) and a binding unit A represented by the following formula (III). It is a silane coupling agent, The rubber composition for treads in any one of Claims 1-4 characterized by the above-mentioned.

(Wherein R ^{101 to} R ¹⁰³ are branched or unbranched alkyl groups having 1 to 12 carbon atoms, branched or unbranched alkoxy groups having 1 to 12 carbon atoms, or —O— (R ¹¹¹ —O) _b. -R ¹¹² (b pieces ^{by R 111} are .b pieces ^{by R 111} are optionally each be the same or different ^{.R 112} representing a divalent hydrocarbon group of branched or unbranched C1-30 is A branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms; Represents an integer of 1 to 30.) R ^{101 to} R ¹⁰³ may be the same or different, and R ¹⁰⁴ is a branched or unbranched alkylene group having 1 to 6 carbon atoms. Represents.)

Wherein R ²⁰¹ is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, branched or unbranched alkenyl group having 2 to 30 carbon atoms, branched or unbranched carbon group having 2 to 30 carbon atoms. An alkynyl group or a group in which the hydrogen at the terminal of the alkyl group is substituted with a hydroxyl group or a carboxyl group, R ²⁰² represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched carbon number of 2 30 represents an alkenylene group or a branched or unbranched alkynylene group having 2 to 30 carbon atoms, and R ²⁰¹ and R ²⁰² may form a ring structure.) The rubber composition for a tread according to any one of claims 1 to 5, wherein the rubber component contains natural rubber and / or butadiene rubber. In 100% by mass of the rubber component, the content of the conjugated diene polymer is 5 to 80% by mass, the content of the natural rubber is 5 to 40% by mass, and the content of butadiene rubber is 5 to 40% by mass. The rubber composition for a tread according to claim 6. A pneumatic tire produced using the rubber composition according to any one of claims 1-7.