JP6228201B2 - Pneumatic tire - Google Patents

Description

The present invention relates to a pneumatic tire.

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-mentioned problems and to provide a pneumatic tire in which fuel economy, wet grip performance, and wear resistance are improved 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。）
化合物（Ｇ）：置換基を有していてもよいアミノ基及びカルボニル基を有する化合物、並びに置換基を有していてもよいアミノ基及びチオカルボニル基を有する化合物からなる化合物群から選ばれる少なくとも１種の化合物。1st this invention contains a rubber component, a silica, and the silane coupling agent represented by following formula (I), The monomer unit based on a conjugated diene in 100 mass% of said rubber components, It has a monomer unit based on the compound represented by the formula (1) and a monomer unit based on the compound represented by the following formula (2), and is co-polymerized by the following compound (G) or an alkoxysilane compound. For treads, wherein the content of the conjugated diene polymer (A) in which at least one end of the coalescence is modified is 5% by mass or more, and the content of the silica with respect to 100 parts by mass of the rubber component is 5 to 150 parts by mass. The present invention relates to a pneumatic tire having a tread produced using a rubber composition.
_{(C p H 2p + 1 O} ) 3 Si-C q H 2q -S-CO-C k H 2k + 1 (I)
(In the formula, p is an integer of 1 to 3, q is an integer of 1 to 5, and k is an integer of 5 to 12.)

(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.)
Compound (G): at least selected from the group consisting of a compound having an amino group and a carbonyl group which may have a substituent, and a compound having an amino group and a thiocarbonyl group which may have a substituent One compound.

（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。）Groups 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.)

（式中、Ｅは、酸素原子又は硫黄原子を表し、Ｚ^１及びＺ^２は、置換アミノ基、水素原子、置換基を有していてもよいヒドロカルビル基、又は、置換基を有していてもよいヒドロカルビルオキシ基を表し、Ｚ^１及びＺ^２の少なくとも１つが置換アミノ基を有する基であるか、あるいは、Ｚ^１とＺ^２とが結合して、置換アミノ基を有する環構造をＺ^１とＺ^２とカルボニル炭素とで形成する基を表す。）

（式中、ｖは１〜１０の整数を表し、Ｒ^４１、Ｒ^４２及びＲ^４３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^４１、Ｒ^４２及びＲ^４３の少なくとも１つがアルコキシ基であり、Ａ^４は置換アミノ基を表す。）It is preferable that the compound (G) is a compound represented by the following formula (3) and the alkoxysilane compound is a compound represented by the following formula (4).

(In the formula, E represents an oxygen atom or a sulfur atom, and Z ¹ and Z ² have a substituted amino group, a hydrogen atom, a hydrocarbyl group which may have a substituent, or a substituent. It represents also good hydrocarbyloxy group, or at least one of Z ¹ and Z ² is a group having a substituted amino group, or by bonding with Z ¹ and Z ^2, the ring structure having a substituted amino group Z ¹ And represents a group formed by Z ² and a carbonyl carbon.)

(In the formula, v represents an integer of 1 to 10, R ⁴¹ , R ⁴² and R ⁴³ each independently represents an alkyl group or an alkoxy group, and at least one of R ⁴¹ , R ⁴² and R ⁴³ is an alkoxy group. And A ⁴ represents a substituted amino group.)

（式中、ｐは０又は１であり、Ｔは炭素原子数１〜１０のヒドロカルビレン基、下記式（３−Ｔａ）で表される基、又は、下記式（３−Ｔｂ）で表される基を表し、Ａ^３は置換アミノ基を表し、式（３）のＺ^２がヒドロカルビル基である場合、Ｚ^１のＡ^３とＺ^２のヒドロカルビル基とは結合していてもよく、式（３）のＺ^２が式（３−Ｚ）で表される基である場合、Ｚ^１のＡ^３とＺ^２のＡ^３とは結合していてもよい。）

（式中、Ｒ^３１は炭素原子数１〜１０のヒドロカルビレン基を表し、Ｒ^３１がＡ^３と結合する。）

（式中、Ｒ^３２は炭素原子数１〜１０のヒドロカルビレン基を表し、Ｒ^３３は水素原子又は炭素原子数１〜１０のヒドロカルビル基を表し、Ｒ^３２がＡ^３と結合する。）In the above formula (3), E is an oxygen atom, Z ¹ is a group represented by the following formula (3-Z), and Z ² is a hydrocarbyl group or a group represented by the following formula (3-Z) It is preferable that

(In the formula, p is 0 or 1, and T is a hydrocarbylene group having 1 to 10 carbon atoms, a group represented by the following formula (3-Ta), or a group represented by the following formula (3-Tb). A ³ represents a substituted amino group, and when Z ^{2 in} Formula (3) is a hydrocarbyl group, A ³ in Z ¹ and the hydrocarbyl group in Z ² may be bonded to each other. when ^{Z 2} of (3) is a group represented by the formula (3-Z), it may be bonded to the ^{a 3} and ^{Z 2} of ^{a 3} of ^{Z 1.)}

^{(Wherein, R 31} represents a hydrocarbylene group having 1 to 10 carbon ^{atoms, R 31} is bonded to ^{A 3.)}

(In the formula, R ³² represents a hydrocarbylene group having 1 to 10 carbon atoms, R ³³ represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms, and R ³² is bonded to A ^3. )

（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 ) Is preferable.

(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 the above formula (1-V1), R ¹¹ is preferably a hydrogen atom and n is preferably 0.

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

（式中、Ｒ^５１は水素原子又はヒドロカルビル基を表し、ｗは０又は１であり、Ｒ^５２はヒドロカルビレン基を表し、Ｘ^５１、Ｘ^５２及びＸ^５３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^５１、Ｘ^５２及びＸ^５３の少なくとも１つが置換アミノ基である。）

（式中、Ｒ^６１は水素原子又はヒドロカルビル基を表し、ｘは０又は１であり、Ｒ^６２はヒドロカルビレン基を表し、Ａ^６は置換アミノ基、又は、含窒素複素環基を表す。）2nd this invention contains a rubber component, a silica, and the silane coupling agent represented by following formula (I), The monomer unit based on a conjugated diene in 100 mass% of said rubber components, The content of the conjugated diene polymer (B) having a monomer unit based on the compound represented by the formula (5) and a monomer unit based on the compound represented by the following formula (6) is 5 mass. It is related with the pneumatic tire which has a tread produced using the rubber composition for tread whose content of the said silica is 5-150 mass parts with respect to 100 mass parts of said rubber components.
_{(C p H 2p + 1 O} ) 3 Si-C q H 2q -S-CO-C k H 2k + 1 (I)
(In the formula, p is an integer of 1 to 3, q is an integer of 1 to 5, and k is an integer of 5 to 12.)

(In the formula, R ⁵¹ represents a hydrogen atom or a hydrocarbyl group, w is 0 or 1, R ⁵² represents a hydrocarbylene group, and X ⁵¹ , X ^52, and X ⁵³ are each independently a substituted amino group. Or an optionally substituted hydrocarbyl group, wherein at least one of X ⁵¹ , X ⁵² and X ⁵³ is a substituted amino group.)

(In the formula, R ⁶¹ represents a hydrogen atom or a hydrocarbyl group, x is 0 or 1, R ⁶² represents a hydrocarbylene group, and A ⁶ represents a substituted amino group or a nitrogen-containing heterocyclic group. )

R ^{51 in the} above formula (5) is preferably a hydrogen atom and w is preferably 0.

（式中、ｙは０〜５の整数を表し、ｙが１〜５の整数である場合、（ＣＨ_２）_ｙはベンゼン環上の置換基であり、（ＣＨ_２）_ｙがＡ^６と結合し、ｙが０である場合、（ＣＨ_２）_ｙはベンゼン環とＡ^６との結合を表す。）In the above formula (6), R ⁶¹ is a hydrogen atom, x is 1, R ⁶² is a group represented by the following formula (6-Y), and A is preferably a substituted amino group.

(In the formula, y represents an integer of 0 to 5, and when y is an integer of 1 to 5, (CH ₂ ) _y is a substituent on the benzene ring, and (CH ₂ ) _y is bonded to A ^6. And when y is 0, (CH ₂ ) _y represents a bond between the benzene ring and A ^6. )

The vinyl bond content of the conjugated diene polymer (B) 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%.

According to the present invention, a conjugated diene polymer (A) having a specific monomer unit and having a terminal modified with a specific compound, and / or a conjugated diene system having a specific monomer unit Since it is a pneumatic tire having a tread produced by using a rubber composition for a tread in which a polymer (B), silica, and a specific silane coupling agent are blended, low fuel consumption, wet grip performance and abrasion resistance Sexually improved.

（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。）
化合物（Ｇ）：置換基を有していてもよいアミノ基及びカルボニル基を有する化合物、並びに置換基を有していてもよいアミノ基及びチオカルボニル基を有する化合物からなる化合物群から選ばれる少なくとも１種の化合物。The conjugated diene polymer (A) according to the first aspect of 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 the following formula (2). And at least one end of the copolymer is modified with the following compound (G) or an alkoxysilane compound. By combining the conjugated diene polymer (A), silica, and a specific silane coupling agent, the fuel efficiency, wet grip performance, and wear resistance (especially wet grip performance and wear resistance) are synergistic. Can be improved.

(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.)
Compound (G): at least selected from the group consisting of a compound having an amino group and a carbonyl group which may have a substituent, and a compound having an amino group and a thiocarbonyl group which may have a substituent One compound.

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 further 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); That.

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, 1-methylene-2-propenyl group, 2-methylene-3-butenyl group; as a group in which R ²¹ is a phenyl group, 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 further 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-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) aminomethylphenyl) -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.

When the conjugated diene polymer (A) is modified with the compound (G), the compound represented by the formula (2) is preferably a group represented by V ² represented by the formula (2-V1). And R ²¹ in the formula (2-V1) is a hydrogen atom or a phenyl group.
More preferably,
A compound in which 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);
A compound wherein R ²¹ is a phenyl group, m is 1, R ²² is a phenylene group, and A ² is a substituted amino group represented by the formula (2-A);
A compound in which R ²¹ is a hydrogen atom, m is 1, R ²² is a group represented by the formula (2-R), and A ² is a substituted amino group represented by the formula (2-A) ;
A compound in which R ²¹ is a phenyl group, m is 1, R ²² is a group represented by the formula (2-R), and A ² is a substituted amino group represented by the formula (2-A) ;
In this compound, R ²¹ 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, A ² is R ²⁵ and R ^{26 in} Formula (2-A) are 1 carbon atom A compound that is a linear alkyl group of ~ 2;
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) are trimethylsilyl groups. Compound;
R ²¹ is a phenyl group, m is 1, R ²² is a para-phenylene group or a meta-phenylene group, A ² is R ²⁵ and R ²⁶ in the formula (2-A) are 1 carbon atom A compound that is a linear alkyl group of ~ 2;
R ²¹ is a phenyl group, 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) are trimethylsilyl groups. Compound;
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 R ²⁵ in the formula (2-A). And R ²⁶ is a linear alkyl group having 1 to 2 carbon atoms;
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 R ²⁵ in the formula (2-A). And R ²⁶ is a trimethylsilyl group;
R ²¹ is a phenyl group, m is 1, R ²² is a group represented by the formula (2-Ra) or (2-Rb), and A ² is R ²⁵ in the formula (2-A). And R ²⁶ is a linear alkyl group having 1 to 2 carbon atoms;
R ²¹ is a phenyl group, m is 1, R ²² is a group represented by the formula (2-Ra) or (2-Rb), and A ² is R ²⁵ in the formula (2-A). And a compound in which R ²⁶ is a trimethylsilyl group; a compound in which m is 0 and A ² is a pyridyl group.
The compound represented by the formula (2), preferably, groups represented by ^{V 2} is represented by the formula (2-V1), ^{R 21} in the formula (2-V1) is a hydrogen atom A compound.
More preferably, R ²¹ is a hydrogen atom, m is 1, R ²² is a group represented by the formula (2-Ra), and A ² is a substituted amino group.
More preferably, R ²¹ is a hydrogen atom, m is 1, R ²² is a group represented by the formula (2-Ra), i in the formula (2-Ra) is 1, and A ² Is a substituted amino group.

When the conjugated diene polymer (A) is modified with the compound (G), the compound represented by the formula (2) is particularly preferably
4-N, N-dimethylaminomethylstyrene,
3-N, N-dimethylaminomethylstyrene,
4-N, N-bis (trimethylsilyl) aminostyrene,
3-N, N-bis (trimethylsilyl) aminostyrene,
4-N, N-bis (trimethylsilyl) aminomethylstyrene,
1- (4-N, N-dimethylaminophenyl) -1-phenylethylene,
1- (3-N, N-dimethylaminophenyl) -1-phenylethylene,
4-vinylpyridine,
2-vinylpyridine, most preferably
4-N, N-dimethylaminomethylstyrene,
4-N, N-bis (trimethylsilyl) aminomethylstyrene,
It is.

If the conjugated diene polymer (A) is modified by an alkoxysilane compound, as the compound represented by formula (2), the table preferably is a group represented by V ² has the formula (2-V1) And R ²¹ in formula (2-V1) is a hydrogen atom.
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.

When the conjugated diene polymer (A) is modified with an alkoxysilane compound, the compound represented by the formula (2) is particularly preferably
3- (1-pyrrolidinyl) ethylstyrene,
4- (1-pyrrolidinyl) ethylstyrene,
4-vinylpyridine,
2-vinylpyridine.

（式中、Ｅは、酸素原子又は硫黄原子を表し、Ｚ^１及びＺ^２は、置換アミノ基、水素原子、置換基を有していてもよいヒドロカルビル基、又は、置換基を有していてもよいヒドロカルビルオキシ基を表し、Ｚ^１及びＺ^２の少なくとも１つが置換アミノ基を有する基であるか、あるいは、Ｚ^１とＺ^２とが結合して、置換アミノ基を有する環構造をＺ^１とＺ^２とカルボニル炭素とで形成する基を表す。）Examples of the compound (G) include a compound represented by the following formula (3).

(In the formula, E represents an oxygen atom or a sulfur atom, and Z ¹ and Z ² have a substituted amino group, a hydrogen atom, a hydrocarbyl group which may have a substituent, or a substituent. It represents also good hydrocarbyloxy group, or at least one of Z ¹ and Z ² is a group having a substituted amino group, or by bonding with Z ¹ and Z ^2, the ring structure having a substituted amino group Z ¹ And represents a group formed by Z ² and a carbonyl carbon.)

In formula (3), E represents an oxygen atom or a sulfur atom. Preferably, it is an oxygen atom.

In formula (3), the substituted amino group of Z ¹ and Z ² is substituted with an amino group having a hydrocarbyl group as a substituent, an amino group having a group having a substituted amino group as a substituent, or a group having a hydrocarbyloxy group Examples thereof include an amino group as a group.

Examples of the amino group having a hydrocarbyl group as a substituent include dialkylamino groups such as a dimethylamino group, a diethylamino group, and a dipropylamino group.

Examples of the amino group having a substituted amino group as a substituent include (dimethylaminomethyl) amino group, (dimethylaminoethyl) amino group, (dimethylaminopropyl) amino group, (diethylaminopropyl) amino group, (dipropyl) (Dialkylaminoalkyl) amino groups such as aminopropyl) amino group; bis (dialkylaminoalkyl) amino groups such as bis (dimethylaminoethyl) amino group and bis (dimethylaminopropyl) amino group.

The amino group having a hydrocarbyloxy group-containing group as a substituent includes (alkoxyalkyl) amino such as (methoxymethyl) amino group, (methoxyethyl) amino group, (methoxypropyl) amino group, and (ethoxymethyl) amino group. (Aryloxyalkyl) amino groups such as (phenoxymethyl) amino group and (phenoxyethyl) amino group; (aralkyloxyalkyl) amino groups such as (benzyloxymethyl) amino group and (benzyloxyethyl) amino group can give.

Examples of the hydrocarbyl group optionally having a substituent for Z ¹ and Z ² include a hydrocarbyl group, a hydrocarbyl group having a substituted amino group as a substituent, and a hydrocarbyl group having a hydrocarbyloxy group as a substituent.

Examples of the hydrocarbyl group include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a methylphenyl group, and an ethylphenyl group An aralkyl group such as a benzyl group; an alkenyl group such as a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a crotyl group, an isocrotyl group, and a methallyl group; and an alkynyl group such as a propargyl group.

Examples of the hydrocarbyl group having a substituted amino group as a substituent include a hydrocarbyl group having a hydrocarbyl-substituted amino group as a substituent. Examples of the hydrocarbyl group having a hydrocarbyl-substituted amino group as a substituent include dialkylaminoalkyl groups such as dimethylaminomethyl group, dimethylaminoethyl group, and dimethylaminopropyl group; dialkylaminoaryl groups such as dimethylaminophenyl group and diethylaminophenyl group. can give.

Examples of the hydrocarbyl group having a hydrocarbyloxy group as a substituent include alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, methoxypropyl group, and ethoxymethyl group; aryloxyalkyl groups such as phenoxymethyl group and phenoxyethyl group; benzyloxy And aralkyloxyalkyl groups such as a methyl group and a benzyloxyethyl group.

Examples of the hydrocarbyloxy group which may have a substituent of Z ¹ and Z ² include a hydrocarbyloxy group, a hydrocarbyloxy group having a hydrocarbyloxy group as a substituent, and a hydrocarbyloxy group having a substituted amino group as a substituent. It is done.

Hydrocarbyloxy groups include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy and butoxy; aryloxy groups such as phenoxy, methylphenoxy and ethylphenoxy; aralkyl such as benzyloxy An oxy group etc. are mention | raise | lifted.

Examples of the hydrocarbyloxy group having a hydrocarbyloxy group as a substituent include an alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, a methoxypropoxy group, and an ethoxymethoxy group; an aryloxyalkoxy group such as a phenoxymethoxy group and a phenoxyethoxy group; Examples thereof include aralkyloxyalkoxy groups such as oxymethoxy group and benzyloxyethoxy group.

Examples of the hydrocarbyloxy group having a substituted amino group as a substituent include a hydrocarbyloxy group having a hydrocarbyl-substituted amino group as a substituent. Examples of the hydrocarbyloxy group having a hydrocarbyl-substituted amino group as a substituent include dialkylaminoalkoxy groups such as a dimethylaminomethoxy group, a dimethylaminoethoxy group, and a dimethylaminopropoxy group.

（式中、ｐは０又は１であり、Ｔは炭素原子数１〜１０のヒドロカルビレン基、下記式（３−Ｔａ）で表される基、又は、下記式（３−Ｔｂ）で表される基を表し、Ａ^３は置換アミノ基を表す。）

（式中、Ｒ^３１は炭素原子数１〜１０のヒドロカルビレン基を表し、Ｒ^３１がＡ^３と結合する。）

（式中、Ｒ^３２は炭素原子数１〜１０のヒドロカルビレン基を表し、Ｒ^３３は水素原子又は炭素原子数１〜１０のヒドロカルビル基を表し、Ｒ^３２がＡ^３と結合する。）The group having a substituted amino group is preferably a group represented by the following formula (3-Z).

(In the formula, p is 0 or 1, and T is a hydrocarbylene group having 1 to 10 carbon atoms, a group represented by the following formula (3-Ta), or a group represented by the following formula (3-Tb). And A ³ represents a substituted amino group.)

^{(Wherein, R 31} represents a hydrocarbylene group having 1 to 10 carbon ^{atoms, R 31} is bonded to ^{A 3.)}

(In the formula, R ³² represents a hydrocarbylene group having 1 to 10 carbon atoms, R ³³ represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms, and R ³² is bonded to A ^3. )

When Z ¹ in Formula (3) is a group represented by Formula (3-Z) and Z ² is a hydrocarbyl group, A ³ in Z ¹ and the hydrocarbyl group in Z ² may be bonded to each other. . Also, when ^{Z 1} and ^{Z 2} of formula (3) is a group represented by the formula (3-Z), it may be bonded to the ^{A 3} and ^{Z 2} of ^{A 3} of ^{Z 1.}

In the formula (3-Z), p represents 0 or 1.

In formula (3-Z), T represents a hydrocarbylene group having 1 to 10 carbon atoms, a group represented by formula (3-Ta), or a group represented by formula (3-Tb). .

Examples of the hydrocarbylene group having 1 to 10 carbon atoms of T include alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group; arylene groups such as phenylene group and naphthylene group Etc.

In the formula (3-Ta), R ³¹ represents a hydrocarbylene group having 1 to 10 carbon atoms, and in the formula (3-Tb), R ³² represents a hydrocarbylene group having 1 to 10 carbon atoms, R ³³ represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms.

Examples of the hydrocarbylene group having 1 to 10 carbon atoms of R ³¹ and R ³² include alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group; phenylene group and naphthylene group An arylene group such as Preferably, they are an ethylene group and a trimethylene group.

Examples of the hydrocarbyl group having 1 to 10 carbon atoms of R ³³ include an alkyl group, an aralkyl group, and an aryl 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 aralkyl group include a benzyl group. A phenyl group etc. can be mention | raise | lifted as an aryl group. An alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. R ³³ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.

Examples of the group represented by the formula (3-Ta) include a group represented by —O—CH ₂ CH ₂ — and a group represented by —O—CH ₂ CH ₂ CH ₂ —.

Examples of the group represented by the formula (3-Tb) include a group represented by —NH—CH ₂ CH ₂ — and a group represented by —NH—CH ₂ CH ₂ CH ₂ —.

（式中、Ｒ^３４及びＲ^３５は、それぞれ、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、又は、トリヒドロカルビルシリル基、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。）The group represented by A ³ in formula (3-Z) is preferably a group represented by the following formula (3-A).

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

Examples of the hydrocarbyl group of R ³⁴ and R ³⁵ 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 ³⁴ and R ³⁵ is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.

The hydrocarbyl group of R ³⁴ and R ³⁵ 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 hydrocarbyl group having a nitrogen atom of R ³⁴ and R ³⁵ include dialkylaminoalkyl groups such as a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, and a diethylaminoethyl group. The number of carbon atoms of the hydrocarbyl group having a nitrogen atom of R ³⁴ and R ³⁵ is preferably 3 to 10, more preferably 3 to 6, and further preferably 3 to 4.

The hydrocarbyl group having an oxygen atom of R ³⁴ and R ³⁵ includes an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, and an ethoxyethyl group; an oxacyclo group such as an oxiranyl group and a tetrahydrofuranyl group. An alkyl group; an oxacycloalkylalkyl group such as a glycidyl group and a tetrahydrofurfuryl group. The number of carbon atoms of the hydrocarbyl group having an oxygen atom of R ³⁴ and R ³⁵ is preferably 2 to 10, more preferably 2 to 6, and further preferably 2 to 4.

In this specification, the oxacycloalkyl group represents a group in which CH ₂ on the alicyclic ring of the cycloalkyl group is replaced with an oxygen atom, and the oxacycloalkylalkyl group is a group in which a hydrogen atom of the alkyl group is replaced with an oxacycloalkyl group. Represents a group.

Examples of the trihydrocarbylsilyl group of R ³⁴ and R ³⁵ include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group.

The trihydrocarbylsilyl group of R ³⁴ and R ³⁵ 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 ³⁴ and R ³⁵ 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 group to which R ³⁴ and R ³⁵ are bonded is preferably 2 to 20, more preferably 2 to 7, and still more preferably 4 to 6.

The hydrocarbylene group which may have a nitrogen atom and / or oxygen atom to which R ³⁴ and R ³⁵ 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 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. And hydrocarbylidene groups such as groups.

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 6.

R ³⁴ and R ³⁵ are preferably a hydrocarbyl group, a trihydrocarbylsilyl group, or a hydrocarbylene group in which R ³⁴ and R ³⁵ are bonded.

Examples of the group represented by the formula (3-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 further 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-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 (3-A) is preferably a group in which R ³⁴ and R ³⁵ are hydrocarbyl groups, a group in which R ³⁴ and R ³⁵ are trihydrocarbylsilyl groups, and R ³⁴ and R ³⁵ are oxa groups. A group that is a cycloalkylalkyl group, and a group that is a hydrocarbylene group to which R ³⁴ and R ³⁵ are bonded. More preferably, R ³⁴ and R ³⁵ are a group that is a linear alkyl group, R ³⁴ and R ³⁵ are a group that is a trialkylsilyl group, and a group that is a polymethylene group to which R ³⁴ and R ³⁵ are bonded.

The group represented by the formula (3-A) is more preferably a dialkylamino group.

Examples of the group represented by the formula (3-Z) in which p = 0 include dihydrocarbylamino groups such as dimethylamino group and diethylamino group; 1-aziridinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexa Cyclic amino groups such as methyleneimino group, 1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1-imidazolidinyl group, 1-piperazinyl group, morpholino group; di (glycidyl) amino group, di (tetrahydrofurfuryl) ) Di (oxacycloalkylalkyl) amino group such as amino group; bis (trimethylsilyl) amino group, bis (triethylsilyl) amino group, bis (t-butyldimethylsilyl) amino group, bis (triisopropylsilyl) amino group, etc. And bis (trialkylsilyl) amino group.

Examples of the group represented by the formula (3-Z) in which p = 1 and T is a hydrocarbylene group include dihydrocarbylaminoalkyl groups such as dimethylaminoethyl group, diethylaminoethyl group, dimethylaminopropyl group, and diethylaminopropyl group. A dihydrocarbylaminoaryl group such as a dimethylaminophenyl group or a diethylaminophenyl group;

The group represented by the formula (3-Z) in which p = 1 and T is a group represented by the formula (3-Ta) is represented by —O—CH ₂ CH ₂ —N (CH ₃ ) _2. that _{group, -O-CH 2 CH 2 -N} (CH 2 CH 3) 2 _, a group represented by _the group represented by _{-O-CH 2 CH 2 CH 2} -N (CH 3) 2, -O- _{CH 2 CH 2 CH 2 -N (} CH 2 CH 3) may be mentioned a group represented by _2.

The group represented by the formula (3-Z) in which p = 1 and T is a group represented by the formula (3-Tb) is represented by —NH—CH ₂ CH ₂ —N (CH ₃ ) _2. that _{group, -NH-CH 2 CH 2 -N} (CH 2 CH 3) 2 , a group represented _{by, -NH-CH 2 CH 2 CH} 2 -N group represented by _{(CH 3) 2 -NH-CH 2 CH 2 CH 2 -N (CH} 2 CH 3) may be mentioned a group represented by _2.

Examples of the compound represented by the formula (3) include a carboxylic acid amide compound, a thiocarboxylic acid amide compound, a carboxylic acid ester compound, and a thiocarboxylic acid ester compound.

As a carboxylic acid amide compound,
Formamide compounds such as N, N-dimethylformamide, N, N-diethylformamide;
N, N-dimethylacetamide, N, N-diethylacetamide, aminoacetamide, N, N-dimethyl-N ′, N′-dimethylaminoacetamide, N, N-dimethylaminoacetamide, N, N-dimethyl-N′- Acetamide compounds such as ethylaminoacetamide, N, N-dimethylaminoacetamide, N-phenyldiacetamide;
Propionamide compounds such as N, N-dimethylpropionamide;
N, N-dimethylbenzamide, N ′, N ′-(p-dimethylamino) benzamide, N ′, N ′-(p-diethylamino) benzamide, N, N-dimethyl-N ′, N ′-(p-dimethyl) Benzamide compounds such as amino) benzamide, N, N-dimethyl-N ′, N ′-(p-diethylamino) benzamide;
Pyridylamide compounds such as N, N-dimethyl-4-pyridylamide;
Examples thereof include phthalamide compounds such as N, N, N ′, N′-tetramethylphthalamide and N, N, N ′, N′-tetraethylphthalamide.

As the thiocarboxylic acid amide compound,
Thioformamide compounds such as N, N-dimethylthioformamide, N, N-diethylthioformamide;
N, N-dimethylthioacetamide, N, N-diethylthioacetamide, aminothioacetamide, N, N-dimethyl-N ′, N′-dimethylaminothioacetamide, N, N-dimethylaminothioacetamide, N, N— Thioacetamide compounds such as dimethyl-N′-ethylaminothioacetamide, N, N-dimethylaminothioacetamide, N-phenyldithioacetamide;
Thiopropionamide compounds such as N, N-dimethylthiopropionamide;
N, N-dimethylthiobenzamide, N ′, N ′-(p-dimethylamino) thiobenzamide, N ′, N ′-(p-diethylamino) thiobenzamide, N, N-dimethyl-N ′, N ′-( thiobenzamide compounds such as p-dimethylaminothiobenzamide, N, N-dimethyl-N ′, N ′-(p-diethylamino) thiobenzamide;
Pyridylthioamide compounds such as N, N-dimethyl-4-pyridylthioamide;
Examples thereof include thiophthalamide compounds such as N, N, N ′, N′-tetramethylthiophthalamide and N, N, N ′, N′-tetraethylthiophthalamide.

As the carboxylic acid ester compound,
N, N-dialkylaminomethyl acetate such as N, N-dimethylaminomethyl acetate, N, N-diethylaminomethyl acetate;
N, N-dialkylaminoethyl acetate such as N, N-dimethylaminoethyl acetate, N, N-diethylaminoethyl acetate;
N, N-dialkylaminopropyl acetate such as N, N-dimethylaminopropyl acetate, N, N-diethylaminopropyl acetate;
N, N-dialkylaminoethyl benzoate such as N, N-dimethylaminoethyl benzoate and N, N-diethylaminoethyl benzoate can be used.

As the thiocarboxylic acid ester compound,
N, N-dialkylaminomethylthioacetate such as N, N-dimethylaminomethylthioacetate, N, N-diethylaminomethylthioacetate;
N, N-dialkylaminoethyl thioacetate such as N, N-dimethylaminoethyl thioacetate, N, N-diethylaminoethyl thioacetate;
N, N-dialkylaminopropylthioacetate such as N, N-dimethylaminopropylthioacetate, N, N-diethylaminopropylthioacetate;
N, N-dialkylaminoethylthiobenzoate such as N, N-dimethylaminoethylthiobenzoate, N, N-diethylaminoethylthiobenzoate and the like can be mentioned.

（式中、Ｅは、酸素原子、又は、硫黄原子を表し、Ｒ^３４Ｒ^３５Ｎ−はベンゼン環上の置換基であり、Ｒ^３４及びＲ^３５は、それぞれ、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、又は、トリヒドロカルビルシリル基、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し、Ｒ^３６は、ヒドロカルビル基、又は、水素原子を表す。）

（式中、Ｅは、酸素原子、又は、硫黄原子を表し、ｒは０〜２の数を表し、Ｒ^３４Ｒ^３５Ｎ−はベンゼン環上の置換基であり、Ｒ^３４及びＲ^３５は、それぞれ、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、又は、トリヒドロカルビルシリル基、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。）As a preferred compound represented by the formula (3), a compound in which Z ¹ is a group represented by the formula (3-Z) and Z ² is a hydrocarbyl group or a hydrogen atom which may have a substituent. Can be given.
The compound is represented by the following formula (3-1) wherein p in the formula (3-Z) is 1 and T is a phenylene group, and represented by the following formula (3-2). Compounds.

(In the formula, E represents an oxygen atom or a sulfur atom, R ³⁴ R ³⁵ N- represents a substituent on the benzene ring, and R ³⁴ and R ³⁵ represent a nitrogen atom and / or an oxygen atom, respectively. Hydrocarbyl group which may have, or trihydrocarbylsilyl group, or hydrocarbylene group which R ³⁴ and R ³⁵ may combine to have a nitrogen atom and / or 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, and R ³⁶ represents a hydrocarbyl group or a hydrogen atom.)

(In the formula, E represents an oxygen atom or a sulfur atom, r represents a number of 0 to 2, R ³⁴ R ³⁵ N- represents a substituent on the benzene ring, and R ³⁴ and R ³⁵ represent Each of the hydrocarbyl group or trihydrocarbylsilyl group which may have a nitrogen atom and / or an oxygen atom, or R ³⁴ and R ³⁵ are bonded, and the nitrogen atom and / or the oxygen atom is used as a hetero atom. The hydrocarbylene group which may have, or R ³⁴ and R ³⁵ are one group and represent a group bonded to the nitrogen atom by a double bond.)

E in Formula (3-1) and Formula (3-2) represents an oxygen atom or a sulfur atom, and preferably an oxygen atom.

R in the formula (3-2) represents a number from 0 to 2.

R ³⁴ R ³⁵ N— in the formula (3-1) and the formula (3-2) is a substituent on the benzene ring. R ³⁴ and, ^the definition of ^{R 35,} exemplary and preferred groups, ^{R 34} of formula (3-A), and ^the definitions described in ^{R 35,} is the same as the illustrative and preferred groups.

As R ^<34 > R ^{< 35} > N- of Formula (3-1) and Formula (3-2), Preferably, it is a dialkylamino group. The alkyl group of the dialkylamino group is preferably an alkyl group having 1 to 4 carbon atoms.

R ^{36 in the} formula (3-1) represents a hydrogen atom or a hydrocarbyl group. Examples of the hydrocarbyl group include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups and other alkyl groups; phenyl groups, methylphenyl groups, ethylphenyl groups, and the like. An aralkyl group such as a benzyl group.

As a compound represented by Formula (3-1),
Dialkylamino-substituted benzaldehyde compounds such as 4-dimethylaminobenzaldehyde and 4-diethylaminobenzaldehyde;
Dialkylamino-substituted acetophenone compounds such as 4-dimethylaminoacetophenone and 4-diethylaminoacetophenone;
Heterocyclic group-substituted acetophenone compounds such as 4′-imidazol-1-yl-acetophenone, 4 ′-(1-pyrazolyl) acetophenone, 4-morpholinoacetophenone;
Dialkylamino-substituted thiobenzaldehyde compounds such as 4-dimethylaminothiobenzaldehyde and 4-diethylaminothiobenzaldehyde;
Dialkylamino-substituted thioacetophenone compounds such as 4-dimethylaminothioacetophenone and 4-diethylaminothioacetophenone;
And heterocyclic group-substituted thioacetophenone compounds such as 4′-imidazol-1-yl-thioacetophenone, 4 ′-(1-pyrazolyl) thioacetophenone, 4-morpholinothioacetophenone, and the like.

As a compound represented by Formula (3-2),
Dialkylamino such as 3-dimethylaminobenzophenone, 3-diethylaminobenzophenone, 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4,4′-bis (dimethylamino) -benzophenone, 4,4′-bis (diethylamino) -benzophenone Substituted benzophenone compounds;
Heterocyclic group-substituted benzophenone compounds such as 4 ′-(imidazol-1-yl) -benzophenone, 4 ′-(1-pyrazolyl) benzophenone, 4-morpholinobenzophenone;
3-dimethylaminothiobenzophenone, 3-diethylaminothiobenzophenone, 4-dimethylaminothiobenzophenone, 4-diethylaminothiobenzophenone, 4,4'-bis (dimethylamino) -thiobenzophenone, 4,4'-bis (diethylamino)- Dialkylamino-substituted thiobenzophenone compounds such as thiobenzophenone;
Examples include heterocyclic group-substituted thiobenzophenone compounds such as 4 ′-(imidazol-1-yl) -thiobenzophenone, 4 ′-(1-pyrazolyl) thiobenzophenone and 4-morpholinothiobenzophenone.

（式中、ｓは０又は１であり、Ｔは炭素原子数１〜１０のヒドロカルビレン基、式（３−Ｔａ）で表される基、又は、式（３−Ｔｂ）で表される基を表し、Ｒ^３４及びＲ^３５は、それぞれ、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、又は、トリヒドロカルビルシリル基、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し、Ｒ^３７は、水素原子、又は、ヒドロカルビル基を表す。）Preferred compounds of the formula (3), E is an oxygen atom, a group Z ¹ is represented by the formula (3-Z), the following formula Z ² is a hydrocarbyl group (3-3 ).

(In the formula, s is 0 or 1, and T is a hydrocarbylene group having 1 to 10 carbon atoms, a group represented by the formula (3-Ta), or a formula (3-Tb). Each of R ³⁴ and R ³⁵ is a hydrocarbyl group or trihydrocarbylsilyl group optionally having a nitrogen atom and / or an oxygen atom, or R ³⁴ and R ³⁵ are bonded to each other; A hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom as a hetero atom, or R ³⁴ and R ³⁵ are one group, and represent a group bonded to the nitrogen atom with a double bond; R ³⁷ represents a hydrogen atom or a hydrocarbyl group.)

The definition, illustration and preferred group of T in the formula (3-3) are the same as the definition, illustration and preferred group described in the formula (3-Z).

The definitions, examples and preferred groups of R ³⁴ and R ³⁵ in formula (3-3) are the same as the definitions, examples and preferred groups described in formula (3-A).

Examples of the hydrocarbyl group for R ³⁷ 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 ³⁷ is preferably a hydrogen atom, a methyl group, a vinyl group or a phenyl group, more preferably a hydrogen atom or a methyl group.

Examples of the compound represented by the formula (3-3) include the following acrylamide compounds in which s is 0 and R ³⁷ is a hydrogen atom.
N, N-dimethylacrylamide,
N, N-diethylacrylamide,
N, N-bistrimethylsilylacrylamide,
N, N-di (glycidyl) acrylamide,
N, N-di (tetrahydrofurfuryl) acrylamide,
Morpholinoacrylamide.

Examples of the compound represented by the formula (3-3) include the following acrylamide compounds in which s is 1, T is a group represented by the formula (3-Tb), and R ³⁷ is a hydrogen atom. be able to.
N- (2-dimethylaminoethyl) acrylamide,
N- (3-dimethylaminopropyl) acrylamide,
N- (4-dimethylaminobutyl) acrylamide,
N- (2-diethylaminoethyl) acrylamide,
N- (3-diethylaminopropyl) acrylamide,
N- (4-diethylaminobutyl) acrylamide,
N- (3-bistrimethylsilylaminopropyl) acrylamide,
N- (3-di (glycidyl) aminopropyl) acrylamide,
N- (3-di (tetrahydrofurfuryl) aminopropyl) acrylamide,
N- (3-morpholinopropyl) acrylamide.

Examples of the compound represented by the formula (3-3) include the following methacrylamide compounds in which s is 0 and R ³⁷ is a methyl group.
N, N-dimethylmethacrylamide,
N, N-diethylmethacrylamide,
N, N-bistrimethylsilylmethacrylamide,
N, N-di (glycidyl) methacrylamide,
N, N-di (tetrahydrofurfuryl) methacrylamide,
Morpholino methacrylamide.

The compound represented by formula (3-3) is the following methacrylamide compound in which s is 1, T is a group represented by formula (3-Tb), and R ³⁷ is a methyl group. Can be illustrated.
N- (2-dimethylaminoethyl) methacrylamide,
N- (3-dimethylaminopropyl) methacrylamide,
N- (4-dimethylaminobutyl) methacrylamide,
N- (2-diethylaminoethyl) methacrylamide,
N- (3-diethylaminopropyl) methacrylamide,
N- (4-diethylaminobutyl) methacrylamide,
N- (3-bistrimethylsilylaminopropyl) methacrylamide,
N- (3-di (glycidyl) aminopropyl) methacrylamide,
N- (3-di (tetrahydrofurfuryl) aminopropyl) methacrylamide,
N- (3-morpholinopropyl) methacrylamide.

Examples of the compound represented by the formula (3-3) include the following acrylate compounds in which s is 1, T is a group represented by the formula (3-Ta), and R ³⁷ is a hydrogen atom. be able to.
2-dimethylaminoethyl acrylate,
3-dimethylaminopropyl acrylate,
4-dimethylaminobutyl acrylate,
2-diethylaminoethyl acrylate,
3-diethylaminopropyl acrylate,
4-diethylaminobutyl acrylate,
3-bistrimethylsilylaminopropyl acrylate,
3-di (glycidyl) aminopropyl acrylate,
3-di (tetrahydrofurfuryl) aminopropyl acrylate,
3-morpholinopropyl acrylate.

Examples of the compound represented by the formula (3-3) include the following methacrylate compounds in which s is 1, T is a group represented by the formula (3-Ta), and R ³⁷ is a methyl group. be able to.
2-dimethylaminoethyl methacrylate,
3-dimethylaminopropyl methacrylate,
4-dimethylaminobutyl methacrylate,
2-diethylaminoethyl methacrylate,
3-diethylaminopropyl methacrylate,
4-diethylaminobutyl methacrylate,
3-bistrimethylsilylaminopropyl methacrylate,
3-di (glycidyl) aminopropyl methacrylate,
3-di (tetrahydrofurfuryl) aminopropyl methacrylate,
3-morpholinopropyl methacrylate.

The compound represented by the formula (3) is preferably a compound represented by the formula (3-3), more preferably s is 1, T is the formula (3-Tb), and R ³⁷ Is an acrylamide compound or a methacrylamide compound in which is a hydrogen atom or a methyl group.

More preferably,
N- (3-dimethylaminopropyl) acrylamide,
N- (3-diethylaminopropyl) acrylamide,
N- (3-dimethylaminopropyl) methacrylamide,
N- (3-diethylaminopropyl) methacrylamide.

（式中、ｔは０〜１０の数を表し、Ｒ^３４は窒素原子及び／又は酸素原子を有していてもよいヒドロカルビル基、又は、トリヒドロカルビルシリル基を表す。）

（式中、ｕは０〜１０の数を表し、Ｒ^３４は窒素原子及び／又は酸素原子を有していてもよいヒドロカルビル基、又は、トリヒドロカルビルシリル基を表す。）As a preferred compound represented by the formula (3), Z ¹ is a group represented by the formula (3-Z), Z ² is a hydrocarbylene group, and A ^{3 of} Z ¹ and hydro of Z ² compound Karubiren group is bonded, is a ^{group Z 1} and ^{Z 2} is represented by the formula (3-Z), ^{the compound a 3} and ^{Z 2} of ^{a 3} of ^{Z 1} is attached and the like . Examples of the compound include a compound represented by the following formula (3-4) in which E is an oxygen atom and p is 0, and a compound represented by the following formula (3-5).

(In the formula, t represents a number of 0 to 10, and R ³⁴ represents a hydrocarbyl group which may have a nitrogen atom and / or an oxygen atom, or a trihydrocarbylsilyl group.)

(In the formula, u represents a number of 0 to 10, and R ³⁴ represents a hydrocarbyl group which may have a nitrogen atom and / or an oxygen atom, or a trihydrocarbylsilyl group.)

In formula, t and u represent the number of 0-10, respectively. From the viewpoint of improving fuel economy, it is preferably 2 or more, and preferably 7 or less from the viewpoint of improving economy during production.

^Wherein the definition of ^{R 34,} exemplary and preferred groups defined written in ^{R 34} of formula (3-A), the same as examples.

R ³⁴ is preferably a hydrocarbyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

Examples of the compound represented by the formula (3-4) include β such as N-methyl-β-propiolactam, N- (t-butyl) -β-propiolactam, N-phenyl-β-propiolactam. A propiolactam compound;
1-methyl-2-pyrrolidone, 1- (t-butyl) -2-pyrrolidone, 1-phenyl-2-pyrrolidone, 1- (p-methylphenyl) -2-pyrrolidone, 1- (p-methoxyphenyl)- 2-pyrrolidone, 1-benzyl-2-pyrrolidone, 1-naphthyl-2-pyrrolidone, 1-phenyl-5-methyl-2-pyrrolidone, 1- (t-butyl) -5-methyl-2-pyrrolidone, 1- 2-pyrrolidone compounds such as (t-butyl) -1,3-dimethyl-2-pyrrolidone;
1- (t-butyl) -2-piperidone, 1-phenyl-2-piperidone, 1- (p-methylphenyl) -2-piperidone, 1- (p-methoxyphenyl) -2-piperidone, 1-naphthyl- 2-piperidone compounds such as 2-piperidone;
N-methyl-ε-caprolactam, N-ethyl-ε-caprolactam, N- (n-propyl) -ε-caprolactam, N-phenyl-ε-caprolactam, N- (p-methoxyphenyl) -ε-caprolactam, N An ε-caprolactam compound such as benzyl-ε-caprolactam;
Mention may be made of ω-laurylactam compounds such as N-phenyl-ω-laurylactam.

The compound represented by the formula (3-4) is preferably a 2-pyrrolidone compound or an ε-caprolactam compound, and more preferably 1-hydrocarbyl substituted-2-pyrrolidone, N-hydrocarbyl substituted-ε-caprolactam. More preferred are 1-alkyl substituted-2-pyrrolidone, 1-aryl substituted-2-pyrrolidone, N-alkyl substituted-ε-caprolactam, N-aryl substituted-ε-caprolactam, particularly preferably 1- Phenyl-2-pyrrolidone, N-methyl-ε-caprolactam.

Examples of the compound represented by the formula (3-5) include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di (n-propyl) -2. -Mentioning 1,3-hydrocarbyl-substituted-2-imidazolidinones such as imidazolidinone, 1,3-di (t-butyl) -2-imidazolidinone, 1,3-diphenyl-2-imidazolidinone Can do.

The compound represented by the formula (3-5) is preferably 1,3-substituted-2-imidazolidinone, more preferably 1,3-hydrocarbyl-substituted-2-imidazolidinone, More preferred is 1,3-dialkyl-2-imidazolidinone. The 1,3-dialkyl-2-imidazolidinone is preferably 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di (n-propyl). ) -2-imidazolidinone, more preferably 1,3-dimethyl-2-imidazolidinone.

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、ｖは１〜１０の整数を表し、Ｒ^４１、Ｒ^４２及びＲ^４３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^４１、Ｒ^４２及びＲ^４３の少なくとも１つがアルコキシ基であり、Ａ^４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 (4).

(In the formula, v represents an integer of 1 to 10, R ⁴¹ , R ⁴² and R ⁴³ each independently represents an alkyl group or an alkoxy group, and at least one of R ⁴¹ , R ⁴² and R ⁴³ is an alkoxy group. And A ⁴ represents a substituted amino group.)

R ⁴¹ , R ⁴² and R ⁴³ each represents an alkyl group or an alkoxy group.

^Examples of the alkyl group for R ⁴¹ , R ⁴² and R ⁴³ 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 ⁴¹ , R ⁴² and R ⁴³ 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-ethylhexanoxy. Etc. 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 ⁴¹ , R ⁴² and R ⁴³ is an alkoxy group, and in order to improve fuel economy, preferably at least two of R ⁴¹ , R ⁴² and R ⁴³ are alkoxy groups, more preferably, Three of R ⁴¹ , R ⁴² and R ⁴³ are alkoxy groups.

（式中、Ｒ^４４及びＲ^４５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^４４とＲ^４５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^４４とＲ^４５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 (4), A ⁴ represents a substituted amino group. The substituted amino group for A ⁴ is preferably a group represented by the following formula (4-A).

(Wherein R ⁴⁴ and R ⁴⁵ are each a hydrogen atom, a nitrogen atom and / or a hydrocarbyl group optionally having an oxygen atom, or R ⁴⁴ and R ⁴⁵ are bonded to each other to form a nitrogen atom and / Alternatively, a hydrocarbylene group which may have an oxygen atom as a hetero atom, or R ⁴⁴ and R ⁴⁵ are one group and represent a group bonded to a nitrogen atom by a double bond.)

R ⁴⁴ and R ⁴⁵ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or R ⁴⁴ and R ⁴⁵ are bonded to form a nitrogen atom and / or an oxygen atom. which may have hydrocarbylene group, or, R ⁴⁴ and R ⁴⁵ form one group represents a group which bonds to a nitrogen atom with a double bond.

Examples of the hydrocarbyl group of R ⁴⁴ and R ⁴⁵ include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups and other alkyl groups; vinyl groups, allyl groups, 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 ⁴⁴ and R ⁴⁵ 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 ⁴⁴ and R ⁴⁵ include alkoxyalkyl groups 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 ⁴⁴ and R ⁴⁵ is preferably 1 to 10, and more preferably 1 to 6.

Examples of the group to which R ⁴⁴ and R ⁴⁵ 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 ⁴⁴ and R ⁴⁵ are bonded is preferably 2 to 20, and more preferably 2 to 12.

Examples of one group in which R ⁴⁴ and R ⁴⁵ are bonded to the nitrogen atom with a double bond include ethylidene group, propylidene group, butylidene group, 1-methylethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene 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 ⁴⁴ and R ⁴⁵ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 12.

R ⁴⁴ and R ⁴⁵ are preferably a hydrocarbyl group, a hydrocarbylene group in which R ³⁴ and R ³⁵ are bonded, or R ³⁴ and R ³⁵ are one group, and 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.

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

As a compound represented by Formula (4), as a compound in which R ⁴⁴ and R ⁴⁵ 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.

Examples of the compound represented by the formula (4) include compounds in which R ⁴⁴ and R ⁴⁵ 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 (4), as a compound in which R ⁴⁴ and R ⁴⁵ are oxiranyl groups,
{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 (4), as a compound in which R ⁴⁴ and R ⁴⁵ 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 (4), as a compound in which R ⁴⁴ and R ⁴⁵ 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 the formula (4), as a compound in which R ⁴⁴ and R ⁴⁵ are tetrahydrofurfuryl groups,
{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 (4), as a compound in which R ⁴⁴ and R ⁴⁵ 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 a compound represented by Formula (4), as a compound in which R ⁴⁴ and R ⁴⁵ 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 (4),
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 (A) in order to improve fuel efficiency. Yes, more preferably 0.02% by mass or more, still more preferably 0.05% by 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% per 100% by mass of the conjugated diene polymer (A) in order to improve fuel economy and wear resistance. It is at least mass%, more preferably at least 0.02 mass%, still more preferably at least 0.05 mass%. 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 (A) according to the first aspect of 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 (A) 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 (A) is preferably 70 mol% or less, more preferably 60 mol% or less, in order to improve fuel economy by setting the content of the conjugated diene unit to 100 mol%. It is. 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 (A) 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 manufacturing method of a conjugated diene polymer (A), the manufacturing method which has the following process A and process B can be mention | raise | lifted.
(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 the compound (G) or 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 step B, the amount of the compound (G) or alkoxysilane compound reacted with the polymer prepared in step A is usually 0.1 to 3 mol per mol of alkali metal derived from the organic alkali metal catalyst, Preferably, it is 0.5-2 mol, More preferably, it is 0.7-1.5 mol.

（式中、Ｒ^５１は水素原子又はヒドロカルビル基を表し、ｗは０又は１であり、Ｒ^５２はヒドロカルビレン基を表し、Ｘ^５１、Ｘ^５２及びＸ^５３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^５１、Ｘ^５２及びＸ^５３の少なくとも１つが置換アミノ基である。）

（式中、Ｒ^６１は水素原子又はヒドロカルビル基を表し、ｘは０又は１であり、Ｒ^６２はヒドロカルビレン基を表し、Ａ^６は置換アミノ基、又は、含窒素複素環基を表す。）The conjugated diene polymer (B) according to the second aspect of the present invention includes a monomer unit based on a conjugated diene, a monomer unit based on a compound represented by the following formula (5), and the following formula (6): Monomer units based on the compounds represented. By combining the conjugated diene polymer (B), silica, and a specific silane coupling agent, the fuel efficiency, wet grip performance, and wear resistance (especially fuel efficiency and wet grip performance) are synergistic. Can be improved.

(In the formula, R ⁵¹ represents a hydrogen atom or a hydrocarbyl group, w is 0 or 1, R ⁵² represents a hydrocarbylene group, and X ⁵¹ , X ^52, and X ⁵³ are each independently a substituted amino group. Or an optionally substituted hydrocarbyl group, wherein at least one of X ⁵¹ , X ⁵² and X ⁵³ is a substituted amino group.)

(In the formula, R ⁶¹ represents a hydrogen atom or a hydrocarbyl group, x is 0 or 1, R ⁶² represents a hydrocarbylene group, and A ⁶ represents a substituted amino group or a nitrogen-containing heterocyclic group. )

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

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

R ^{51 in} formula (5) represents a hydrogen atom or a hydrocarbyl group.

^Examples of the hydrocarbyl group for R ⁵¹ include an alkyl group and an alkenyl group.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group is preferable. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group, and a vinyl group is preferable.

R ⁵¹ is preferably a hydrogen atom, a methyl group, or a vinyl group.

Examples of the hydrocarbylene group for R ⁵² 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, it is preferable that the carbon atom of an alkylene group couple | bonds the group which the arylene group and the alkylene group couple | bonded with the silicon atom of Formula (5).

（式中、ｚは、１〜１０の整数を表す。）In a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), depending on the position of the carbon atom on the benzene ring from which a hydrogen atom is removed and the phenylene group to which the alkylene group is bonded, a para-phenylene-alkylene group ( For example, a group represented by the following formula (5a)), a meta-phenylene-alkylene group (for example, a group represented by the following formula (5b)), an ortho-phenylene-alkylene group (for example, the following formula (5c )))).

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

The group in which an arylene group and an alkylene group are bonded is preferably a group in which a phenylene group and an alkylene group are bonded, and more preferably a group represented by the above formula (5a) or the above formula (5b). And more preferably a para-phenylene-methylene group (a group represented by the formula (5a) where z = 1) and a meta-phenylene-methylene group (a formula (5b) where z = 1). Group, a para-phenylene-ethylene group (a group represented by the formula (5a) where z = 2), a meta-phenylene-ethylene group (a formula (5b) where z = 2). Group).

When R ⁵¹ is a hydrogen atom or a methyl group and w is 1, R ⁵² is preferably a group in which an arylene group and an alkylene group are bonded or an arylene group, more preferably a phenylene group and an alkylene group. And a phenylene group, more preferably a phenylene group.

When R ⁵¹ is a vinyl group and w is 1, R ⁵² is preferably an alkylene group, more preferably a methylene group or an ethylene group.

In the formula (5), R ⁵¹ is preferably a hydrogen atom and w is 0.

The hydrocarbyl group which may have a substituent of X ⁵¹ , X ⁵² and X ⁵³ is a hydrocarbyl group which may have 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 ⁵¹ , X ⁵² and X ⁵³ 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 ⁵¹ , X ⁵² and X ⁵³ include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group and an ethoxyethyl group.

Examples of the hydrocarbyl group having a nitrogen atom of X ⁵¹ , X ⁵² and X ⁵³ include dialkylaminoalkyl groups such as a dimethylaminomethyl group, a dimethylaminoethyl group, a diethylaminomethyl group and a diethylaminoethyl group.

Examples of the hydrocarbyl group having a silicon atom of X ⁵¹ , X ⁵² and X ⁵³ 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 ⁵¹ , X ⁵² and X ⁵³ is preferably 1 to 10, more preferably 1 to 4.

The hydrocarbyl group which may have a substituent of X ⁵¹ , X ⁵² and X ⁵³ 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^５３及びＲ^５４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^５３とＲ^５４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^５３とＲ^５４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 ⁵¹ , X ⁵² and X ⁵³ is preferably a group represented by the following formula (5-X).

(In the formula, each of R ⁵³ and R ⁵⁴ has a hydrocarbyl group, a trihydrocarbyl silyl group, or R ⁵³ and R ⁵⁴ 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 ⁵³ and R ⁵⁴ are one group and represent a group bonded to the nitrogen atom by a double bond.)

Examples of the hydrocarbyl group of R ⁵³ and R ⁵⁴ 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 ⁵³ and R ⁵⁴ is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.

The hydrocarbyl group of R ⁵³ and R ⁵⁴ is preferably an alkyl group, more preferably a linear alkyl group.

The trihydrocarbyl silyl group R ⁵³ and R ^54, may be mentioned trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, a trialkylsilyl group such as tert- butyldimethylsilyl group.

The trihydrocarbylsilyl group of R ⁵³ and R ⁵⁴ 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 oxygen atom to which R ⁵³ and R ⁵⁴ 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 in the hydrocarbylene group which may have a nitrogen atom and / or oxygen atom to which R ⁵³ and R ⁵⁴ 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 ⁵³ and R ⁵⁴ 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 ⁵³ and R ⁵⁴ 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 ⁵³ and R ⁵⁴ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 6.

R ⁵³ and R ⁵⁴ are preferably an alkyl group, a trialkylsilyl group, an alkylene group in which R ¹³ and R ¹⁴ are bonded, and more preferably an alkyl group.

Examples of the group represented by the formula (5-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 further 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 (5-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 (5), at least one of X ⁵¹ , X ⁵² and X ⁵³ is a substituted amino group, preferably two or more of X ⁵¹ , X ⁵² and X ⁵³ are substituted amino groups, more preferably, Two of X ⁵¹ , X ⁵² and X ⁵³ are substituted amino groups.

Examples of the compound represented by formula (5) include the following compounds as compounds in which R ⁵¹ is a hydrogen atom and one of X ⁵¹ , X ⁵² and X ⁵³ is a dialkylamino group.

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

Examples of the compound represented by the formula (5) include the following compounds as compounds in which R ⁵¹ is a hydrogen atom and two of X ⁵¹ , X ⁵² and X ⁵³ are dialkylamino groups.

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

Examples of the compound represented by the formula (5) include the following compounds as compounds in which R ⁵¹ is a methyl group and two of X ⁵¹ , X ⁵² and X ⁵³ are dialkylamino groups.

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

Examples of the compound represented by formula (5) include the following compounds as compounds in which R ⁵¹ is a vinyl group and two of X ⁵¹ , X ⁵² and X ⁵³ are dialkylamino groups.

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

Examples of the compound represented by the formula (5) include the following compounds as compounds in which R ⁵¹ is a hydrogen atom and three of X ⁵¹ , X ⁵² and X ⁵³ are dialkylamino groups.

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

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

Examples of the compound represented by formula (5) include the following compounds as compounds in which R ⁵¹ is a methyl group and three of X ⁵¹ , X ⁵² and X ⁵³ are dialkylamino groups.

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

Examples of the compound represented by formula (5) include the following compounds as compounds in which R ⁵¹ is a vinyl group and three of X ⁵¹ , X ⁵² and X ⁵³ are dialkylamino groups.

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

The compound represented by the formula (5) is preferably a compound in which two of X ⁵¹ , X ⁵² and X ⁵³ are dialkylamino groups, more preferably R ⁵¹ is a hydrogen atom, and w = A compound that is zero. More preferred is a compound in which the remaining one of X ⁵¹ , X ⁵² and X ⁵³ is an alkyl group or an alkoxyalkyl group. Particularly preferably,
Bis (dimethylamino) methylvinylsilane,
Bis (diethylamino) methylvinylsilane,
Bis (di-n-propylamino) methylvinylsilane,
Bis (di-n-butylamino) methylvinylsilane,
Bis (dimethylamino) ethylvinylsilane,
Bis (diethylamino) ethylvinylsilane,
Bis (di-n-propylamino) ethylvinylsilane,
Bis (di-n-butylamino) ethylvinylsilane.

R ^{61 in the} above formula (6) represents a hydrogen atom or a hydrocarbyl group.

^Examples of the hydrocarbyl group for R ⁶¹ include an alkyl group and an alkenyl group.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group is preferable. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group, and a vinyl group is preferable.

R ⁶¹ is preferably a hydrogen atom, a methyl group, or a vinyl group.

Examples of the hydrocarbylene group for R ⁶² include an alkylene group, an arylene group, and a group in which an arylene group and an alkylene group are bonded.

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

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

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

In the group in which the arylene group and the alkylene group are bonded, the carbon atom of the arylene group is preferably bonded to the carbon atom to which R ^{61 in} the formula (6) is bonded.

（式中、ｂは１〜１０の整数を表す。）In a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), depending on the position of the carbon atom on the benzene ring from which a hydrogen atom has been removed and the phenylene group to which the alkylene group is bonded, For example, a group represented by the following formula (6a).), A meta-phenylene-alkylene group (for example, a group represented by the following formula (6b)), an ortho-phenylene-alkylene group (for example, the following formula (6c )))).

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

The group in which an arylene group and an alkylene group are bonded is preferably a group in which a phenylene group and an alkylene group are bonded, and more preferably a group represented by the above formula (6a) or the above formula (6b). And more preferably a para-phenylene-methylene group (a group represented by the formula (6a) where b = 1), a meta-phenylene-methylene group (a formula (6b) where b = 1). Group, a para-phenylene-ethylene group (a group represented by the formula (6a) where b = 2), a meta-phenylene-ethylene group (a formula (6b) where b = 2). Group).

（式中、ｙは０〜５の整数を表し、ｙが１〜５の整数である場合、（ＣＨ_２）_ｙはベンゼン環上の置換基であり、（ＣＨ_２）_ｙがＡ^６と結合し、ｙが０である場合、（ＣＨ_２）_ｙはベンゼン環とＡ^６との結合を表す。）

（式中、ｙは０〜５の整数を表し、ｙが１〜５の整数である場合、（ＣＨ_２）_ｙがＡ^６と結合し、ｙが０である場合、（ＣＨ_２）_ｙはベンゼン環とＡ^６との結合を表す。）When R ⁶¹ is a hydrogen atom or a methyl group and x is 1, R ⁶² is preferably a group in which an arylene group and an alkylene group are bonded or an arylene group, more preferably a phenylene group and an alkylene group. And a phenylene group, more preferably a group represented by the following formula (6-Y), particularly preferably a group represented by the following formula (6-Ya) or the following formula ( 6-Yb). Moreover, y is 0-5 in a formula, Preferably it is 0-2.

(In the formula, y represents an integer of 0 to 5, and when y is an integer of 1 to 5, (CH ₂ ) _y is a substituent on the benzene ring, and (CH ₂ ) _y is bonded to A ^6. And when y is 0, (CH ₂ ) _y represents a bond between the benzene ring and A ^6. )

(In the formula, y represents an integer of 0 to 5, and when y is an integer of 1 to 5, (CH ₂ ) _y is bonded to A ⁶ and when y is 0, (CH ₂ ) _y is It represents a bond between the benzene ring and a ^6.)

When R ⁶¹ is a vinyl group and x is 1, R ⁶² is preferably an alkylene group, more preferably a methylene group or an ethylene group.

A ⁶ represents a substituted amino group or a nitrogen-containing heterocyclic group.

（式中、Ｒ^６３及びＲ^６４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^６３とＲ^６４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^６３とＲ^６４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 ⁶ is preferably a group represented by the following formula (6-X).

(In the formula, each of R ⁶³ and R ⁶⁴ has a hydrocarbyl group, a trihydrocarbyl silyl group, or R ⁶³ and R ⁶⁴ 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 ⁶³ and R ⁶⁴ are one group and represent a group bonded to the nitrogen atom by a double bond.)

Examples of the hydrocarbyl group of R ⁶³ and R ⁶⁴ 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 ⁶³ and R ⁶⁴ is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.

The hydrocarbyl group of R ⁶³ and R ⁶⁴ 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 ⁶³ and R ⁶⁴ include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group.

The trihydrocarbylsilyl group of R ⁶³ and R ⁶⁴ 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 ⁶³ and R ⁶⁴ are bonded as a hetero atom includes a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and an oxygen atom. And hydrocarbylene groups. Examples of the hydrocarbylene group include an alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. As the hydrocarbylene group having a nitrogen atom, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH—N A group represented by ═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified. Examples of the hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the hydrocarbylene group which may have a nitrogen atom and / or oxygen atom to which R ⁶³ and R ⁶⁴ 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 ⁶³ and R ⁶⁴ 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 ⁶³ and R ⁶⁴ are bonded to the nitrogen atom with a double bond is ethylidene group, propylidene group, butylidene group, 1-methylethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene. And hydrocarbylidene groups such as groups.

The number of carbon atoms of one group in which R ⁶³ and R ⁶⁴ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 6.

R ⁶³ and R ⁶⁴ are preferably a hydrocarbyl group, a trihydrocarbyl silyl group, or a hydrocarbylene group in which R ⁶³ and R ⁶⁴ are bonded.

Examples of the group represented by the formula (6-X) include an acyclic amino group and a cyclic amino group.

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

Examples of the acyclic amino group further 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-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 (6-X) is preferably a group in which R ⁶³ and R ⁶⁴ are hydrocarbyl groups, a group in which R ⁶³ and R ⁶⁴ are trihydrocarbylsilyl groups, and R ⁶³ and R ⁶⁴ are bonded. Group which is a hydrocarbylene group. More preferably, R ⁶³ and R ⁶⁴ are a group that is a linear alkyl group, R ²³ and R ²⁴ are a group that is a trialkylsilyl group, and a group that is a polymethylene group to which R ⁶³ and R ⁶⁴ are bonded.

The group represented by the formula (6-X) is more preferably a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, a di (n-butyl) amino group, a bis (trimethylsilyl) amino group, A bis (tert-butyldimethylsilyl) amino group, a 1-pyrrolidinyl group, a 1-piperidinyl group, and a 1-hexamethyleneimino group, particularly preferably a 1-pyrrolidinyl group.

Examples of the nitrogen-containing heterocyclic group represented by A ⁶ 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 ⁶ 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 the 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 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 ⁶ 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 ⁶ 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 the 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 heterocyclic group represented by A ⁶ is preferably a nitrogen-containing aromatic heterocyclic group, more preferably a nitrogen-containing aromatic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring, More preferred are a group having an imidazole ring, a group having a pyridine ring, and a group having a quinoline ring, and particularly preferred is a group having a pyridine ring.

Examples of the compound represented by formula (6) include the following compounds as compounds in which R ⁶¹ is a hydrogen atom, x is 0, and A ⁶ is a substituted amino group.

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

As a compound represented by the formula (6), R ⁶¹ is a hydrogen atom, x is 1, R ⁶² is a group represented by the formula (6-Y), and A ⁶ is a substituted amino group. The following compound can be mention | raise | lifted as a certain compound.

Compound in which y in formula (6-Y) is 0:
4-N, N-dimethylaminostyrene,
3-N, N-dimethylaminostyrene,
4-N, N-diethylaminostyrene,
3-N, N-diethylaminostyrene,
4-N, N-di-n-propylaminostyrene,
3-N, N-di-n-propylaminostyrene,
4-N, N-di-n-butylaminostyrene,
3-N, N-di-n-butylaminostyrene,
4-N, N-diallylaminostyrene,
3-N, N-diallylaminostyrene,
4-N, N-bis (trimethylsilyl) aminostyrene,
3-N, N-bis (trimethylsilyl) aminostyrene,
4-N, N-bis (tert-butyldimethylsilyl) aminostyrene,
3-N, N-bis (tert-butyldimethylsilyl) aminostyrene,
4- (1-aziridinyl) styrene,
3- (1-aziridinyl) styrene,
4- (1-pyrrolidinyl) styrene,
3- (1-pyrrolidinyl) styrene,
4- (1-piperidinyl) styrene,
3- (1-piperidinyl) styrene,
4- (1-hexamethyleneimino) styrene,
3- (1-Hexamethyleneimino) styrene.

Compound in which y in formula (6-Y) is 1:
4-N, N-dimethylaminomethylstyrene,
3-N, N-dimethylaminomethylstyrene,
4-N, N-diethylaminomethylstyrene,
3-N, N-diethylaminomethylstyrene,
4-N, N-di-n-propylaminomethylstyrene,
3-N, N-di-n-propylaminomethylstyrene,
4-N, N-di-n-butylaminomethylstyrene,
3-N, N-di-n-butylaminomethylstyrene,
4-N, N-diallylaminomethylstyrene,
3-N, N-diallylaminomethylstyrene,
4-N, N-bis (trimethylsilyl) aminomethylstyrene,
3-N, N-bis (trimethylsilyl) aminomethylstyrene,
4-N, N-bis (tert-butyldimethylsilyl) aminomethylstyrene,
3-N, N-bis (tert-butyldimethylsilyl) aminomethylstyrene,
4- (1-aziridinyl) methylstyrene,
3- (1-aziridinyl) methylstyrene,
4- (1-pyrrolidinyl) methylstyrene,
3- (1-pyrrolidinyl) methylstyrene,
4- (1-piperidinyl) methylstyrene,
3- (1-piperidinyl) methylstyrene,
4- (1-hexamethyleneimino) methylstyrene,
3- (1-Hexamethyleneimino) methylstyrene.

Compound in which y in formula (6-Y) is 2:
4-N, N-dimethylaminoethylstyrene,
3-N, N-dimethylaminoethylstyrene,
4-N, N-diethylaminoethylstyrene,
3-N, N-diethylaminoethylstyrene,
4-N, N-di-n-propylaminoethylstyrene,
3-N, N-di-n-propylaminoethylstyrene,
4-N, N-di-n-butylaminoethylstyrene,
3-N, N-di-n-butylaminoethylstyrene,
4-N, N-diallylaminoethylstyrene,
3-N, N-diallylaminoethylstyrene,
4-N, N-bis (trimethylsilyl) aminoethylstyrene,
3-N, N-bis (trimethylsilyl) aminoethylstyrene,
4-N, N-bis (tert-butyldimethylsilyl) aminoethylstyrene,
3-N, N-bis (tert-butyldimethylsilyl) aminoethylstyrene,
4- (1-aziridinyl) ethylstyrene,
3- (1-aziridinyl) ethylstyrene,
4- (1-pyrrolidinyl) ethylstyrene,
3- (1-pyrrolidinyl) ethylstyrene,
4- (1-piperidinyl) ethylstyrene,
3- (1-piperidinyl) ethylstyrene,
4- (1-hexamethyleneimino) ethylstyrene,
3- (1-Hexamethyleneimino) ethylstyrene.

Examples of the compound represented by formula (6) include the following compounds as compounds in which R ⁶¹ is a methyl group, x is 0, and A ⁶ is a substituted amino group.

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

As a compound represented by the formula (6), R ⁶¹ is a methyl group, x is 1, R ⁶² is a group represented by the formula (6-Y), and A ⁶ is a substituted amino group. The following compound can be mention | raise | lifted as a certain compound.

Compound in which y in formula (6-Y) is 0:
4-N, N-dimethylaminoisopropenylbenzene,
3-N, N-dimethylaminoisopropenylbenzene,
4-N, N-diethylaminoisopropenylbenzene,
3-N, N-diethylaminoisopropenylbenzene,
4-N, N-di-n-propylaminoisopropenylbenzene,
3-N, N-di-n-propylaminoisopropenylbenzene,
4-N, N-di-n-butylaminoisopropenylbenzene,
3-N, N-di-n-butylaminoisopropenylbenzene,
4-N, N-diallylaminoisopropenylbenzene,
3-N, N-diallylaminoisopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminoisopropenylbenzene,
3-N, N-bis (trimethylsilyl) aminoisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminoisopropenylbenzene, 3-N, N-bis (tert-butyldimethylsilyl) aminoisopropenylbenzene, 4- (1-aziridinyl) isopropenylbenzene,
3- (1-aziridinyl) isopropenylbenzene,
4- (1-pyrrolidinyl) isopropenylbenzene,
3- (1-pyrrolidinyl) isopropenylbenzene,
4- (1-piperidinyl) isopropenylbenzene,
3- (1-piperidinyl) isopropenylbenzene,
4- (1-hexamethyleneimino) isopropenylbenzene,
3- (1-Hexamethyleneimino) isopropenylbenzene.

Compound in which y in formula (6-Y) is 1:
4-N, N-dimethylaminomethylisopropenylbenzene,
3-N, N-dimethylaminomethylisopropenylbenzene,
4-N, N-diethylaminomethylisopropenylbenzene,
3-N, N-diethylaminomethylisopropenylbenzene,
4-N, N-di-n-propylaminomethylisopropenylbenzene,
3-N, N-di-n-propylaminomethylisopropenylbenzene,
4-N, N-di-n-butylaminomethylisopropenylbenzene,
3-N, N-di-n-butylaminomethylisopropenylbenzene,
4-N, N-diallylaminomethylisopropenylbenzene,
3-N, N-diallylaminomethylisopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminomethylisopropenylbenzene,
3-N, N-bis (trimethylsilyl) aminomethylisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminomethylisopropenylbenzene,
3-N, N-bis (tert-butyldimethylsilyl) aminomethylisopropenylbenzene,
4- (1-aziridinyl) methylisopropenylbenzene,
3- (1-aziridinyl) methyl isopropenylbenzene,
4- (1-pyrrolidinyl) methylisopropenylbenzene,
3- (1-pyrrolidinyl) methylisopropenylbenzene,
4- (1-piperidinyl) methyl isopropenylbenzene,
3- (1-piperidinyl) methylisopropenylbenzene,
4- (1-hexamethyleneimino) methylisopropenylbenzene,
3- (1-Hexamethyleneimino) methylisopropenylbenzene.

Compound in which y in formula (6-Y) is 2:
4-N, N-dimethylaminoethylisopropenylbenzene,
3-N, N-dimethylaminoethylisopropenylbenzene,
4-N, N-diethylaminoethylisopropenylbenzene,
3-N, N-diethylaminoethylisopropenylbenzene,
4-N, N-di-n-propylaminoethylisopropenylbenzene,
3-N, N-di-n-propylaminoethylisopropenylbenzene,
4-N, N-di-n-butylaminoethylisopropenylbenzene,
3-N, N-di-n-butylaminoethyl isopropenylbenzene,
4-N, N-diallylaminoethyl isopropenylbenzene,
3-N, N-diallylaminoethylisopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminoethylisopropenylbenzene,
3-N, N-bis (trimethylsilyl) aminoethylisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminoethylisopropenylbenzene,
3-N, N-bis (tert-butyldimethylsilyl) aminoethylisopropenylbenzene,
4- (1-aziridinyl) ethyl isopropenylbenzene,
3- (1-aziridinyl) ethyl isopropenylbenzene,
4- (1-pyrrolidinyl) ethyl isopropenylbenzene,
3- (1-pyrrolidinyl) ethyl isopropenylbenzene,
4- (1-piperidinyl) ethyl isopropenylbenzene,
3- (1-piperidinyl) ethyl isopropenylbenzene,
4- (1-hexamethyleneimino) ethyl isopropenylbenzene,
3- (1-Hexamethyleneimino) ethyl isopropenylbenzene.

Examples of the compound represented by formula (6) include the following compounds as compounds in which R ⁶¹ is a vinyl group, x is 0, and A is a substituted amino group.

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

Examples of the compound represented by the formula (6) include the following compounds as compounds in which R ⁶¹ is a vinyl group, x is 1, R ⁶² is an alkylene group, and A ⁶ is a substituted amino group. be able to.

Compound R ⁶² 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 ^R62 is an ethylene group:
5-N, N-dimethylamino-3-methylene-1-pentene,
5-N, N-diethylamino-3-methylene-1-pentene,
5-N, N-di-n-propylamino-3-methylene-1-pentene,
5-N, N-di-n-butylamino-3-methylene-1-pentene,
5-N, N-diallylamino-3-methylene-1-pentene,
5-N, N-bis (trimethylsilyl) amino-3-methylene-1-pentene,
5-N, N-bis (tert-butyldimethylsilyl) amino-3-methylene-1-pentene,
5- (1-aziridinyl) -3-methylene-1-pentene,
5- (1-pyrrolidinyl) -3-methylene-1-pentene,
5- (1-piperidinyl) -3-methylene-1-pentene,
5- (1-hexamethyleneimino) -3-methylene-1-pentene,
1- (3-methylene-4-pentenyl) pyrrole,
1- (3-methylene-4-pentenyl) imidazole,
1- (3-methylene-4-pentenyl) pyrazole.

As the compound represented by the formula (6), R ⁶¹ is a hydrogen atom, x is 1, R ⁶² is a group represented by the formula (6-Y), and A ⁶ is a nitrogen-containing aliphatic. Examples of the compound that is a heterocyclic group include the following compounds.

Compound in which y in formula (6-Y) is 0:
4-N-methyl-2-aziridinylstyrene,
4-N-methyl-2-pyrrolidinylstyrene,
4-N-methyl-3-pyrrolidinylstyrene,
4-N-methyl-2-hexamethyleneiminostyrene,
4-N-methyl-3-hexamethyleneiminostyrene,
4-N-methyl-4-hexamethyleneiminostyrene.

Compound in which y in formula (6-Y) is 1:
4-N-methyl-2-aziridinylmethylstyrene,
4-N-methyl-2-pyrrolidinylmethylstyrene,
4-N-methyl-3-pyrrolidinylmethylstyrene,
4-N-methyl-2-hexamethyleneiminomethylstyrene,
4-N-methyl-3-hexamethyleneiminomethylstyrene,
4-N-methyl-4-hexamethyleneiminomethylstyrene.

Compound in which y in formula (6-Y) is 2:
4-N-methyl-2-aziridinylethylstyrene,
4-N-methyl-2-pyrrolidinylethylstyrene,
4-N-methyl-3-pyrrolidinylethylstyrene,
4-N-methyl-2-hexamethyleneiminoethylstyrene,
4-N-methyl-3-hexamethyleneiminoethylstyrene,
4-N-methyl-4-hexamethyleneiminoethylstyrene.

As the compound represented by the formula (6), R ⁶¹ is a methyl group, x is 1, R ⁶² is a group represented by the formula (6-Y), and A ⁶ is a nitrogen-containing aliphatic group. Examples of the compound that is a heterocyclic group include the following compounds.

Compound in which y in formula (6-Y) is 0:
4-N-methyl-2-aziridinylisopropenylbenzene,
4-N-methyl-2-pyrrolidinylisopropenylbenzene,
4-N-methyl-3-pyrrolidinylisopropenylbenzene,
4-N-methyl-2-hexamethyleneiminoisopropenylbenzene,
4-N-methyl-3-hexamethyleneiminoisopropenylbenzene,
4-N-methyl-4-hexamethyleneiminoisopropenylbenzene.

Compound in which y in formula (6-Y) is 1:
4-N-methyl-2-aziridinylmethyl isopropenylbenzene,
4-N-methyl-2-pyrrolidinylmethylisopropenylbenzene,
4-N-methyl-3-pyrrolidinylmethylisopropenylbenzene,
4-N-methyl-2-hexamethyleneiminomethylisopropenylbenzene,
4-N-methyl-3-hexamethyleneiminomethylisopropenylbenzene,
4-N-methyl-4-hexamethyleneiminomethylisopropenylbenzene.

Compound in which y in formula (6-Y) is 2:
4-N-methyl-2-aziridinylethyl isopropenylbenzene,
4-N-methyl-2-pyrrolidinylethyl isopropenylbenzene,
4-N-methyl-3-pyrrolidinylethyl isopropenylbenzene,
4-N-methyl-2-hexamethyleneiminoethylisopropenylbenzene,
4-N-methyl-3-hexamethyleneiminoethyl isopropenylbenzene,
4-N-methyl-4-hexamethyleneiminoethylisopropenylbenzene.

Examples of the compound represented by formula (6) include the following compounds as compounds in which R ⁶¹ is a vinyl group, x is 0, and A ⁶ is a nitrogen-containing aliphatic heterocyclic group.

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

Examples of the compound represented by the formula (6) include compounds in which R ⁶¹ is a vinyl group, x is 1, R ⁶² is an alkylene group, and A ⁶ is a nitrogen-containing aliphatic heterocyclic group. Can be mentioned.

Compound R ⁶² is a methylene group:
N-methyl-2- (2-methylene-3-butenyl) aziridine,
N-methyl-2- (2-methylene-3-butenyl) pyrrolidine,
N-methyl-3- (2-methylene-3-butenyl) pyrrolidine,
N-methyl-2- (2-methylene-3-butenyl) hexamethyleneimine,
N-methyl-3- (2-methylene-3-butenyl) hexamethyleneimine,
N-methyl-4- (2-methylene-3-butenyl) hexamethyleneimine.

Compound in which ^R62 is an ethylene group:
N-methyl-2- (3-methylene-4-pentenyl) aziridine,
N-methyl-2- (3-methylene-4-pentenyl) pyrrolidine,
N-methyl-3- (3-methylene-4-pentenyl) pyrrolidine,
N-methyl-2- (3-methylene-4-pentenyl) hexamethyleneimine,
N-methyl-3- (3-methylene-4-pentenyl) hexamethyleneimine,
N-methyl-4- (3-methylene-4-pentenyl) hexamethyleneimine.

Examples of the compound represented by formula (6) include the following compounds as compounds in which R ⁶¹ is a hydrogen atom, x is 0, and A ⁶ is a nitrogen-containing aromatic heterocyclic group.

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

Examples of the compound represented by formula (6) include the following compounds as compounds in which R ⁶¹ is a methyl group, x is 0, and A ⁶ is a nitrogen-containing aromatic heterocyclic group.

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

Examples of the compound represented by formula (6) include the following compounds as compounds in which R ⁶¹ is a vinyl group, x is 0, and A ⁶ is a nitrogen-containing aromatic heterocyclic group.

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

Examples of the compound represented by the formula (6) include compounds in which R ⁶¹ is a vinyl group, x is 1, R ⁶² is an alkylene group, and A ⁶ is a nitrogen-containing aromatic heterocyclic group. Can be mentioned.

Compound R ⁶² 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 ^R62 is an ethylene group:
N-methyl-2- (3-methylene-4-pentenyl) imidazole,
N-methyl-4- (3-methylene-4-pentenyl) imidazole,
N-methyl-5- (3-methylene-4-pentenyl) imidazole,
2- (3-methylene-4-pentenyl) pyridine,
3- (3-methylene-4-pentenyl) pyridine,
4- (3-methylene-4-pentenyl) pyridine,
2- (3-methylene-4-pentenyl) quinoline,
3- (3-methylene-4-pentenyl) quinoline,
4- (3-Methylene-4-pentenyl) quinoline.

As the compound represented by the formula (6), preferably, R ⁶¹ is a hydrogen atom, x is 1, R ⁶² is a group represented by the formula (6-Y), and A ⁶ is substituted. It is a compound that is an amino group. More preferably, R ⁶¹ is a hydrogen atom, x is 1, R ⁶² is a group represented by the formula (6-Y), and A ⁶ is a group represented by the formula (6-X). It is a certain compound. More preferably, the compound ^{R 63} and ^{R 64} is a straight-chain alkyl group having a carbon number of 1-2 of the formula (6-X), the compound ^{R 63} and ^{R 64} is a trimethylsilyl group of the formula (6-X) And R ⁶³ and R ⁶⁴ in formula (6-X) are bonded to each other, and the group is a polymethylene group having 4 to 6 carbon atoms.

As the compound represented by the formula (6), particularly preferably,
4-N, N-bis (trimethylsilyl) aminostyrene,
3-N, N-bis (trimethylsilyl) aminostyrene,
4-N, N-dimethylaminomethylstyrene,
3-N, N-dimethylaminomethylstyrene,
4- (1-pyrrolidinyl) ethylstyrene,
3- (1-pyrrolidinyl) ethylstyrene.

The content of the monomer unit based on the compound represented by the formula (5) is preferably 0.01% by mass or more per 100% by mass of the conjugated diene polymer (B) in order to improve fuel efficiency. Yes, more preferably 0.02% by mass or more, still more preferably 0.05% by mass or more. In order to improve economy and wear resistance, the content is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

In the monomer unit based on the compound represented by the formula (5), the groups represented by X ⁵¹ , X ⁵² and X ⁵³ may be a hydroxyl group by hydrolysis or the like.

The content of the monomer unit based on the compound represented by the formula (6) is preferably 0.01% per 100% by mass of the conjugated diene polymer (B) in order to improve fuel efficiency and wear resistance. It is at least mass%, more preferably at least 0.02 mass%, still more preferably at least 0.05 mass%. In order to improve economy and wear resistance, the content is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

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

The molecular weight distribution of the conjugated diene polymer (B) is preferably 1 to 5 and more preferably 1 to 2 in order to improve fuel economy. 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 method for producing the conjugated diene polymer (B), a conjugated diene, a monomer represented by the above formula (5) and a formula represented by the above formula (6) are represented by an alkali metal catalyst in a hydrocarbon solvent. A method of polymerizing a monomer component containing the monomer to be produced can be mentioned.

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

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

A monomer component containing a conjugated diene, a compound represented by the above formula (5), and a compound represented by the above formula (6) is polymerized with an alkali metal catalyst in a hydrocarbon solvent to obtain a single monomer based on the conjugated diene. A polymer having a monomer unit, a monomer unit based on the compound represented by the above formula (5) and a monomer unit based on the compound represented by the above formula (6) 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 (5) 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 (6) is preferably 0.01% by mass in order to improve the fuel efficiency and wear resistance by setting the total amount of the monomer components used in the polymerization to 100% by mass. % Or more, more preferably 0.02 mass% or more, still more preferably 0.05 mass% or more. In order to improve economic efficiency and wear resistance, it is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. is there.

Polymerization may be carried out by combining a conjugated diene, a compound represented by formula (5) and a compound represented by formula (6) with a vinyl aromatic hydrocarbon. Examples of the vinyl aromatic hydrocarbon include styrene, α -Methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and the like can be mentioned. Styrene is preferable.

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

In the polymerization reaction, the total amount of the conjugated diene, the compound represented by the formula (5), the compound represented by the formula (6) and the vinyl aromatic hydrocarbon is 100. In order to increase the strength, it is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and still more preferably 100% by mass.

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

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

In the method for producing the conjugated diene polymers (A) and (B), if necessary, the conjugated diene polymer can be 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. A coupling agent may be added. An example of the coupling agent is a compound represented by the following formula (7).

R ⁷¹ _a ML _4-a (7)
Wherein R ⁷¹ 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 is an integer of 0 to 2. Represents.)

As the coupling agent represented by the above formula (7), 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 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 a conjugated diene polymer, (2) steam is added to the hydrocarbon solution of a 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 polymers (A) and (B) can be used as rubber components, and other rubber components and additives such as silica can be blended to obtain the rubber composition of the present invention. .

Content of the said conjugated diene polymer (A) and (B) in 100 mass% of rubber components is 5 mass% or more, Preferably it is 20 mass% or more, More preferably, it is 40 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 polymers (A) and (B) 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 polymers (A) and (B) 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 commercial products of silica, trade names made by Evonik Degussa, Ultrasil VN3-G, trade names made by Tosoh Silica, Inc., trade names VN3, AQ, ER, RS-150, trade names made by Rhodia, etc. Use Zeosil 1115MP, 1165MP, etc. Can do.

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 represented by the following formula (I) as a silane coupling agent. By blending the silane coupling agent represented by the following formula (I) together with the conjugated diene polymer and silica, the silica is dispersed well, resulting in low fuel consumption, wet grip performance and wear resistance (particularly low Fuel consumption and wet grip performance) can be significantly improved.
_{(C p H 2p + 1 O} ) 3 Si-C q H 2q -S-CO-C k H 2k + 1 (I)
(In the formula, p is an integer of 1 to 3, q is an integer of 1 to 5, and k is an integer of 5 to 12.)

p is an integer of 1 to 3, but 2 is preferable. When p is 4 or more, the coupling reaction tends to be slow.

Although q is an integer of 1-5, 2-4 are preferable and 3 is more preferable. When q is 0 or 6 or more, synthesis is difficult.

k is an integer of 5 to 12, preferably 5 to 10, more preferably 6 to 8, and still more preferably 7.

Examples of the silane coupling agent represented by the above formula (I) include NXT manufactured by GE Toshiba Silicone Co., Ltd. The silane coupling agent represented by the above formula (I) may be used alone or in combination of two or more.

The content of the silane coupling agent represented by the above formula (I) is preferably 0.1 parts by mass or more, more preferably 2 parts by mass or more, further preferably 4 parts by mass or more with respect to 100 parts by mass of silica. It is. If the amount is less than 0.1 parts by mass, it is difficult to sufficiently disperse silica, which may deteriorate the fuel efficiency. The content of the silane coupling agent having a mercapto group is preferably 20 parts by mass or less, more preferably 16 parts by mass or less, and still more preferably 12 parts by mass 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 Co., Ltd. trade name Dia Black N339, Tokai Carbon Co., Ltd. trade name Seast 6, Seast 7HM, Seast KH, Evonik Degussa, 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 being subjected to a 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, 2.06 g of 4-N, N-dimethylaminomethylstyrene, 6.1 ml of tetrahydrofuran, ethylene glycol diethyl ether 4.0 ml was charged into the polymerization reactor. Next, 2.74 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 15.90 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, styrene, 4-N, N— were continuously fed into the polymerization reactor while 1,3-butadiene and styrene were continuously fed into the polymerization reactor. A copolymerization reaction of dimethylaminomethylstyrene and 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-N, N-dimethylaminomethylstyrene charged was 0.10% by mass and the amount of bis (diethylamino) methylvinylsilane charged was 0.14%. %Met.
Next, the obtained polymerization reaction solution was stirred at a stirring speed of 130 rpm, 12.80 mmol of N- (3-dimethylaminopropyl) acrylamide was added, and the mixture was stirred for 15 minutes.
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 1.

<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 industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, 3.37 g of 4-bis (trimethylsilyl) aminostyrene, 6.1 ml of tetrahydrofuran, ethylene glycol diethyl ether 4. 0 ml was charged into the polymerization reactor. Next, 2.74 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 15.55 mmol) were charged into the polymerization reactor to initiate the polymerization reaction. .
1,3-butadiene, styrene, 4-bis (trimethylsilyl), while stirring speed is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. A copolymerization reaction of aminostyrene and bis (diethylamino) methylvinylsilane 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. In the total amount of monomers charged / supplied to the polymerization reactor, the charged amount of 4-bis (trimethylsilyl) aminostyrene was 0.17% by mass, and the charged amount of bis (diethylamino) methylvinylsilane was 0.14% by mass. there were.
Next, the obtained polymerization reaction solution was stirred at a stirring speed of 130 rpm, 12.80 mmol of N- (3-dimethylaminopropyl) acrylamide was added, and the mixture was stirred for 15 minutes.
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 2.

<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 (content of n-butyllithium 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>
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 4 was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

<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, 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 6.

<Preparation of copolymer 7>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 137 g of 1,3-butadiene, 43 g of styrene, a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene. 53 g, 1.52 ml of tetrahydrofuran, and 1.18 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, 0.64 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 3.98 mmol) were charged into the polymerization reactor to initiate the polymerization reaction. .

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

10 ml of hexane solution containing 0.5 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 1 was added to the polymer solution. 0.8 g, 0.9 g of pentaerythrityltetrakis (3-laurylthiopropionate) (trade name: Sumilizer TP-D, manufactured by Sumitomo Chemical Co., Ltd.) was added, and then the polymer solution was evaporated at room temperature for 24 hours. And dried under reduced pressure at 55 ° C. for 12 hours to obtain a copolymer 7.

<Preparation of copolymer 8>
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 81 g, 1.52 ml of tetrahydrofuran and 1.18 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, 3.81 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

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 / supplied to the polymerization reactor, the charged amount of the mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene was 0.40% by mass.

10 ml of hexane solution containing 0.5 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 1 was added to the polymer solution. 0.8 g, 0.9 g of pentaerythrityltetrakis (3-laurylthiopropionate) (trade name: Sumilizer TP-D, manufactured by Sumitomo Chemical Co., Ltd.) was added, and then the polymer solution was evaporated at room temperature for 24 hours. And dried under reduced pressure at 55 ° C. for 12 hours to obtain a copolymer 8.

<Preparation of copolymer 9>
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.

10 ml of hexane solution containing 0.5 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 1 was added to the polymer solution. 0.8 g, 0.9 g of pentaerythrityltetrakis (3-laurylthiopropionate) (trade name: Sumilizer TP-D, manufactured by Sumitomo Chemical Co., Ltd.) was added, and then the polymer solution was evaporated at room temperature for 24 hours. And dried under reduced pressure at 55 ° C. for 12 hours to obtain a copolymer 9.

<Creation of copolymer 10>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 137 g of 1,3-butadiene, 43 g of styrene, 0.43 g of 4-dimethylaminomethylstyrene, 1.52 ml of tetrahydrofuran, 1.18 ml of ethylene glycol diethyl ether Charged into the polymerization reactor. Next, 0.64 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 3.59 mmol) were charged into the polymerization reactor to initiate the polymerization reaction. .

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

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

<Preparation of copolymer 11>
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, 2.04 g of 4-dimethylaminomethylstyrene, 6.1 ml of tetrahydrofuran, 4.0 ml of ethylene glycol diethyl ether Charged into the polymerization reactor. Next, 15.89 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to start the polymerization reaction.

The stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene, styrene, and 4-dimethylamino were continuously fed into the polymerization reactor while 1,3-butadiene and styrene were continuously fed into the polymerization reactor. The copolymerization reaction of methylstyrene 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-dimethylaminomethylstyrene charged was 0.10% 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 11.

<Creation of copolymer 12>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 137 g of 1,3-butadiene, 43 g of styrene, 0.70 g of 4-bis (trimethylsilyl) aminostyrene, 1.52 ml of tetrahydrofuran, ethylene glycol diethyl ether 18 ml was charged into the polymerization reactor. Next, 0.64 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 3.66 mmol) were put into the polymerization reactor to initiate the polymerization reaction. .

1,3-butadiene, styrene, bis (diethylamino) methylvinylsilane while stirring rate is 130 rpm, polymerization reactor temperature is 65 ° C., and 1,3-butadiene and styrene are continuously fed into the polymerization reactor. And 4-bis (trimethylsilyl) aminostyrene were copolymerized 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 / supplied to the polymerization reactor, the charged amount of 4-bis (trimethylsilyl) aminostyrene was 0.16% by mass and the charged amount of bis (diethylamino) methylvinylsilane was 0.14% by weight. .

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

<Creation of copolymer 13>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 1,3-butadiene 137 g, styrene 43 g, tetrahydrofuran 1.52 ml, ethylene glycol diethyl ether 1.18 ml, 4-bis (trimethylsilyl) aminostyrene,. 70 g was charged into the polymerization reactor. Next, 3.81 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

While the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene and styrene were continuously fed into the polymerization reactor, 1,3-butadiene, styrene, and 4-bis ( The copolymerization reaction of trimethylsilyl) aminostyrene 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 amount of 4-bis (trimethylsilyl) aminostyrene charged was 0.16% by mass.

10 ml of hexane solution containing 0.5 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 1 was added to the polymer solution. 0.8 g, 0.9 g of pentaerythrityltetrakis (3-laurylthiopropionate) (trade name: Sumilizer TP-D, manufactured by Sumitomo Chemical Co., Ltd.) was added, and then the polymer solution was evaporated at room temperature for 24 hours. And dried under reduced pressure at 55 ° C. for 12 hours to obtain a copolymer 13.

The obtained copolymers 1 to 13 were analyzed by the following method. The results are shown in Tables 1-3.

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

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

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 13: Synthetic carbon black prepared 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 Evonik Degussa (N ₂ SA: 175 m ₂ / g)
NXT: NXT manufactured by GE Toshiba Silicone Co. (compound with p = 2, q = 3, k = 7 in the silane coupling agent represented by the above formula (I))
Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Evonik 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 JX Nippon Oil & Energy Corporation
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 DPG: Soxinol D manufactured by Sumitomo Chemical Co., Ltd.

(Examples and Comparative Examples)
In accordance with the formulation shown in Tables 4-6, 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, Ltd., and mixed. A kneaded paste was 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 unvulcanized rubber composition, vulcanized rubber composition, and a test tire. The results are shown in Tables 4-6. The reference comparative example in Table 4 was set as Comparative Example 3, the reference comparative example in Table 5 was set as Comparative Example 6, and the reference comparative example in Table 6 was set as Comparative Example 10.

<Evaluation items and test methods>
<Tan δ>
A test piece on a strip having a width of 1 mm or 2 mm and a length of 40 mm was punched out from the obtained vulcanized rubber composition and subjected to the test. In the measurement, a loss tangent (tan δ (70 ° C.)) of a test piece at a temperature of 70 ° C. was measured under the conditions of a strain of 1% and a frequency of 10 Hz using a viscoelasticity measuring device (manufactured by Ueshima Seisakusho). The result was expressed as an index. The larger the index, the better the fuel efficiency.
<Rolling resistance>
Using a rolling resistance tester, the rolling resistance when the test tire was run at a rim (15 × 6JJ), internal pressure (230 kPa), load (3.43 kN), speed (80 km / h) was measured, and the standard The index was expressed as an index when the comparative example was 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) = (braking distance of reference comparative example) / (braking 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 Tables 4 to 6 are relative values when the volume loss amount of the reference comparative example is 100. The larger the value, the better the wear resistance.

<Processability>
The sheet properties immediately after the kneading extrusion were visually evaluated according to the following criteria. The worse the sheet properties, the lower the workability.
A: The sheet is very good.
○: Good sheet shape.
Δ: Sheet shape is a little bad.
X: The sheet shape is tattered.

As shown in Table 4, a conjugated diene polymer (copolymers 1 and 2) having a specific monomer unit and having a terminal modified with a specific compound, silica, and a specific silane coupling Example in which an agent (NXT) is blended synergistically improves fuel economy, wet grip performance and wear resistance (particularly wet grip performance and wear resistance) compared to the rubber composition of the comparative example. These performances were obtained at a high level and in a well-balanced manner.

As shown in Table 5, a conjugated diene polymer (copolymers 4 and 5) having a specific monomer unit and having a terminal modified with a specific compound, silica, and a specific silane coupling In comparison with the rubber composition of the comparative example, the examples blended with the agent (NXT) synergistically improved fuel economy, wet grip performance and wear resistance, and these performances were obtained in a high-dimensional and well-balanced manner. It was.

As shown in Table 6, an example in which a conjugated diene polymer (copolymers 7, 10, 12) having specific monomer units, silica, and a specific silane coupling agent (NXT) were blended. Compared with the rubber composition of the comparative example, the fuel efficiency, wet grip performance and wear resistance (particularly the fuel efficiency and wet grip performance (particularly fuel efficiency)) are synergistically improved. The performance was obtained in a high-order and well-balanced manner.

Claims (12)

Containing a rubber component, silica, and a silane coupling agent represented by the following formula (I),
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 (A) having a body unit and at least one end of the copolymer modified with the following compound (G) or alkoxysilane compound is 5% by mass or more,
The pneumatic tire which has a tread produced using the rubber composition for tread whose content of the said silica with respect to 100 mass parts of said rubber components is 5-150 mass parts.
_{(C p H 2p + 1 O} ) 3 Si-C q H 2q -S-CO-C k H 2k + 1 (I)
(In the formula, p is an integer of 1 to 3, q is an integer of 1 to 5, and k is an integer of 5 to 12.)

(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.)
Compound (G): at least selected from the group consisting of a compound having an amino group and a carbonyl group which may have a substituent, and a compound having an amino group and a thiocarbonyl group which may have a substituent One compound. Formula (2) groups represented by V ² in pneumatic tire according to claim 1, wherein 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 pneumatic tire according to claim 1 or 2, wherein the 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 compound (G) is a compound represented by the following formula (3),
The pneumatic tire according to any one of claims 1 to 3, wherein the alkoxysilane compound is a compound represented by the following formula (4).

(In the formula, E represents an oxygen atom or a sulfur atom, and Z ¹ and Z ² have a substituted amino group, a hydrogen atom, a hydrocarbyl group which may have a substituent, or a substituent. It represents also good hydrocarbyloxy group, or at least one of Z ¹ and Z ² is a group having a substituted amino group, or by bonding with Z ¹ and Z ^2, the ring structure having a substituted amino group Z ¹ And represents a group formed by Z ² and a carbonyl carbon.)

(In the formula, v represents an integer of 1 to 10, R ⁴¹ , R ⁴² and R ⁴³ each independently represents an alkyl group or an alkoxy group, and at least one of R ⁴¹ , R ⁴² and R ⁴³ is an alkoxy group. And A ⁴ represents a substituted amino group.) In the formula (3), E is an oxygen atom, Z ¹ is a group represented by the following formula (3-Z), and Z ² is a hydrocarbyl group or a group represented by the following formula (3-Z). The pneumatic tire according to claim 4.

(In the formula, p is 0 or 1, and T is a hydrocarbylene group having 1 to 10 carbon atoms, a group represented by the following formula (3-Ta), or a group represented by the following formula (3-Tb). A ³ represents a substituted amino group, and when Z ^{2 in} Formula (3) is a hydrocarbyl group, A ³ in Z ¹ and the hydrocarbyl group in Z ² may be bonded to each other. when ^{Z 2} of (3) is a group represented by the formula (3-Z), it may be bonded to the ^{a 3} and ^{Z 2} of ^{a 3} of ^{Z 1.)}

^{(Wherein, R 31} represents a hydrocarbylene group having 1 to 10 carbon ^{atoms, R 31} is bonded to ^{A 3.)}

(In the formula, R ³² represents a hydrocarbylene group having 1 to 10 carbon atoms, R ³³ represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms, and R ³² is bonded to A ^3. ) 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 pneumatic tire according to claim 1, wherein the pneumatic tire is a group represented by

(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 pneumatic tire according to claim 6, wherein R ^{11 in the} formula (1-V1) is a hydrogen atom, and n is 0. The vinyl bond content of the conjugated diene polymer (A) is 20 mol% or more and 70 mol% or less, where the content of the constituent unit based on the conjugated diene is 100 mol%. Pneumatic tires. Containing a rubber component, silica, and a silane coupling agent represented by the following formula (I),
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 (5), and a single amount based on a compound represented by the following formula (6) The content of the conjugated diene polymer (B) having a body unit is 5% by mass or more,
The pneumatic tire which has a tread produced using the rubber composition for tread whose content of the said silica with respect to 100 mass parts of said rubber components is 5-150 mass parts.
_{(C p H 2p + 1 O} ) 3 Si-C q H 2q -S-CO-C k H 2k + 1 (I)
(In the formula, p is an integer of 1 to 3, q is an integer of 1 to 5, and k is an integer of 5 to 12.)

(In the formula, R ⁵¹ represents a hydrogen atom or a hydrocarbyl group, w is 0 or 1, R ⁵² represents a hydrocarbylene group, and X ⁵¹ , X ^52, and X ⁵³ are each independently a substituted amino group. Or an optionally substituted hydrocarbyl group, wherein at least one of X ⁵¹ , X ⁵² and X ⁵³ is a substituted amino group.)

(In the formula, R ⁶¹ represents a hydrogen atom or a hydrocarbyl group, x is 0 or 1, R ⁶² represents a hydrocarbylene group, and A ⁶ represents a substituted amino group or a nitrogen-containing heterocyclic group. ) The pneumatic tire according to claim 9, wherein R ^{51 in the} formula (5) is a hydrogen atom, and w is 0. The R ^{61 in the} formula (6) is a hydrogen atom, x is 1, R ⁶² is a group represented by the following formula (6-Y), and A is a substituted amino group. Pneumatic tire described in 2.

(In the formula, y represents an integer of 0 to 5, and when y is an integer of 1 to 5, (CH ₂ ) _y is a substituent on the benzene ring, and (CH ₂ ) _y is bonded to A ^6. And when y is 0, (CH ₂ ) _y represents a bond between the benzene ring and A ^6. ) The vinyl bond content of the conjugated diene polymer (B) is 20 mol% or more and 70 mol% or less, where the content of the constituent unit based on the conjugated diene is 100 mol%. Pneumatic tires.