JP2014001306A - Rubber composition for tread and pneumatic tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition for a tread that can improve high mileage and wet grip performance, and abrasion resistance in favorable balance; a pneumatic tire using the same.SOLUTION: To provide a rubber composition for a tread includes: a rubber constituent; silica; and a silane coupling agent having a mercapto group. In the rubber composition, a content of a conjugated diene polymer obtained by reacting an alkoxysilane compound to one terminal of a copolymer that has a monomer unit based on a conjugated diene, a monomer unit based on a compound shown by the formula (1), and a monomer unit based on a compound shown by the formula (2) is at least 5 mass% in 100 mass% of the rubber constituent, and a content of the silica is 5-150 parts by mass based on 100 parts by mass of the rubber constituent. In the formula, Vand Vdenote a hydrocarbyl group having a polymerizable carbon-carbon double bond; Sdenotes a substituted silyl group; and Adenotes a substituted amino group or a nitrogen-containing heterocyclic group.

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、Ｖ^１は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ｓ^１は置換シリル基を表す。）

（式中、Ｖ^２は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ａ^２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. A conjugated diene polymer obtained by reacting an alkoxysilane compound with one end of a copolymer having a monomer unit based on a compound and a monomer unit based on a compound represented by the following formula (2) The present invention relates to a tread rubber composition having a content of 5% by mass or more and a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

(In the formula, V ¹ represents a hydrocarbyl group having a polymerizable carbon-carbon double bond, and S ¹ represents a substituted silyl group.)

(In the formula, V ² represents a hydrocarbyl group having a polymerizable carbon-carbon double bond, and A ² represents a substituted amino group or a nitrogen-containing heterocyclic group.)

（式中、ｐは１〜１０の整数を表し、Ｒ^３１、Ｒ^３２及びＲ^３３は、それぞれ独立にアルキル基又はアルコキシ基を表し、Ｒ^３１、Ｒ^３２及びＲ^３３の少なくとも１つがアルコキシ基であり、Ａ^３は置換アミノ基を表す。） The alkoxysilane compound is preferably a compound represented by the following formula (3).

(In the formula, p represents an integer of 1 to 10, R ³¹ , R ³² and R ³³ each independently represents an alkyl group or an alkoxy group, and at least one of R ³¹ , R ³² and R ³³ is an alkoxy group. And A ³ represents a substituted amino group.)

（式中、Ｒ^１１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^１２はヒドロカルビレン基を表す。）

（式中、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。） The group represented by V ¹ in the formula (1) is a group represented by the following formula (1-V1), and the group represented by S ¹ in the formula (1) is represented by the following formula (1-S). It is preferable that it is group represented by these.

(In the formula, R ¹¹ represents a hydrogen atom or a hydrocarbyl group, n is 0 or 1, and R ¹² represents a hydrocarbylene group.)

(Wherein X ¹ , X ² and X ³ each independently represents 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 formula (1-V1), R ¹¹ is preferably a hydrogen atom, and n is preferably 0.

（式中、Ｒ^２１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^２２はヒドロカルビレン基を表す。） The group represented by V ² in the formula (2) is preferably a group represented by the following formula (2-V1).

(Wherein R ²¹ represents a hydrogen atom or a hydrocarbyl group, m is 0 or 1, and R ²² represents a hydrocarbylene group.)

（式中、Ｒ^２５及びＲ^２６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^２５とＲ^２６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^２５とＲ^２６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。） It is preferred substituted amino group of A ² in the formula (2) is a group represented by the following formula (2-A).

(In the formula, each of R ²⁵ and R ²⁶ has a hydrocarbyl group, a trihydrocarbyl silyl group, or R ²⁵ and R ²⁶ 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 ²⁵ and R ²⁶ are one group and represent a group bonded to the nitrogen atom with a double bond.)

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 represent a branched or unbranched C 1-12 alkyl group, a branched or unbranched C 1-12 alkoxy group, 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 from each other. R ¹⁰⁴ represents a branched or unbranched alkylene group having 1 to 6 carbon atoms. ]

[Wherein, R ²⁰¹ represents 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 hydrogen at the terminal of the alkyl group is substituted with a hydroxyl group or a carboxyl group is represented. R ²⁰² represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenylene group having 2 to 30 carbon atoms, or a branched or unbranched alkynylene group having 2 to 30 carbon atoms. 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, for a tread comprising a conjugated diene polymer having a specific monomer unit and having a terminal modified with a specific compound, silica, and a silane coupling agent having a mercapto group. Since it is a rubber composition, it is possible to provide a pneumatic tire with improved fuel efficiency, wet grip performance and wear resistance in a well-balanced manner.

（式中、Ｖ^１は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ｓ^１は置換シリル基を表す。）

（式中、Ｖ^２は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ａ^２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 includes 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). It is obtained by reacting an alkoxysilane compound with one end of a copolymer having a monomer unit based thereon.

(In the formula, V ¹ represents a hydrocarbyl group having a polymerizable carbon-carbon double bond, and S ¹ represents a substituted silyl group.)

(In the formula, V ² represents a hydrocarbyl group having a polymerizable carbon-carbon double bond, and A ² 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. A nitrogen-containing 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 heterocyclic ring, and the nitrogen-containing heterocyclic ring is an aromatic having a nitrogen atom as a hetero atom constituting the ring. Represents a family heterocycle.

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.

V ¹ in formula (1) represents a hydrocarbyl group having a polymerizable carbon-carbon double bond.

V ¹ is preferably a group represented by the following formula (1-V).

（式中、ｎは０又は１であり、Ｒ^１１、Ｒ^１３及びＲ^１４は、それぞれ独立に水素原子又はヒドロカルビル基を表し、Ｒ^１２はヒドロカルビレン基を表す。）

(In the formula, n is 0 or 1, R ¹¹ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a hydrocarbyl group, and R ¹² represents a hydrocarbylene group.)

In the formula (1-V), n represents 0 or 1.

Examples of the hydrocarbyl group of R ¹¹ , R ¹³ and R ¹⁴ include an alkyl group, an alkenyl group and an aryl 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. Examples of the aryl group include a phenyl group, a methylphenyl group, and an ethylphenyl group, and a phenyl group is preferable.

R ¹¹ , R ¹³ and R ¹⁴ are preferably a hydrogen atom, a methyl group, a vinyl group or a phenyl group, and more preferably a hydrogen atom.

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. .
Moreover, as the group in which the arylene group and the alkylene group are bonded, it is preferable that the carbon atom of the arylene group of the group is bonded to the carbon atom to which R ^{11 in} the formula (1-V) is bonded.

In a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group (for example, a group represented by the following formula (1-R))), the position of a carbon atom on a benzene ring from which a hydrogen atom is removed and Depending on the position of the carbon atom on the benzene ring to which the alkylene group is bonded, a para-phenylene-alkylene group (for example, a group represented by the following formula (1-Ra)), a meta-phenylene-alkylene group (for example, A group represented by the following formula (1-Rb)), and an ortho-phenylene-alkylene group (for example, a group represented by the following formula (1-Rc)).

（式中、ｄは１〜１０の整数を表し、（ＣＨ_２）_ｄはベンゼン環上の置換基である。）

(In the formula, d represents an integer of 1 to 10, and (CH ₂ ) _d is a substituent on the benzene ring.)

（式中、ｅ、ｆ、ｇは、それぞれ、１〜１０の整数を表す。）

(In the formula, e, f and g each represent 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 (1-Ra), the above formula (1 -Rb), more preferably a para-phenylene-methylene group (a group represented by the formula (1-Ra) where e = 1), a meta-phenylene-methylene group (f = 1). Group represented by formula (1-Rb), para-phenylene-ethylene group (group represented by formula (1-Ra) where e = 2), meta-phenylene-ethylene group (f = 2). A group represented by the formula (1-Rb).

Examples of the group represented by the formula (1-V) include the following groups.

Examples of the group in which R ¹¹ , R ¹³ and R ¹⁴ are hydrogen atoms include a vinyl group, vinylmethyl group, vinylethyl group, 4-vinylphenyl group, 3-vinylphenyl group, (4-vinylphenyl) methyl group, 2- ( 4-vinylphenyl) ethyl group, (3-vinylphenyl) methyl group, 2- (3-vinylphenyl) ethyl group and the like can be mentioned.

Examples of the group in which R ¹¹ is a methyl group and R ¹³ and R ¹⁴ are hydrogen atoms include an isopropenyl group, a methallyl group, a 4-isopropenylphenyl group, a 3-isopropenylphenyl group, and (4-isopropenylphenyl) methyl. Group, 2- (4-isopropenylphenyl) ethyl group, (3-isopropenylphenyl) methyl group, 2- (3-isopropenylphenyl) ethyl group and the like.

Examples of the group in which R ¹¹ is a vinyl group and R ¹³ and R ¹⁴ are hydrogen atoms include a 1-methylene-2-propenyl group and a 2-methylene-3-butenyl group.

Examples of groups in which R ¹¹ is a phenyl group and R ¹³ and R ¹⁴ are hydrogen atoms include 4- (1-phenylvinyl) phenyl group, 3- (1-phenylvinyl) phenyl group, and 2- (1-phenylvinyl). ) A phenyl group can be mentioned.

Examples of the group in which R ¹¹ is a hydrogen atom, R ¹³ is a methyl group, and R ¹⁴ is a hydrogen atom include 1-propenyl group, crotyl group, 4- (1-propenyl) phenyl group, 4- (1-propenyl) ) Phenylmethyl group, 2- {4- (1-propenyl) phenyl} ethyl group, 3- (1-propenyl) phenyl group, 3- (1-propenyl) phenylmethyl group, 2- {3- (1-propenyl) ) Phenyl} ethyl group and the like.

（式中、Ｒ^１１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^１２はヒドロカルビレン基を表す。） The group represented by the formula (1-V) is preferably a group represented by the following formula (1-V1).

(In the formula, R ¹¹ represents a hydrogen atom or a hydrocarbyl group, n is 0 or 1, and R ¹² represents a hydrocarbylene group.)

The group represented by the formula (1-V1) is preferably a group in which R ¹¹ is a hydrogen atom, such as vinyl group, 4-vinylphenyl group, 3-vinylphenyl group, (4-vinylphenyl) methyl group, 2 -(4-vinylphenyl) ethyl group, (3-vinylphenyl) methyl group, 2- (3-vinylphenyl) ethyl group; R ¹¹ is a methyl group, such as 4-isopropenylphenyl group, 3-iso A propenylphenyl group, a (4-isopropenylphenyl) methyl group, a 2- (4-isopropenylphenyl) ethyl group, a (3-isopropenylphenyl) methyl group, a 2- (3-isopropenylphenyl) ethyl group; R ¹¹ As a group wherein is a vinyl group, 1-methylene-2-propenyl group, 2-methylene-3-butenyl group; as a group where R ¹¹ is a phenyl group, 4- (1- Phenylvinyl) phenyl group.

The group represented by the formula (1-V1) is more preferably a vinyl group.

S ¹ in the formula (1) represents a substituted silyl group.

Examples of the substituted silyl group represented by S ¹ include a silyl group in which a hydrogen atom bonded to a silicon atom is substituted with a substituent such as an optionally substituted hydrocarbyl group, hydrocarbyloxy group, or substituted amino group. be able to. The substituents bonded to the silicon atom may be the same or different.

（式中、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。） The substituted silyl group represented by S ¹ is preferably a group represented by the following formula (1-S).

(Wherein X ¹ , X ² and X ³ each independently represents 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.)

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^１５及びＲ^１６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^１５とＲ^１６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^１５とＲ^１６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 ¹⁵ and R ¹⁶ has a hydrocarbyl group, a trihydrocarbylsilyl group, or R ¹⁵ and R ¹⁶ bonded to each other, and has a nitrogen atom and / or an oxygen atom as a hetero atom. The hydrocarbylene group which may be used, or R ¹⁵ and R ¹⁶ are one group and represent a group bonded to the nitrogen atom by a double bond.)

Examples of the hydrocarbyl group of R ¹⁵ and R ¹⁶ 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 ¹⁵ and R ¹⁶ is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.

The hydrocarbyl group of R ¹⁵ and R ¹⁶ is preferably an alkyl group, more preferably a linear alkyl group.

Examples of the trihydrocarbylsilyl group of R ¹⁵ and R ¹⁶ include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group.

The trihydrocarbylsilyl group of R ¹⁵ and R ¹⁶ 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 ¹⁵ and R ¹⁶ 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 ¹⁵ and R ¹⁶ 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 ¹⁵ and R ¹⁶ are bonded as a hetero atom is preferably a hydrocarbylene group, more preferably an alkylene group, A polymethylene group is preferred.

One group in which R ¹⁵ and R ¹⁶ are bonded to the nitrogen atom with a double bond is an ethylidene group, a propylidene group, a butylidene group, a 1-methylethylidene group, a 1-methylpropylidene group, or 1,3-dimethylbutylidene. And hydrocarbylidene groups such as groups.

The number of carbon atoms of one group in which R ¹⁵ and R ¹⁶ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 6.

R ¹⁵ and R ¹⁶ are preferably an alkyl group, a trialkylsilyl group, an alkylene group in which R ¹⁵ and R ¹⁶ 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. 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-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.

In formula (1-S), at least one of X ¹ , X ² and X ³ is a substituted amino group, preferably two or more of X ¹ , X ² and X ³ are substituted amino groups, and more Preferably, ^{two of} X ¹ , X ² and X ³ are substituted amino groups.

As the compound represented by the formula (1), V ¹ is a group represented by the formula (1-V1), S ¹ is a group represented by the formula (1-S), and the formula (1- Examples of the compound in which R ^{11 in} V1) is a hydrogen atom and ^one of X ¹ , X ² and X ³ in formula (1-S) is a dialkylamino group include the following compounds.

Compound in which n in formula (1-V1) 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 n in formula (1-V1) 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.

As the compound represented by the formula (1), V ¹ is a group represented by the formula (1-V1), S ¹ is a group represented by the formula (1-S), and the formula (1- Examples of the compound in which R ^{11 in} V1) is a hydrogen atom and ^two of X ¹ , X ² and X ³ in formula (1-S) are dialkylamino groups include the following compounds.

Compound in which n in formula (1-V1) 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 n in formula (1-V1) 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.

As the compound represented by the formula (1), V ¹ is a group represented by the formula (1-V1), S ¹ is a group represented by the formula (1-S), and the formula (1- Examples of the compound in which R ^{11 in} V1) is a methyl group and ^two of X ¹ , X ² and X ³ in formula (1-S) are dialkylamino groups include the following compounds.

Compound in which n in formula (1-V1) 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.

As the compound represented by the formula (1), V ¹ is a group represented by the formula (1-V1), S ¹ is a group represented by the formula (1-S), and the formula (1- Examples of the compound in which R ^{11 in} V1) is a vinyl group and ^two of X ¹ , X ² and X ^{3 in} the formula (1-S) are dialkylamino groups include the following compounds.

Compound in which n in formula (1-V1) 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.

As the compound represented by the formula (1), V ¹ is a group represented by the formula (1-V1), S ¹ is a group represented by the formula (1-S), and the formula (1- Examples of the compound in which R ^{11 in} V1) is a phenyl group and ^two of X ¹ , X ² and X ^{3 in} the formula (1-S) are dialkylamino groups include the following compounds.

Compound in which n in formula (1-V1) is 1:
1- (4-bis (dimethylamino) methylsilyl) -1-phenylethylene,
1- (4-bis (diethylamino) methylsilyl) -1-phenylethylene,
1- (4-bis (di-n-propylamino) methylsilyl) -1-phenylethylene,
1- (4-bis (di-n-butylamino) methylsilyl) -1-phenylethylene,
1- (4-bis (dimethylamino) ethylsilyl) -1-phenylethylene,
1- (4-bis (diethylamino) ethylsilyl) -1-phenylethylene,
1- (4-bis (di-n-propylamino) ethylsilyl) -1-phenylethylene,
1- (4-Bis (di-n-butylamino) ethylsilyl) -1-phenylethylene.

As the compound represented by the formula (1), V ¹ is a group represented by the formula (1-V1), S ¹ is a group represented by the formula (1-S), and the formula (1- Examples of the compound in which R ^{11 in} V1) is a hydrogen atom and ^three of X ¹ , X ² and X ³ in formula (1-S) are dialkylamino groups include the following compounds.

Compound in which n in formula (1-V1) is 0:
Tris (dimethylamino) vinylsilane,
Tris (diethylamino) vinylsilane,
Tris (di-n-propylamino) vinylsilane,
Tris (di-n-butylamino) vinylsilane.

Compound in which n in formula (1-V1) 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.

As the compound represented by the formula (1), V ¹ is a group represented by the formula (1-V1), S ¹ is a group represented by the formula (1-S), and the formula (1- Examples of the compound in which R ^{11 in} V1) is a methyl group and ^three of X ¹ , X ² and X ³ in formula (1-S) are dialkylamino groups include the following compounds.

Compound in which n in formula (1-V1) 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.

As the compound represented by the formula (1), V ¹ is a group represented by the formula (1-V1), S ¹ is a group represented by the formula (1-S), and the formula (1- Examples of the compound in which R ^{11 in} V1) is a vinyl group and ^three of X ¹ , X ² and X ^{3 in} the formula (1-S) are dialkylamino groups include the following compounds.

Compound in which n in formula (1-V1) 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.

As the compound represented by the formula (1), V ¹ is a group represented by the formula (1-V1), S ¹ is a group represented by the formula (1-S), and the formula (1- Examples of the compound in which R ^{11 in} V1) is a phenyl group and ^three of X ¹ , X ² and X ³ in formula (1-S) are dialkylamino groups include the following compounds.

Compound in which n in formula (1-V1) is 1:
1- (4-tris (dimethylamino) silyl) -1-phenylethylene,
1- (4-tris (diethylamino) silyl) -1-phenylethylene,
1- (4-Tris (di-n-propylamino) methylsilyl) -1-phenylethylene, 1- (4-tris (di-n-butylamino) methylsilyl) -1-phenylethylene.

The compound represented by the formula (1) is preferably a compound in which V ¹ is a group represented by the formula (1-V1) and S ¹ is a group represented by the formula (1-S). More preferably, a compound in which two of X ¹ , X ² and X ^{3 in} the formula (1-S) are dialkylamino groups, and more preferably, R ¹¹ in the formula (1-V1) is It is a compound which is a hydrogen atom and n in the formula (1-V1) is 0. Particularly preferred is a compound wherein the remaining ^one of X ¹ , X ² and X ³ is an alkyl group or an alkoxyalkyl group. Most 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.

V ² in the formula (2), the polymerizable carbon - represents a hydrocarbyl group having a carbon-carbon double bond.

V ² is preferably a group represented by the following formula (2-V).

（式中、ｍは０又は１であり、Ｒ^２１、Ｒ^２３及びＲ^２４は、それぞれ独立に水素原子又はヒドロカルビル基を表し、Ｒ^２２はヒドロカルビレン基を表す。）

(In the formula, m is 0 or 1, R ²¹ , R ²³ and R ²⁴ each independently represent a hydrogen atom or a hydrocarbyl group, and R ²² represents a hydrocarbylene group.)

In the formula (2-V), m represents 0 or 1.

Examples of the hydrocarbyl group of R ²¹ , R ²³ and R ²⁴ include an alkyl group, an alkenyl group and an aryl 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. Examples of the aryl group include a phenyl group, a methylphenyl group, and an ethylphenyl group, and a phenyl group is preferable.

R ²¹ , R ²³ and R ²⁴ are preferably a hydrogen atom, a methyl group, a vinyl group, or a phenyl group, and more preferably a hydrogen atom.

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. More preferred are a para-phenylene group and a meta-phenylene group.

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. .
Examples of a group and arylene group and an alkylene group is bonded, the carbon atom to which R ²¹ of formula (2-V) is attached, it is preferable that the carbon atoms of the arylene group in the group is attached.

In a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group (for example, a group represented by the following formula (2-R))), the position of a carbon atom on the benzene ring from which a hydrogen atom is removed and Depending on the position of the carbon atom on the benzene ring to which the alkylene group is bonded, a para-phenylene-alkylene group (for example, a group represented by the following formula (2-Ra)), a meta-phenylene-alkylene group (for example, A group represented by the following formula (2-Rb)), and an ortho-phenylene-alkylene group (for example, a group represented by the following formula (2-Rc)).

（式中、ｈは１〜１０の整数を表し、（ＣＨ_２）_ｈはベンゼン環上の置換基である。）

(In the formula, h represents an integer of 1 to 10, and (CH ₂ ) _h is a substituent on the benzene ring.)

（式中、ｉ、ｊ、ｋは、それぞれ、１〜１０の整数を表す。）

(Wherein, i, j and k each represent an integer of 1 to 10)

H in formula (2-R), i in formula (2-Ra), j in formula (2-Rb), and k in formula (2-Rc) are preferably 1 to 5, more preferably 1 to 5. 2, more preferably 1.

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 (2-Ra) or the above formula (2 -Rb), more preferably a para-phenylene-methylene group (a group represented by the formula (2-Ra) where i = 1), a meta-phenylene-methylene group (j = 1). A group represented by the formula (2-Rb), a para-phenylene-ethylene group (a group represented by the formula (2-Ra) where i = 2), a meta-phenylene-ethylene group (j = 2). Particularly preferably a para-phenylene-methylene group (a group represented by the formula (2-Ra) where i = 1), meta-phenylene- A methylene group (a group represented by the formula (2-Rb) where j = 1).

Examples of the group represented by the formula (2-V) include the following groups.

Examples of the group in which R ²¹ , R ²³ and R ²⁴ are hydrogen atoms include vinyl group, vinylmethyl group, vinylethyl group, 4-vinylphenyl group, 3-vinylphenyl group, (4-vinylphenyl) methyl group, 2- ( 4-vinylphenyl) ethyl group, (3-vinylphenyl) methyl group, 2- (3-vinylphenyl) ethyl group and the like can be mentioned.

Examples of the group in which R ²¹ is a methyl group and R ²³ and R ²⁴ are hydrogen atoms include an isopropenyl group, a methallyl group, a 4-isopropenylphenyl group, a 3-isopropenylphenyl group, and (4-isopropenylphenyl) methyl. Group, 2- (4-isopropenylphenyl) ethyl group, (3-isopropenylphenyl) methyl group, 2- (3-isopropenylphenyl) ethyl group and the like.

Examples of the group in which R ²¹ is a vinyl group and R ²³ and R ²⁴ are hydrogen atoms include a 1-methylene-2-propenyl group and a 2-methylene-3-butenyl group.

Examples of the group in which R ²¹ is a phenyl group and R ²³ and R ²⁴ are hydrogen atoms include 4- (1-phenylvinyl) phenyl group, 3- (1-phenylvinyl) phenyl group, 2- (1-phenylvinyl) ) A phenyl group can be mentioned.

Examples of the group in which R ²¹ is a hydrogen atom, R ²³ is a methyl group, and R ²⁴ is a hydrogen atom include 1-propenyl group, crotyl group, 4- (1-propenyl) phenyl group, 4- (1-propenyl) ) Phenylmethyl group, 2- {4- (1-propenyl) phenyl} ethyl group, 3- (1-propenyl) phenyl group, 3- (1-propenyl) phenylmethyl group, 2- {3- (1-propenyl) ) Phenyl} ethyl group and the like.

（式中、Ｒ^２１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^２２はヒドロカルビレン基を表す。） The group represented by the formula (2-V) is preferably a group represented by the following formula (2-V1).

(Wherein R ²¹ represents a hydrogen atom or a hydrocarbyl group, m is 0 or 1, and R ²² represents a hydrocarbylene group.)

The group represented by the formula (2-V1) is preferably a group in which R ²¹ is a hydrogen atom, such as vinyl group, 4-vinylphenyl group, 3-vinylphenyl group, (4-vinylphenyl) methyl group, 2 -(4-vinylphenyl) ethyl group, (3-vinylphenyl) methyl group, 2- (3-vinylphenyl) ethyl group; R ²¹ is a methyl group, such as 4-isopropenylphenyl group, 3-iso A propenylphenyl group, a (4-isopropenylphenyl) methyl group, a 2- (4-isopropenylphenyl) ethyl group, a (3-isopropenylphenyl) methyl group, a 2- (3-isopropenylphenyl) ethyl group; R ²¹ As a group in which is a vinyl group, a 1-methylene-2-propenyl group, a 2-methylene-3-butenyl group; a group in which R ²¹ is a phenyl group as 4- (1- Phenylvinyl) phenyl group.

The group represented by the formula (2-V1) is more preferably a vinyl group, (4-vinylphenyl) ethyl group or (3-vinylphenyl) ethyl group in which R ²¹ is a hydrogen atom.

In formula (2), A ² represents a substituted amino group or a nitrogen-containing heterocyclic group.

（式中、Ｒ^２５及びＲ^２６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^２５とＲ^２６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^２５とＲ^２６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 ² is preferably a group represented by the following formula (2-A).

(In the formula, each of R ²⁵ and R ²⁶ has a hydrocarbyl group, a trihydrocarbyl silyl group, or R ²⁵ and R ²⁶ 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 ²⁵ and R ²⁶ are one group and represent a group bonded to the nitrogen atom with a double bond.)

Examples of the hydrocarbyl group for R ²⁵ and R ²⁶ 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 ²⁵ and R ²⁶ is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.

The hydrocarbyl group for R ²⁵ and R ²⁶ is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and still more preferably a linear alkyl group.

Examples of the trihydrocarbylsilyl group of R ²⁵ and R ²⁶ include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group.

The trihydrocarbylsilyl group of R ²⁵ and R ²⁶ 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 ²⁵ and R ²⁶ 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 ²⁵ and R ²⁶ 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 an oxygen atom to which R ²⁵ and R ²⁶ are bonded as a hetero atom is preferably a hydrocarbylene group, more preferably an alkylene group, A polymethylene group is preferred.

One group in which R ²⁵ and R ²⁶ are bonded to the nitrogen atom with a double bond is an ethylidene group, a propylidene group, a butylidene group, a 1-methylethylidene group, a 1-methylpropylidene group, or 1,3-dimethylbutylidene. And hydrocarbylidene groups such as groups.

The number of carbon atoms in one group in which R ²⁵ and R ²⁶ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 6.

R ²⁵ and R ²⁶ are preferably a hydrocarbyl group, a trihydrocarbyl silyl group, or a hydrocarbylene group to which R ²⁵ and R ²⁶ are bonded.

Examples of the group represented by the formula (2-A) 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.

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-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-A) is preferably a group in which R ²⁵ and R ²⁶ are hydrocarbyl groups, a group in which R ²⁵ and R ²⁶ are trihydrocarbylsilyl groups, and R ²⁵ and R ²⁶ are bonded. Group which is a hydrocarbylene group. More preferably, R ²⁵ and R ²⁶ are a group that is a linear alkyl group, R ²⁵ and R ²⁶ are a group that is a trialkylsilyl group, and a group that is a polymethylene group to which R ²⁵ and R ²⁶ are bonded.

The group represented by the formula (2-A) 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 represented by A ² 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 represented by A ² includes a group having only a nitrogen atom as a hetero atom constituting a ring, a group having a nitrogen atom and an oxygen atom as a hetero atom constituting a ring, and a hetero atom constituting a ring. Examples thereof include a group having a nitrogen 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 represented by A ² 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 represented by A ² 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 a hetero atom constituting the ring. Examples thereof include a group having a nitrogen 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 aromatic heterocyclic group for A ² is preferably a nitrogen-containing aromatic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring, more preferably a group having an imidazole ring or a pyridine ring. And a group having a quinoline ring, more preferably a group having a pyridine ring.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a hydrogen atom, and m is 0. As the compounds wherein A ² is a substituted amino group, the following compounds can be exemplified.

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

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a hydrogen atom, and m is 1. , R ²² is a phenylene group, and A ² is a substituted amino group, the following compounds can be exemplified.

4-N, N-dimethylaminostyrene,
4-N, N-diethylaminostyrene,
4-N, N-di-n-propylaminostyrene,
4-N, N-di-n-butylaminostyrene,
4-N, N-diallylaminostyrene,
4-N, N-bis (trimethylsilyl) aminostyrene,
4-N, N-bis (tert-butyldimethylsilyl) aminostyrene,
4- (1-aziridinyl) styrene,
4- (1-pyrrolidinyl) styrene,
4- (1-piperidinyl) styrene,
4- (1-hexamethyleneimino) styrene,
3-N, N-dimethylaminostyrene,
3-N, N-diethylaminostyrene,
3-N, N-di-n-propylaminostyrene,
3-N, N-di-n-butylaminostyrene,
3-N, N-diallylaminostyrene,
3-N, N-bis (trimethylsilyl) aminostyrene,
3-N, N-bis (tert-butyldimethylsilyl) aminostyrene,
3- (1-aziridinyl) styrene,
3- (1-pyrrolidinyl) styrene,
3- (1-piperidinyl) styrene,
3- (1-Hexamethyleneimino) styrene.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a hydrogen atom, and m is 1. , R ²² is a group represented by the formula (2-Ra), and A ² is a substituted amino group, the following compounds can be exemplified.

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

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

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a hydrogen atom, and m is 1. , R ²² is a group represented by the formula (2-Rb), and A ² is a substituted amino group, the following compounds can be exemplified.

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

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

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a methyl group, and m is 0. As the compounds wherein A ² is a substituted amino group, the following compounds can be exemplified.

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), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a methyl group, and m is 1. , R ²² is a phenylene group, and A ² is a substituted amino group, the following compounds can be exemplified.

4-N, N-dimethylaminoisopropenylbenzene,
4-N, N-diethylaminoisopropenylbenzene,
4-N, N-di-n-propylaminoisopropenylbenzene,
4-N, N-di-n-butylaminoisopropenylbenzene,
4-N, N-diallylaminoisopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminoisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminoisopropenylbenzene, 4- (1-aziridinyl) isopropenylbenzene,
4- (1-pyrrolidinyl) isopropenylbenzene,
4- (1-piperidinyl) isopropenylbenzene,
4- (1-hexamethyleneimino) isopropenylbenzene,
3-N, N-dimethylaminoisopropenylbenzene,
3-N, N-diethylaminoisopropenylbenzene,
3-N, N-di-n-propylaminoisopropenylbenzene,
3-N, N-di-n-butylaminoisopropenylbenzene,
3-N, N-diallylaminoisopropenylbenzene,
3-N, N-bis (trimethylsilyl) aminoisopropenylbenzene,
3-N, N-bis (tert-butyldimethylsilyl) aminoisopropenylbenzene, 3- (1-aziridinyl) isopropenylbenzene,
3- (1-pyrrolidinyl) isopropenylbenzene,
3- (1-piperidinyl) isopropenylbenzene,
3- (1-Hexamethyleneimino) isopropenylbenzene.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a methyl group, and m is 1. , R ²² is a group represented by the formula (2-Ra), and A ² is a substituted amino group, the following compounds can be exemplified.

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

Compound in which i of formula (2-Ra) is 2:
4-N, N-dimethylaminoethylisopropenylbenzene,
4-N, N-diethylaminoethylisopropenylbenzene,
4-N, N-di-n-propylaminoethylisopropenylbenzene,
4-N, N-di-n-butylaminoethylisopropenylbenzene,
4-N, N-diallylaminoethyl isopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminoethylisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminoethylisopropenylbenzene,
4- (1-aziridinyl) ethyl isopropenylbenzene,
4- (1-pyrrolidinyl) ethyl isopropenylbenzene,
4- (1-piperidinyl) ethyl isopropenylbenzene,
4- (1-Hexamethyleneimino) ethyl isopropenylbenzene.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a methyl group, and m is 1. , R ²² is a group represented by the formula (2-Rb), and A ² is a substituted amino group, the following compounds can be exemplified.

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

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

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a vinyl group, and m is 0. As the compounds wherein A ² is a substituted amino group, the following compounds can be exemplified.

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.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a vinyl group, and m is 1. , R ²² is an alkylene group, and A ² is a substituted amino group, the following compounds can be exemplified.

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 a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a phenyl group, and m is 1. , R ²² is a phenylene group, and A ² is a substituted amino group, the following compounds can be exemplified.

1- (4-N, N-dimethylaminophenyl) -1-phenylethylene,
1- (4-N, N-diethylaminophenyl) -1-phenylethylene,
1- (4-N, N-dipropylaminophenyl) -1-phenylethylene,
1- (4-N, N-diisopropylaminophenyl) -1-phenylethylene,
1- (4-N, N-dibutylaminophenyl) -1-phenylethylene,
1- (4-N, N-diisobutylaminophenyl) -1-phenylethylene,
1- (4-N, N-di (tert-butyl) aminophenyl) -1-phenylethylene, 1- (4-N, N-diphenylaminophenyl) -1-phenylethylene,
1- (4- (1-aziridinyl) phenyl) -1-phenylethylene,
1- (4- (1-pyrrolidinyl) phenyl) -1-phenylethylene,
1- (4- (1-piperidinyl) phenyl) -1-phenylethylene,
1- (4-hexamethyleneiminophenyl) -1-phenylethylene,
1- (4-morpholinophenyl) -1-phenylethylene,
1- (4- (N, N-bis (trimethylsilyl) amino) phenyl) -1-phenylethylene,
1- (4- (N, N-bis (tert-butyldimethylsilyl) amino) phenyl) -1-phenylethylene,
1- (4- (N, N-bis (triisopropylsilyl) amino) phenyl) -1-phenylethylene,
1- (3-N, N-dimethylaminophenyl) -1-phenylethylene,
1- (3-N, N-diethylaminophenyl) -1-phenylethylene,
1- (3-N, N-dipropylaminophenyl) -1-phenylethylene,
1- (3-N, N-diisopropylaminophenyl) -1-phenylethylene,
1- (3-N, N-dibutylaminophenyl) -1-phenylethylene,
1- (3-N, N-diisobutylaminophenyl) -1-phenylethylene,
1- (3-N, N-di (tert-butyl) aminophenyl) -1-phenylethylene, 1- (3-N, N-diphenylaminophenyl) -1-phenylethylene,
1- (3- (1-aziridinyl) phenyl) -1-phenylethylene,
1- (3- (1-pyrrolidinyl) phenyl) -1-phenylethylene,
1- (3- (1-piperidinyl) phenyl) -1-phenylethylene,
1- (3-hexamethyleneiminophenyl) -1-phenylethylene,
1- (3-morpholinophenyl) -1-phenylethylene,
1- (3- (N, N-bis (trimethylsilyl) amino) phenyl) -1-phenylethylene,
1- (3- (N, N-bis (tert-butyldimethylsilyl) aminophenyl) -1-phenylethylene,
1- (3- (N, N-bis (triisopropylsilyl) amino) phenyl) -1-phenylethylene.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a phenyl group, and m is 1. , R ²² is a group represented by the formula (2-Ra), and A ² is a substituted amino group, the following compounds can be exemplified.

Compound in which i of formula (2-Ra) is 1:
1- (4-N, N-dimethylaminomethylphenyl) -1-phenylethylene,
1- (4-N, N-diethylaminomethylphenyl) -1-phenylethylene,
1- (4-N, N-dipropylaminomethylphenyl) -1-phenylethylene,
1- (4-N, N-diisopropylaminomethylphenyl) -1-phenylethylene,
1- (4-N, N-dibutylaminomethylphenyl) -1-phenylethylene,
1- (4-N, N-diisobutylaminomethylphenyl) -1-phenylethylene,
1- (4-N, N-di (tert-butyl) aminomethylphenyl) -1-phenylethylene,
1- (4-N, N-diphenylaminomethylphenyl) -1-phenylethylene,
1- (4- (1-aziridinylmethyl) phenyl) -1-phenylethylene,
1- (4- (1-pyrrolidinylmethyl) phenyl) -1-phenylethylene,
1- (4- (1-piperidinylmethyl) phenyl) -1-phenylethylene,
1- (4-hexamethyleneiminomethylphenyl) -1-phenylethylene,
1- (4-morpholinomethylphenyl) -1-phenylethylene,
1- (4- (N, N-bis (trimethylsilyl) aminomethyl) phenyl) -1-phenylethylene,
1- (4- (N, N-bis (tert-butyldimethylsilyl) amino) methylphenyl) -1-phenylethylene,
1- (4- (N, N-bis (triisopropylsilyl) amino) methylphenyl) -1-phenylethylene.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a phenyl group, and m is 1. , R ²² is a group represented by the formula (2-Rb), and A ² is a substituted amino group, the following compounds can be exemplified.

Compound in which j in formula (2-Rb) is 1:
1- (3-N, N-dimethylaminomethylphenyl) -1-phenylethylene,
1- (3-N, N-diethylaminomethylphenyl) -1-phenylethylene,
1- (3-N, N-dipropylaminomethylphenyl) -1-phenylethylene,
1- (3-N, N-diisopropylaminomethylphenyl) -1-phenylethylene,
1- (3-N, N-dibutylaminomethylphenyl) -1-phenylethylene,
1- (3-N, N-diisobutylaminomethylphenyl) -1-phenylethylene,
1- (3-N, N-di (tert-butyl) aminomethylphenyl) -1-phenylethylene,
1- (3-N, N-diphenylaminomethylphenyl) -1-phenylethylene,
1- (3- (1-aziridinylmethyl) phenyl) -1-phenylethylene,
1- (3- (1-pyrrolidinylmethyl) phenyl) -1-phenylethylene,
1- (3- (1-piperidinylmethyl) phenyl) -1-phenylethylene,
1- (3-hexamethyleneiminomethylphenyl) -1-phenylethylene,
1- (3-morpholinomethylphenyl) -1-phenylethylene,
1- (3- (N, N-bis (trimethylsilyl) aminomethyl) phenyl) -1-phenylethylene,
1- (3- (N, N-bis (tert-butyldimethylsilyl) amino) methylphenyl) -1-phenylethylene,
1- (3- (N, N-bis (triisopropylsilyl) amino) methylphenyl) -1-phenylethylene.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a hydrogen atom, and m is 0. As the compounds wherein A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

N-methyl-3-vinylpyrrolidine,
N-methyl-4-vinylpiperidine,
N-methyl-3-vinylhexamethyleneimine,
N-methyl-4-vinylhexamethyleneimine.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a hydrogen atom, and m is 1. , R ²² is a phenylene group and A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

N-methyl-3- (4-vinylphenyl) pyrrolidine,
N-methyl-4- (4-vinylphenyl) piperidine,
N-methyl-3- (4-vinylphenyl) hexamethyleneimine,
N-methyl-4- (4-vinylphenyl) hexamethyleneimine,
N-methyl-3- (3-vinylphenyl) pyrrolidine,
N-methyl-4- (3-vinylphenyl) piperidine,
N-methyl-3- (3-vinylphenyl) hexamethyleneimine,
N-methyl-4- (3-vinylphenyl) hexamethyleneimine.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a hydrogen atom, and m is 1. , R ²² is a group represented by the formula (2-Ra), and A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

Compound in which i of formula (2-Ra) is 1:
N-methyl-3- (4-vinylphenylmethyl) pyrrolidine,
N-methyl-4- (4-vinylphenylmethyl) piperidine,
N-methyl-3- (4-vinylphenylmethyl) hexamethyleneimine,
N-methyl-4- (4-vinylphenylmethyl) hexamethyleneimine.

Compound in which i of formula (2-Ra) is 2:
N-methyl-3- (4-vinylphenylethyl) pyrrolidine,
N-methyl-4- (4-vinylphenylethyl) piperidine,
N-methyl-3- (4-vinylphenylethyl) hexamethyleneimine,
N-methyl-4- (4-vinylphenylethyl) hexamethyleneimine.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a hydrogen atom, and m is 1. , R ²² is a group represented by the formula (2-Rb), and A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

Compound in which j in formula (2-Rb) is 1:
N-methyl-3- (3-vinylphenylmethyl) pyrrolidine,
N-methyl-4- (3-vinylphenylmethyl) piperidine,
N-methyl-3- (3-vinylphenylmethyl) hexamethyleneimine,
N-methyl-4- (3-vinylphenylmethyl) hexamethyleneimine.

Compound in which j in formula (2-Rb) is 2:
N-methyl-3- (3-vinylphenylethyl) pyrrolidine,
N-methyl-4- (3-vinylphenylethyl) piperidine,
N-methyl-3- (3-vinylphenylethyl) hexamethyleneimine,
N-methyl-4- (3-vinylphenylethyl) hexamethyleneimine.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a methyl group, and m is 0. As the compounds wherein A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

N-methyl-3-isopropenylpyrrolidine,
N-methyl-4-isopropenylpiperidine,
N-methyl-3-isopropenylhexamethyleneimine,
N-methyl-4-isopropenylhexamethyleneimine.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a methyl group, and m is 1. , R ²² is a phenylene group and A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

N-methyl-3- (4-isopropenylphenyl) pyrrolidine,
N-methyl-4- (4-isopropenylphenyl) piperidine,
N-methyl-3- (4-isopropenylphenyl) hexamethyleneimine,
N-methyl-4- (4-isopropenylphenyl) hexamethyleneimine.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a methyl group, and m is 1. , R ²² is a group represented by the formula (2-Ra), and A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

Compound in which i of formula (2-Ra) is 1:
N-methyl-3- (4-isopropenylphenylmethyl) pyrrolidine,
N-methyl-4- (4-isopropenylphenylmethyl) piperidine,
N-methyl-3- (4-isopropenylphenylmethyl) hexamethyleneimine,
N-methyl-4- (4-isopropenylphenylmethyl) hexamethyleneimine.

Compound in which i of formula (2-Ra) is 2:
N-methyl-3- (4-isopropenylphenylethyl) pyrrolidine,
N-methyl-4- (4-isopropenylphenylethyl) piperidine,
N-methyl-3- (4-isopropenylphenylethyl) hexamethyleneimine,
N-methyl-4- (4-isopropenylphenylethyl) hexamethyleneimine.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a vinyl group, and m is 0. As the compounds wherein A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

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

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a vinyl group, and m is 1. , R ²² is an alkylene group, and A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

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

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a phenyl group, and m is 1. , R ²² is a phenylene group and A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

1- (4-N-methyl-3-pyrrolidinophenyl) -1-phenylethylene,
1- (4-N-methyl-3-piperidinophenyl) -1-phenylethylene,
1- (4-N-methyl-4-piperidinophenyl) -1-phenylethylene,
1- (4-N-methyl-3-hexamethyleneiminophenyl) -1-phenylethylene,
1- (4-N-methyl-4-hexamethyleneiminophenyl) -1-phenylethylene,
1- (3-N-methyl-3-pyrrolidinophenyl) -1-phenylethylene,
1- (3-N-methyl-3-piperidinophenyl) -1-phenylethylene,
1- (3-N-methyl-4-piperidinophenyl) -1-phenylethylene,
1- (3-N-methyl-3-hexamethyleneiminophenyl) -1-phenylethylene,
1- (3-N-methyl-4-hexamethyleneiminophenyl) -1-phenylethylene.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a phenyl group, and m is 1. , R ²² is a group represented by the formula (2-Ra), and A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

Compound in which i of formula (2-Ra) is 1:
1- (4-N-methyl-3-pyrrolidinomethylphenyl) -1-phenylethylene,
1- (4-N-methyl-3-piperidinomethylphenyl) -1-phenylethylene,
1- (4-N-methyl-4-piperidinomethylphenyl) -1-phenylethylene,
1- (4-N-methyl-3-hexamethyleneiminomethylphenyl) -1-phenylethylene.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a phenyl group, and m is 1. , R ²² is a group represented by the formula (2-Rb), and A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

Compound in which j in formula (2-Rb) is 1:
1- (3-N, N-dimethylaminomethylphenyl) -1-phenylethylene,
1- (3-N, N-diethylaminomethylphenyl) -1-phenylethylene,
1- (3-N, N-dipropylaminomethylphenyl) -1-phenylethylene,
1- (3-N, N-diisopropylaminomethylphenyl) -1-phenylethylene.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a hydrogen atom, and m is 0. As the compounds wherein A ² is a nitrogen-containing aromatic heterocyclic group, the following compounds can be exemplified.

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.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a methyl group, and m is 0. As the compounds wherein A ² is a nitrogen-containing aromatic heterocyclic group, the following compounds can be exemplified.

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.

As a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a vinyl group, and m is 0. As the compounds wherein A ² is a nitrogen-containing aromatic heterocyclic group, the following compounds can be exemplified.

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 a compound represented by the formula (2), V ² is a group represented by the formula (2-V1), R ²¹ in the formula (2-V1) is a vinyl group, and m is 1. , R ²² is an alkylene group, and A ² is a nitrogen-containing aromatic heterocyclic group, the following compounds can be exemplified.

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.

The compound represented by the formula (2) is preferably a compound in which the group represented by V ² is represented by the formula (2-V1), and R ²¹ in the formula (2-V1) is a hydrogen atom. is there.
More preferably, R ²¹ is a hydrogen atom, m is 1, R ²² is a phenylene group, and A ² is a substituted amino group represented by the formula (2-A); R ²¹ is hydrogen an atom, m is ^{1, R 22} is a ^group represented by the formula (2-R), compound ^{a 2} is a substituted amino group represented by the formula ^{(2-a); R 21} is It is a compound that is a hydrogen atom, m is 0, and A ² is a nitrogen-containing aromatic heterocyclic group.
More preferably, R ²¹ is a hydrogen atom, m is 1, R ²² is a para-phenylene group or a meta-phenylene group, and A ² is R ²⁵ and R ^{26 in the} formula (2-A). A compound which is a bonded polymethylene group; R ²¹ is a hydrogen atom, m is 1, R ²² is a group represented by the formula (2-Ra) or (2-Rb), and A ² is a group represented by the formula ( A compound in which R ²⁵ and R ^{26 in} 2-A) are bonded to each other as a polymethylene group; R ²¹ is a hydrogen atom, m is 0, and A ² is a pyridyl group.

As the compound represented by the formula (2), particularly preferably,
3- (1-pyrrolidinyl) ethylstyrene,
4- (1-pyrrolidinyl) ethylstyrene,
4-vinylpyridine,
2-vinylpyridine.

Examples of the alkoxysilane compound include a tetraalkoxysilane compound, an alkoxysilane compound having an alkyl group, an alkoxysilane compound having a halogen atom, an alkoxysilane compound having an epoxy group, an alkoxysilane compound having a mercapto group, and an alkoxysilane having a substituted amino group. Compound etc. can be mentioned.

Examples of the tetraalkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-tert-butoxysilane, tetra- (2 -Ethylhexanoxy) silane and the like.

Examples of the alkoxysilane compound having an alkyl group include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltriisobutoxysilane, methyltri-tert- Butoxysilane, methyltri- (2-ethylhexanoxy) silane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldiisobutoxysilane, dimethyldi -Tert-butoxysilane, dimethyldi- (2-ethylhexanoxy) silane, etc. can be mentioned.

Examples of the alkoxysilane compound having a halogen atom include trimethoxychlorosilane, triethoxychlorosilane, tri-n-propoxychlorosilane, triisopropoxychlorosilane, tri-n-butoxychlorosilane, triisobutoxychlorosilane, tri-tert-butoxychlorosilane, tri -(2-ethylhexanoxy) chlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, di-n-propoxydichlorosilane, diisopropoxydichlorosilane, di-n-butoxydichlorosilane, diisobutoxydichlorosilane, di-tert -Butoxydichlorosilane, di- (2-ethylhexanoxy) dichlorosilane, methoxytrichlorosilane, ethoxytrichlorosilane, trimethoxybromosilane, trieth Sibromosilane, tri-n-propoxybromosilane, triisopropoxybromosilane, tri-n-butoxybromosilane, dimethoxydibromosilane, diethoxydibromosilane, di-n-propoxydibromosilane, diisopropoxydibromosilane, di-n -Butoxydibromosilane, methoxytribromosilane, ethoxytribromosilane, trimethoxyiodosilane, triethoxyiodosilane, tri-n-propoxyiodosilane, triisopropoxyiodosilane, tri-n-butoxyiodosilane, dimethoxydiiodo Silane, diethoxydiiodosilane, di-n-propoxydiiodosilane, diisopropoxydiiodosilane, di-n-butoxydiiodosilane, methoxytriiodosilane, ethoxytriiodosila , And the like.

Examples of the alkoxysilane compound having an epoxy group include 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 4-glycidoxybutyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltriethoxysilane, 2-glycidoxyethyltripropoxysilane, 3-glycidoxypropyltripropoxysilane, 4-glycidoxybutyltripropoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropyldimethylmethyl Xysilane, 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropyldiethylmethoxysilane, 3-glycidoxypropyldiethylethoxysilane, bis (3-glycidoxypropyl) dimethoxysilane, bis (3-glycid Xylpropyl) diethoxysilane, bis (3-glycidoxypropyl) dipropoxysilane, bis (3-glycidoxypropyl) methylmethoxysilane, bis (3-glycidoxypropyl) methylethoxysilane, bis (3- Glycidoxypropyl) ethylmethoxysilane, bis (3-glycidoxypropyl) ethylethoxysilane, tris (3-glycidoxypropyl) methoxysilane, tris (3-glycidoxypropyl) ethoxysilane, tris (3- Glycidoxypropyl) dipro Xysilane, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) propyl-triethoxysilane, β- (3,4-epoxycyclohexyl) propyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) propyl-methyldimethoxysilane, β- ( 3,4-epoxycyclohexyl) pro Ru-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) propyl -Dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) propyl-dimethylethoxysilane, and the like.

Examples of the alkoxysilane compound having a mercapto group include 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 4-mercaptobutyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 4-mercaptobutyltriethoxysilane, 2-mercaptoethyltripropoxysilane, 3-mercaptopropyltripropoxysilane, 4-mercaptobutyltripropoxysilane, 2-mercaptoethylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 4- Mercaptobutylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 4-mercaptobuty It may be mentioned methyl diethoxy silane, and the like.

（式中、ｐは１〜１０の整数を表し、Ｒ^３１、Ｒ^３２及びＲ^３３は、それぞれ独立にアルキル基又はアルコキシ基を表し、Ｒ^３１、Ｒ^３２及びＲ^３３の少なくとも１つがアルコキシ基であり、Ａ^３は置換アミノ基を表す。） Examples of the alkoxysilane compound having a substituted amino group include compounds represented by the following formula (3).

(In the formula, p represents an integer of 1 to 10, R ³¹ , R ³² and R ³³ each independently represents an alkyl group or an alkoxy group, and at least one of R ³¹ , R ³² and R ³³ is an alkoxy group. And A ³ represents a substituted amino group.)

R ³¹ , R ³² , and R ³³ each represents an alkyl group or an alkoxy group.

^Examples of the alkyl group for R ³¹ , R ³² , and R ³³ 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. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group.

Examples of the alkoxy group of R ³¹ , R ³² and R ³³ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and 2-ethylhexano group. Kishi can be given. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, and further preferably a methoxy group or an ethoxy group.

At least one of R ³¹ , R ³² , and R ³³ is an alkoxy group, and in order to improve fuel efficiency, preferably at least two of R ³¹ , R ³² , and R ³³ are alkoxy groups, and more preferably In the ^formula , three of R ³¹ , R ³² and R ³³ are alkoxy groups.

（式中、Ｒ^３４及びＲ^３５は、それぞれ、水素原子、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビル基、あるいは、Ｒ^３４とＲ^３５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^３４とＲ^３５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。） In formula (3), A ³ represents a substituted amino group. The substituted amino group for A ³ is preferably a group represented by the following formula (3-A).

(Wherein R ³⁴ and R ³⁵ are each a hydrogen atom, a nitrogen atom and / or a hydrocarbyl group optionally having an oxygen atom, or R ³⁴ and R ³⁵ are bonded to form a nitrogen atom and / Alternatively, a hydrocarbylene group which may have an oxygen atom as a hetero atom, or R ³⁴ and R ³⁵ are one group and represent a group bonded to a nitrogen atom by a double bond.)

R ³⁴ and R ³⁵ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or a combination of R ³⁴ and R ³⁵ to form a nitrogen atom and / or an oxygen atom. The hydrocarbylene group which may have, or R ^<34> and R ^<35> are one group, Comprising: The group couple | bonded with a nitrogen atom with a double bond is represented.

Examples of the hydrocarbyl group of R ³⁴ and R ³⁵ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group; vinyl group, allyl group, Examples thereof include alkenyl groups such as 1-propenyl group and 1-methylethenyl group; alkynyl groups such as ethynyl group and propargyl group; aryl groups such as phenyl group, tolyl group and xylyl group; and aralkyl groups such as benzyl group.

Examples of the hydrocarbyl group having a nitrogen atom of R ³⁴ and R ³⁵ include dialkylaminoalkyl groups such as dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, diethylaminomethyl group, diethylaminoethyl group, and diethylaminopropyl group. Can do.

Examples of the hydrocarbyl group having an oxygen atom of R ³⁴ and R ³⁵ include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, and an ethoxypropyl group; a 2-oxiranyl group, 2 A monooxacycloalkyl group such as an oxetanyl group or 2-tetrahydrofuranyl group; a dioxacycloalkyl group such as a 2-dioxolanyl group; an alkyl group substituted with a monooxacycloalkyl group such as a glycidyl group or a tetrahydrofurfuryl group; A 3,4-epoxycyclohexyl group can be mentioned.

In this specification, the monooxacycloalkyl group represents a group in which one CH ₂ of the cycloalkyl group is replaced with an oxygen atom. The dioxacycloalkyl group represents a group in which _two CH ₂ of the cycloalkyl group are replaced with an oxygen atom.

The number of carbon atoms of the hydrocarbyl group which may have a nitrogen atom and / or an oxygen atom of R ³⁴ and R ³⁵ is preferably 1 to 10, and more preferably 1 to 6.

Examples of the group to which R ³⁴ and R ³⁵ are bonded include a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and a hydrocarbylene group having an oxygen atom. Examples of the hydrocarbylene group include alkylene groups such as trimethylene group, tetramethylene group, pentamethylene group, and 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 group to which R ³⁴ and R ³⁵ are bonded is preferably 2 to 20, and more preferably 2 to 12.

One group in which R ³⁴ and R ³⁵ are bonded to the nitrogen atom with a double bond is an ethylidene group, a propylidene group, a butylidene group, a 1-methylethylidene group, a 1-methylpropylidene group, or 1,3-dimethylbutylidene. A hydrocarbylidene group such as a group; 4-N, N-dimethylaminobenzylidene group and the like.

The number of carbon atoms of one group in which R ³⁴ and R ³⁵ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 12.

R ³⁴ and R ³⁵ are preferably a hydrocarbyl group, or a hydrocarbylene group in which R ³⁴ and R ³⁵ are bonded, or R ³⁴ and R ³⁵ are one group, and a nitrogen atom Is a hydrocarbylidene group which is a group bonded by a double bond, more preferably a hydrocarbyl group, and still more preferably an alkyl group. The alkyl group is preferably a methyl group or an ethyl group.

p is a number of 1 to 10, preferably 2 to 4, and more preferably 3.

As the compound represented by the formula (3), compounds in which R ³⁴ and R ³⁵ are alkyl groups,
[3- (dimethylamino) propyl] trimethoxysilane,
[3- (diethylamino) propyl] trimethoxysilane,
[3- (ethylmethylamino) propyl] trimethoxysilane,
[3- (dimethylamino) propyl] triethoxysilane,
[3- (diethylamino) propyl] triethoxysilane,
[3- (dialkylamino) propyl] trialkoxysilanes such as [3- (ethylmethylamino) propyl] triethoxysilane;

[3- (dimethylamino) propyl] methyldimethoxysilane,
[3- (diethylamino) propyl] methyldimethoxysilane,
[3- (ethylmethylamino) propyl] methyldimethoxysilane,
[3- (dimethylamino) propyl] ethyldimethoxysilane,
[3- (diethylamino) propyl] ethyldimethoxysilane,
[3- (ethylmethylamino) propyl] ethyldimethoxysilane,
[3- (dimethylamino) propyl] methyldiethoxysilane,
[3- (diethylamino) propyl] methyldiethoxysilane,
[3- (ethylmethylamino) propyl] methyldiethoxysilane,
[3- (dimethylamino) propyl] ethyldiethoxysilane,
[3- (diethylamino) propyl] ethyldiethoxysilane,
[3- (dialkylamino) propyl] alkyl dialkoxysilanes such as [3- (ethylmethylamino) propyl] ethyldiethoxysilane;

[3- (dimethylamino) propyl] dimethylmethoxysilane,
[3- (diethylamino) propyl] dimethylmethoxysilane,
[3- (dimethylamino) propyl] diethylmethoxysilane,
[3- (diethylamino) propyl] diethylmethoxysilane,
[3- (dimethylamino) propyl] dimethylethoxysilane,
[3- (diethylamino) propyl] dimethylethoxysilane,
[3- (dimethylamino) propyl] diethylethoxysilane,
[3- (Dialkylamino) propyl] dialkylalkoxysilanes such as [3- (diethylamino) propyl] diethylethoxysilane can be mentioned.

As a compound represented by Formula (3), as a compound in which R ³⁴ and R ³⁵ are alkoxyalkyl groups,
{3- [bis (methoxymethyl) amino] propyl} trimethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} trimethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} trimethoxysilane,
{3- [bis (ethoxyethyl) amino] propyl} trimethoxysilane,
{3- [bis (methoxymethyl) amino] propyl} triethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} triethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} triethoxysilane,
{3- [bis (alkoxyalkyl) amino] propyl} trialkoxysilanes such as {3- [bis (ethoxyethyl) amino] propyl} triethoxysilane;

{3- [bis (methoxymethyl) amino] propyl} methyldimethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} methyldimethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} methyldimethoxysilane,
{3- [bis (ethoxyethyl) amino] propyl} methyldimethoxysilane,
{3- [bis (methoxymethyl) amino] propyl} ethyldimethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} ethyldimethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} ethyldimethoxysilane,
{3- [bis (ethoxyethyl) amino] propyl} ethyldimethoxysilane,
{3- [bis (methoxymethyl) amino] propyl} methyldiethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} methyldiethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} methyldiethoxysilane,
{3- [bis (ethoxyethyl) amino] propyl} methyldiethoxysilane,
{3- [bis (methoxymethyl) amino] propyl} ethyldiethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} ethyldiethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} ethyldiethoxysilane,
{3- [bis (alkoxyalkyl) amino] propyl} alkyl dialkoxysilanes such as {3- [bis (ethoxyethyl) amino] propyl} ethyldiethoxysilane;

{3- [bis (methoxymethyl) amino] propyl} dimethylmethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} dimethylmethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} dimethylmethoxysilane,
{3- [bis (ethoxyethyl) amino] propyl} dimethylmethoxysilane,
{3- [bis (methoxymethyl) amino] propyl} diethylmethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} diethylmethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} diethylmethoxysilane,
{3- [bis (ethoxyethyl) amino] propyl} diethylmethoxysilane,
{3- [bis (methoxymethyl) amino] propyl} dimethylethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} dimethylethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} dimethylethoxysilane,
{3- [bis (ethoxyethyl) amino] propyl} dimethylethoxysilane,
{3- [bis (methoxymethyl) amino] propyl} diethylethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} diethylethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} diethylethoxysilane,
Mention may be made of {3- [bis (alkoxyalkyl) amino] propyl} dialkylalkoxysilanes such as {3- [bis (ethoxyethyl) amino] propyl} diethylethoxysilane.

As a compound represented by Formula (3), as a compound in which R ³⁴ and R ³⁵ are an oxiranyl group,
{3- [di (oxiranyl) amino] propyl} trimethoxysilane,
{3- [di (oxiranyl) amino] propyl} triethoxysilane,
{3- [di (oxiranyl) amino] propyl} methyldimethoxysilane,
{3- [di (oxiranyl) amino] propyl} ethyldimethoxysilane,
{3- [di (oxiranyl) amino] propyl} methyldiethoxysilane,
{3- [di (oxiranyl) amino] propyl} ethyldiethoxysilane,
{3- [di (oxiranyl) amino] propyl} dimethylmethoxysilane,
{3- [di (oxiranyl) amino] propyl} diethylmethoxysilane,
{3- [di (oxiranyl) amino] propyl} dimethylethoxysilane,
Examples include {3- [di (oxiranyl) amino] propyl} diethylethoxysilane.

As the compound represented by the formula (3), as a compound in which R ³⁴ and R ³⁵ are tetrahydrofuranyl groups,
{3- [di (tetrahydrofuranyl) amino] propyl} trimethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} triethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} methyldimethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} ethyldimethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} methyldiethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} ethyldiethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} dimethylmethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} diethylmethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} dimethylethoxysilane,
Examples include {3- [di (tetrahydrofuranyl) amino] propyl} diethylethoxysilane.

As a compound represented by Formula (3), as a compound in which R ³⁴ and R ³⁵ are glycidyl groups,
{3- [di (glycidyl) amino] propyl} trimethoxysilane,
{3- [di (glycidyl) amino] propyl} triethoxysilane,
{3- [di (glycidyl) amino] propyl} methyldimethoxysilane,
{3- [di (glycidyl) amino] propyl} ethyldimethoxysilane,
{3- [di (glycidyl) amino] propyl} methyldiethoxysilane,
{3- [di (glycidyl) amino] propyl} ethyldiethoxysilane,
{3- [di (glycidyl) amino] propyl} dimethylmethoxysilane,
{3- [di (glycidyl) amino] propyl} diethylmethoxysilane,
{3- [di (glycidyl) amino] propyl} dimethylethoxysilane,
Examples include {3- [di (glycidyl) amino] propyl} diethylethoxysilane.

As a compound represented by Formula (3), as a compound in which R ³⁴ and R ³⁵ are a tetrahydrofurfuryl group,
{3- [di (tetrahydrofurfuryl) amino] propyl} trimethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} triethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} methyldimethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} ethyldimethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} methyldiethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} ethyldiethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} dimethylmethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} diethylmethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} dimethylethoxysilane,
Examples include {3- [di (tetrahydrofurfuryl) amino] propyl} diethylethoxysilane.

As the compound represented by the formula (3), as a compound in which R ³⁴ and R ³⁵ are bonded,
3- (1-piperidinyl) propyltrimethoxysilane,
3- (1-piperidinyl) propyltriethoxysilane,
3- (1-piperidinyl) propylmethyldimethoxysilane,
3- (1-piperidinyl) propylethyldimethoxysilane,
3- (1-piperidinyl) propylmethyldiethoxysilane,
3- (1-piperidinyl) propylethyldiethoxysilane,
3- (1-hexamethyleneimino) propyltrimethoxysilane,
3- (1-hexamethyleneimino) propyltriethoxysilane,
3- (1-hexamethyleneimino) propylmethyldimethoxysilane,
3- (1-hexamethyleneimino) propylethyldimethoxysilane,
3- (1-hexamethyleneimino) propylmethyldiethoxysilane,
3- (1-hexamethyleneimino) propylethyldiethoxysilane,
3-morpholinopropyltrimethoxysilane,
3-morpholinopropyltriethoxysilane,
3-morpholinopropylmethyldimethoxysilane,
3-morpholinopropylethyldimethoxysilane,
3-morpholinopropylmethyldiethoxysilane,
There may be mentioned 3-morpholinopropylethyldiethoxysilane.

As the compound represented by the formula (3), as a compound in which R ³⁴ and R ³⁵ are one group bonded to a nitrogen atom by a double bond,
N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine,
N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine can be mentioned.

As a compound represented by Formula (3),
Preferably,
[3- (dialkylamino) propyl] trialkoxysilane,
More preferably,
[3- (dimethylamino) propyl] trimethoxysilane,
[3- (diethylamino) propyl] trimethoxysilane,
[3- (dimethylamino) propyl] triethoxysilane,
[3- (diethylamino) propyl] triethoxysilane,
More preferably,
[3- (Diethylamino) propyl] trimethoxysilane.

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 economic efficiency and wear resistance, the content is preferably 20% by mass or less, more preferably 2% by mass or less, and still more preferably 1% 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 economic efficiency and wear resistance, the content is preferably 20% by mass or less, more preferably 2% by mass or less, and still more preferably 1% 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 70 mol% or less, and more preferably 60 mol% or less, in order to improve 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 20 mol% or more, More preferably, it is 40 mol% or more, More preferably, it is 50 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 suitable production method of the conjugated diene polymer, a production method having the following step A and step B can be mentioned.
(Step A): In a hydrocarbon solvent, 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. A polymer unit having a monomer unit based on a conjugated diene, a monomer unit based on a compound represented by the above formula (1), and a monomer unit based on a compound represented by the above formula (2) A step of obtaining a polymer having an alkali metal derived from an alkali metal catalyst at one end.
(Step B): A step of reacting the polymer obtained in Step A with an alkoxysilane compound.

Examples of the alkali metal catalyst used in Step A 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 used in the step A 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. 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.

In step A, 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 in a hydrocarbon solvent with an alkali metal catalyst. A polymer having a monomer unit based on a diene, a monomer unit based on a compound represented by the above formula (1), and a monomer unit based on a 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.

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 determined by the amount of the monomer component used in the polymerization. In order to increase the wear resistance when the total use amount is 100% by mass, it is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and further preferably 100% by mass.

In step A, the conjugated diene, the compound represented by the formula (1) and the compound represented by the formula (2) may be combined with a vinyl aromatic hydrocarbon to perform polymerization. Styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, divinyl naphthalene, and the like. 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 in step A 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.

Step A may be a multistage step. For example, it may be a step having the following steps a1, a2, and a3.
(Step a1): In a hydrocarbon solvent, a conjugated diene, a compound represented by the formula (1) and a vinyl aromatic hydrocarbon are polymerized with an alkali metal catalyst, and the alkali metal derived from the catalyst is used as a polymer chain end. Step of obtaining a conjugated diene-based polymer (step a2): adding the compound represented by the formula (2) to the hydrocarbon solution obtained in the step a1, and converting the compound represented by the formula (2) into the step A structure in which an alkali metal derived from an alkali metal catalyst is bonded to a monomer unit based on the compound represented by the formula (2) by reacting with a polymer chain end of the conjugated diene polymer obtained in a1. Step of obtaining a conjugated diene polymer having a chain end (step a3): adding the conjugated diene and vinyl aromatic hydrocarbon to the hydrocarbon solution obtained in step a2, Obtained in step a2. Step of polymerizing the polymer chain end of the conjugated diene polymer

In the step B, the amount of the alkoxysilane compound reacted with the polymer prepared in the step A is usually 0.1 to 3 mol per 1 mol of the alkali metal derived from the organic alkali metal catalyst, preferably 0. It is 5-2 mol, More preferably, it is 0.7-1.5 mol.

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 (4).

R ⁴¹ _a ML _4-a (4)
Wherein R ⁴¹ 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 (4), 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 represent a branched or unbranched C 1-12 alkyl group, a branched or unbranched C 1-12 alkoxy group, 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 from each other. R ¹⁰⁴ represents a branched or unbranched alkylene group having 1 to 6 carbon atoms. ]

[Wherein, R ²⁰¹ represents 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 hydrogen at the terminal of the alkyl group is substituted with a hydroxyl group or a carboxyl group is represented. R ²⁰² represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenylene group having 2 to 30 carbon atoms, or a branched or unbranched alkynylene group having 2 to 30 carbon atoms. 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>
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene 58 g, 6.1 ml of tetrahydrofuran, and 4.1 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, 2.74 g of bis (diethylamino) methylvinylsilane and n-hexane solution of n-butyllithium (n-butyllithium content 15.04 mmol) were charged into the polymerization reactor to initiate the polymerization reaction.
The stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene and styrene, 3- (1-pyrrolidinyl) were continuously fed into the polymerization reactor. ) Ethylstyrene, 4- (1-pyrrolidinyl) ethylstyrene, and bis (diethylamino) methylvinylsilane were copolymerized for 3 hours. The amount of 1,3-butadiene supplied was 912 g, and the amount of styrene supplied was 288 g. In 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 0.13% by mass, and bis (diethylamino ) The amount of methylvinylsilane charged was 0.14% by mass.
Next, the obtained polymerization reaction solution was stirred at a stirring speed of 130 rpm, 12.8 mmol of [3- (diethylamino) propyl] trimethoxysilane was added to the polymer solution, and further stirred for 15 minutes. Next, 20 ml of hexane solution containing 0.8 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
To the polymer solution, 8.0 g of 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM), 4.0 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) is added, and then the polymer solution is evaporated at room temperature for 24 hours. The copolymer 1 was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

<Creation of copolymer 2>
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 10.2 kg of hexane (density 680 kg / m ³ ), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 ml of tetrahydrofuran, and 4.7 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, 15.38 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.
The stirring reaction rate is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and the copolymerization reaction of 1,3-butadiene and styrene is performed for 3 hours while continuously supplying 1,3-butadiene and styrene into the polymerization reactor. went. The amount of 1,3-butadiene supplied was 821 g, and the amount of styrene supplied was 259 g.
Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 12.80 mmol of [3- (diethylamino) propyl] trimethoxysilane was added and stirred for 15 minutes. 20 ml of a hexane solution containing 0.8 ml of methanol in the polymer solution was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
To the polymer solution, 8.0 g of 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM), 4.0 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) is added, and then the polymer solution is evaporated at room temperature for 24 hours. The copolymer 2 was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

<Creation of copolymer 3>
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, 6.1 ml of tetrahydrofuran, and 4.4 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, 2.63 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (n-butyllithium content 14.68 mmol) were charged into the polymerization reactor 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 bis (diethylamino) The copolymerization reaction of methyl vinyl silane was performed for 3 hours. The amount of 1,3-butadiene supplied was 912 g, and the amount of styrene supplied was 288 g. In the total amount of monomers charged / supplied to the polymerization reactor, the charged amount of bis (diethylamino) methylvinylsilane was 0.13% by mass.
20 ml of hexane solution containing 0.8 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-methylphenylacrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 8 was added to the polymer solution. 0.0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) 4.0 g 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.

<Preparation of copolymer 4>
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, 3.73 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.
The stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene and styrene, 3- (1-pyrrolidinyl) were continuously fed into the polymerization reactor. ) Copolymerization reaction of ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene was carried out for 2 hours. The supply amount of 1,3-butadiene was 205 g, and the supply amount of styrene was 65 g. In the total amount of monomers charged and supplied to the polymerization reactor, the charged amount of the mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene was 0.12% by mass.
20 ml of hexane solution containing 0.8 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-methylphenylacrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 8 was added to the polymer solution. 0.0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) 4.0 g 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 4.

<Preparation of copolymer 5>
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, 1.41 g of 4-vinylpyridine, 6.1 ml of tetrahydrofuran, 4.0 ml of ethylene glycol diethyl ether It was put into the vessel. Next, 2.88 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (n-butyllithium content 17.84 mmol) were charged into the polymerization reactor 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, 4-vinylpyridine, and The copolymerization reaction of bis (diethylamino) methylvinylsilane was performed for 3 hours. The amount of 1,3-butadiene supplied was 912 g, and the amount of styrene supplied was 288 g.
Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of 4-vinylpyridine added was 0.07% by mass, and the amount of bis (diethylamino) methylvinylsilane added was 0.14% by mass.
Next, the obtained polymerization reaction solution was stirred at a stirring speed of 130 rpm, 13.4 mmol of [3- (diethylamino) propyl] trimethoxysilane was added to the polymer solution, and further stirred for 15 minutes. Next, 20 ml of hexane solution containing 0.8 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
To the polymer solution, 8.0 g of 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM), 4.0 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) is added, and then the polymer solution is evaporated at room temperature for 24 hours. The copolymer 5 was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

<Preparation of copolymer 6>
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, 1.41 g of 4-vinylpyridine, 6.1 ml of tetrahydrofuran, 4.0 ml of ethylene glycol diethyl ether It was put into the vessel. Next, 18.52 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-vinylpyridine The copolymerization reaction of was carried out for 3 hours. The amount of 1,3-butadiene supplied was 912 g, and the amount of styrene supplied was 288 g. Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of 4-vinylpyridine charged was 0.07% by mass.
20 ml of hexane solution containing 0.8 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-methylphenylacrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 8 was added to the polymer solution. 0.0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) 4.0 g 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 6.

The obtained copolymers 1 to 6 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）
老化防止剤：住友化学（株）製のアンチゲン３Ｃ
ワックス：大内新興化学工業（株）製のサンノックＮ
オイル：（株）ジャパンエナジー製のＸ−１４０
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
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 to 6: Synthetic carbon black by the above method: Diablack N220 manufactured by Mitsubishi Chemical Corporation (N ₂ SA: 111 m ² / g, DBP absorption: 115 ml / 100 g)
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
Anti-aging agent: Antigen 3C manufactured by Sumitomo Chemical Co., Ltd.
Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Stearic acid: Beads manufactured by NOF Corporation Zinc stearate zinc oxide: Zinc flower No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Sulfur powder vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd. CZ: Sumitomo Chemical ( Soxinol CZ manufactured by
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. It was displayed as an index when Example 1 was 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 1) / (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 1 is 100. The larger the value, the better the wear resistance.

As shown in Table 2, a conjugated diene polymer (copolymers 1 and 5) 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 (9)

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 obtained by reacting the alkoxysilane compound with one end of the copolymer 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.

(In the formula, V ¹ represents a hydrocarbyl group having a polymerizable carbon-carbon double bond, and S ¹ represents a substituted silyl group.)

(In the formula, V ² represents a hydrocarbyl group having a polymerizable carbon-carbon double bond, and A ² represents a substituted amino group or a nitrogen-containing heterocyclic group.) The rubber composition for a tread according to claim 1, wherein the alkoxysilane compound is a compound represented by the following formula (3).

(In the formula, p represents an integer of 1 to 10, R ³¹ , R ³² and R ³³ each independently represents an alkyl group or an alkoxy group, and at least one of R ³¹ , R ³² and R ³³ is an alkoxy group. And A ³ represents a substituted amino group.) The group represented by V ¹ in the formula (1) is a group represented by the following formula (1-V1), and the group represented by S ¹ in the formula (1) is represented by the following formula (1-S). The rubber composition for a tread according to claim 1, wherein the rubber composition is represented by the formula:

(In the formula, R ¹¹ represents a hydrogen atom or a hydrocarbyl group, n is 0 or 1, and R ¹² represents a hydrocarbylene group.)

(Wherein X ¹ , X ² and X ³ each independently represents 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.) The rubber composition for a tread according to claim 3, wherein R ^{11 in the} formula (1-V1) is a hydrogen atom, and n is 0. Groups represented by V ² in the formula (2) is a tread rubber composition according to claim 1 is a group represented by the following formula (2-V1).

(Wherein R ²¹ represents a hydrogen atom or a hydrocarbyl group, m is 0 or 1, and R ²² represents a hydrocarbylene group.) Equation (2) a tread rubber composition according to any one of claims 1 to 5 substituted amino group of A ² is a group represented by the following formula (2-A) in.

(In the formula, each of R ²⁵ and R ²⁶ has a hydrocarbyl group, a trihydrocarbyl silyl group, or R ²⁵ and R ²⁶ 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 ²⁵ and R ²⁶ are one group and represent a group bonded to the nitrogen atom with a double bond.) 7. The tread according to claim 1, wherein the vinyl bond content of the conjugated diene polymer is 20 mol% or more and 70 mol% or less, with the content of the constituent unit based on the conjugated diene being 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 1-7 characterized by the above-mentioned.

[Wherein R ^{101 to} R ¹⁰³ represent a branched or unbranched C 1-12 alkyl group, a branched or unbranched C 1-12 alkoxy group, 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 from each other. R ¹⁰⁴ represents a branched or unbranched alkylene group having 1 to 6 carbon atoms. ]

[Wherein, R ²⁰¹ represents 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 hydrogen at the terminal of the alkyl group is substituted with a hydroxyl group or a carboxyl group is represented. R ²⁰² represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenylene group having 2 to 30 carbon atoms, or a branched or unbranched alkynylene group having 2 to 30 carbon atoms. R ²⁰¹ and R ²⁰² may form a ring structure. ] The pneumatic tire produced using the rubber composition in any one of Claims 1-8.