JP2015101664A - Pneumatic tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pneumatic tire including a base tread composed of a rubber composition with improved fuel consumption and anti-bursting strength in a well balanced manner.SOLUTION: The pneumatic tire includes a base tread composed of a rubber composition which contains a rubber component and a specific silica. In 100 mass% of the rubber component, the content of a conjugated diene polymer having a specific monomer unit is 5 mass% or more in mass 100% of the rubber component. Relative to 100 parts by mass of the rubber component, the content of the silica is 5 to 150 parts by mass.

Description

The present invention relates to a pneumatic tire provided with a base tread composed of a rubber composition.

Conventionally, a method of blending silica as a filler is known as a technique for reducing rolling resistance of a tire (reducing fuel consumption of a vehicle). For example, rolling resistance can be reduced by blending silica in a tread. At the same time, WET traction performance can be improved at the same time. Patent Documents 1 to 3 disclose a method of improving fuel efficiency by blending two types of silica having different nitrogen adsorption specific surface areas and particle diameters into a tread. However, there is a limit to the improvement in fuel efficiency when only the tread is improved, and the base tread is also required to have excellent low heat generation.

Unlike the tread, carbon black having a large particle size has been used for the base tread in order to improve fuel efficiency. Therefore, even if part or all of the carbon black is replaced with silica, the effect of reducing rolling resistance is not so great. Moreover, there is also a problem that the fracture strength is reduced by substitution. As another technique capable of reducing the rolling resistance, a method of reducing the content of the filler is also known, but this method also has a problem that the fracture resistance is lowered. Therefore, there is a demand for a method for improving fuel economy and fracture strength in a well-balanced manner.

JP 2006-233177 A JP 2008-50570 A JP 2008-101127 A

An object of the present invention is to solve the above-mentioned problems and to provide a pneumatic tire including a base tread composed of a rubber composition having improved fuel economy and fracture strength in a well-balanced manner.

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

（式中、Ｖ^２は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ａ^２は置換アミノ基、又は、含窒素複素環基を表す。） The present invention contains a rubber component and silica, and 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 the following formula The content of a conjugated diene polymer obtained by reacting an alkoxysilane compound with one end of a copolymer having a monomer unit based on the compound represented by (2) is 5% by mass or more, and the silica when the particles adjacent to one particle has three or more particles branches particles Z, the average length W ¹ of branch intergranular Z-Z including the branch particles Z is intended 30～400Nm, The present invention relates to a pneumatic tire including a base tread composed of a rubber composition having a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

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

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

The present invention also relates to a pneumatic tire including a base tread composed of a rubber composition obtained by kneading the conjugated diene polymer and silica sol.

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

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

（式中、Ｒ^１１は水素原子又はヒドロカルビル基を表し、ｎは０又は１であり、Ｒ^１２はヒドロカルビレン基を表す。）

（式中、Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立に、置換アミノ基、又は、置換基を有していてもよいヒドロカルビル基を表し、Ｘ^１、Ｘ^２及びＸ^３の少なくとも１つが置換アミノ基である。） The group represented by V ¹ in the formula (1) is a group represented by the following formula (1-V1), and the group represented by S ¹ in the formula (1) is represented by the following formula (1-S). It is preferable that it is group represented by these.

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

(Wherein X ¹ , X ² and X ³ each independently represents a substituted amino group or a hydrocarbyl group which may have a substituent, and at least one of X ¹ , X ² and X ³ is A substituted amino group.)

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

（式中、Ｒ^２１は水素原子又はヒドロカルビル基を表し、ｍは０又は１であり、Ｒ^２２はヒドロカルビレン基を表す。） The group represented by V ² in the formula (2) is preferably a group represented by the following formula (2-V1).

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

（式中、Ｒ^２５及びＲ^２６は、それぞれ、ヒドロカルビル基、又は、トリヒドロカルビルシリル基、あるいは、Ｒ^２５とＲ^２６とが結合して、窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基、又は、Ｒ^２５とＲ^２６は１つの基であって、窒素原子に二重結合で結合する基を表す。） It is preferred substituted amino group of A ² in the formula (2) is a group represented by the following formula (2-A).

(In the formula, each of R ²⁵ and R ²⁶ has a hydrocarbyl group, a trihydrocarbyl silyl group, or R ²⁵ and R ²⁶ bonded to each other, and has a nitrogen atom and / or an oxygen atom as a hetero atom. The hydrocarbylene group which may be substituted, or R ²⁵ and R ²⁶ are one group and represent a group bonded to the nitrogen atom with a double bond.)

The vinyl bond content of the conjugated diene polymer is preferably 20 mol% or more and 70 mol% or less, where the content of monomer units based on the conjugated diene is 100 mol%.

According to the present invention, since it is a rubber composition in which a conjugated diene polymer having a specific monomer unit and a specific silica are respectively blended, air with improved fuel economy and fracture resistance in a well-balanced manner. Provided tires.

2 is a schematic diagram of branched particles Z. FIG. Outline of average primary particle diameter D of silica, average length of branched ZZ including branched particles Z (W ¹ ), and average length of branched ZZ not including branched particles Z (W ² ) It is a schematic diagram.

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

（式中、Ｖ^２は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ａ^２は置換アミノ基、又は、含窒素複素環基を表す。） The rubber composition according to the present invention includes a monomer unit based on a conjugated diene, a monomer unit based on a compound represented by the following formula (1), and a single unit based on a compound represented by the following formula (2). When one end of a copolymer having a monomer unit is a conjugated diene polymer obtained by reacting an alkoxysilane compound, and a particle adjacent to one particle has three or more particles as branched particles Z , average length ^{W 1} of branch intergranular Z-Z including the branch particles Z comprises silica (structure silica (straight silica)) is 30～400Nm. The rubber composition containing the structure silica can be produced, for example, by kneading the conjugated diene polymer and silica sol.

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

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

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

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

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

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

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

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

In the formula (1-V), 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。）

（式中、ｅ、ｆ、ｇは、それぞれ、１〜１０の整数を表す。）

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

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

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

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

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

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

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

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

（式中、Ｒ^１１は水素原子又はヒドロカルビル基を表し、ｎは０又は１であり、Ｒ^１２はヒドロカルビレン基を表す。） The group represented by the formula (1-V) is preferably a group represented by the following formula (1-V1).

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

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

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

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

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

（式中、Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立に、置換アミノ基、又は、置換基を有していてもよいヒドロカルビル基を表し、Ｘ^１、Ｘ^２及びＸ^３の少なくとも１つが置換アミノ基である。） The substituted silyl group represented by S ¹ is preferably a group represented by the following formula (1-S).

(Wherein X ¹ , X ² and X ³ each independently represents a substituted amino group or a hydrocarbyl group which may have a substituent, and at least one of X ¹ , X ² and X ³ is A substituted amino group.)

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

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

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

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

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

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

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

（式中、Ｒ^１５及びＲ^１６は、それぞれ、ヒドロカルビル基、又は、トリヒドロカルビルシリル基、あるいは、Ｒ^１５とＲ^１６とが結合して、窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基、又は、Ｒ^１５とＲ^１６は１つの基であって、窒素原子に二重結合で結合する基を表す。） The substituted amino group for X ¹ , X ² and X ³ is preferably a group represented by the following formula (1-X).

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

Examples of the hydrocarbyl group of R ¹⁵ and R ¹⁶ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group. Examples of the alkynyl group include an ethynyl group and a propargyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group.

The number of carbon atoms of the hydrocarbyl group of R ¹⁵ and R ¹⁶ is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.

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

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

The trihydrocarbylsilyl group of R ¹⁵ and R ¹⁶ is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably an alkyl group bonded to a silicon atom having 1 to 3 carbon atoms. A trialkylsilyl group which is an alkyl group, and more preferably a trimethylsilyl group.

The hydrocarbylene group optionally having a nitrogen atom and / or an oxygen atom to which R ¹⁵ and R ¹⁶ are bonded as a hetero atom includes a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and an oxygen atom. And hydrocarbylene groups. Examples of the hydrocarbylene group include an alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. As the hydrocarbylene group having a nitrogen atom, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH—N A group represented by ═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified. Examples of the hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom to which R ¹⁵ and R ¹⁶ are bonded as a hetero atom is preferably 2 to 20, more preferably 2 to 7. Yes, more preferably 4-6.

The hydrocarbylene group which may have a nitrogen atom and / or oxygen atom to which R ¹⁵ and R ¹⁶ are bonded as a hetero atom is preferably a hydrocarbylene group, more preferably an alkylene group, A polymethylene group is preferred.

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

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

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

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

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

Examples of the acyclic amino group include an ethylideneamino group, a 1-methylpropylideneamino group, a 1,3-dimethylbutylideneamino group, a 1-methylethylideneamino group, and a 4-N, N-dimethylaminobenzylideneamino group. You can also give it.

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

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

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

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

Compound in which n in formula (1-V1) is 0:
(Dimethylamino) dimethylvinylsilane,
(Diethylamino) dimethylvinylsilane,
(Di-n-propylamino) dimethylvinylsilane,
(Di-n-butylamino) dimethylvinylsilane,
(Dimethylamino) diethylvinylsilane,
(Diethylamino) diethylvinylsilane,
(Di-n-propylamino) diethylvinylsilane,
(Di-n-butylamino) diethylvinylsilane.

Compound in which n in formula (1-V1) is 1:
(Dimethylamino) dimethyl-4-vinylphenylsilane,
(Dimethylamino) dimethyl-3-vinylphenylsilane,
(Diethylamino) dimethyl-4-vinylphenylsilane,
(Diethylamino) dimethyl-3-vinylphenylsilane,
(Di-n-propylamino) dimethyl-4-vinylphenylsilane,
(Di-n-propylamino) dimethyl-3-vinylphenylsilane,
(Di-n-butylamino) dimethyl-4-vinylphenylsilane,
(Di-n-butylamino) dimethyl-3-vinylphenylsilane,
(Dimethylamino) diethyl-4-vinylphenylsilane,
(Dimethylamino) diethyl-3-vinylphenylsilane,
(Diethylamino) diethyl-4-vinylphenylsilane,
(Diethylamino) diethyl-3-vinylphenylsilane,
(Di-n-propylamino) diethyl-4-vinylphenylsilane,
(Di-n-propylamino) diethyl-3-vinylphenylsilane,
(Di-n-butylamino) diethyl-4-vinylphenylsilane,
(Di-n-butylamino) diethyl-3-vinylphenylsilane.

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

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

Compound in which n in formula (1-V1) is 1:
Bis (dimethylamino) methyl-4-vinylphenylsilane,
Bis (dimethylamino) methyl-3-vinylphenylsilane,
Bis (diethylamino) methyl-4-vinylphenylsilane,
Bis (diethylamino) methyl-3-vinylphenylsilane,
Bis (di-n-propylamino) methyl-4-vinylphenylsilane,
Bis (di-n-propylamino) methyl-3-vinylphenylsilane,
Bis (di-n-butylamino) methyl-4-vinylphenylsilane,
Bis (di-n-butylamino) methyl-3-vinylphenylsilane,
Bis (dimethylamino) ethyl-4-vinylphenylsilane,
Bis (dimethylamino) ethyl-3-vinylphenylsilane,
Bis (diethylamino) ethyl-4-vinylphenylsilane,
Bis (diethylamino) ethyl-3-vinylphenylsilane,
Bis (di-n-propylamino) ethyl-4-vinylphenylsilane,
Bis (di-n-propylamino) ethyl-3-vinylphenylsilane,
Bis (di-n-butylamino) ethyl-4-vinylphenylsilane,
Bis (di-n-butylamino) ethyl-3-vinylphenylsilane.

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

Compound in which n in formula (1-V1) is 1:
Bis (dimethylamino) methyl-4-isopropenylphenylsilane,
Bis (dimethylamino) methyl-3-isopropenylphenylsilane,
Bis (diethylamino) methyl-4-isopropenylphenylsilane,
Bis (diethylamino) methyl-3-isopropenylphenylsilane,
Bis (di-n-propylamino) methyl-4-isopropenylphenylsilane,
Bis (di-n-propylamino) methyl-3-isopropenylphenylsilane,
Bis (di-n-butylamino) methyl-4-isopropenylphenylsilane,
Bis (di-n-butylamino) methyl-3-isopropenylphenylsilane,
Bis (dimethylamino) ethyl-4-isopropenylphenylsilane,
Bis (dimethylamino) ethyl-3-isopropenylphenylsilane,
Bis (diethylamino) ethyl-4-isopropenylphenylsilane,
Bis (diethylamino) ethyl-3-isopropenylphenylsilane,
Bis (di-n-propylamino) ethyl-4-isopropenylphenylsilane,
Bis (di-n-propylamino) ethyl-3-isopropenylphenylsilane,
Bis (di-n-butylamino) ethyl-4-isopropenylphenylsilane,
Bis (di-n-butylamino) ethyl-3-isopropenylphenylsilane.

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

Compound in which n in formula (1-V1) is 0:
Bis (dimethylamino) methyl (1-methylene-2-propenyl) silane,
Bis (diethylamino) methyl (1-methylene-2-propenyl) silane,
Bis (di-n-propylamino) methyl (1-methylene-2-propenyl) silane,
Bis (di-n-butylamino) methyl (1-methylene-2-propenyl) silane,
Bis (dimethylamino) ethyl (1-methylene-2-propenyl) silane,
Bis (diethylamino) ethyl (1-methylene-2-propenyl) silane,
Bis (di-n-propylamino) ethyl (1-methylene-2-propenyl) silane,
Bis (di-n-butylamino) ethyl (1-methylene-2-propenyl) silane.

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

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

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

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

Compound in which n in formula (1-V1) is 1:
Tris (dimethylamino) -4-vinylphenylsilane,
Tris (dimethylamino) -3-vinylphenylsilane,
Tris (diethylamino) -4-vinylphenylsilane,
Tris (diethylamino) -3-vinylphenylsilane,
Tris (di-n-propylamino) -4-vinylphenylsilane,
Tris (di-n-propylamino) -3-vinylphenylsilane,
Tris (di-n-butylamino) -4-vinylphenylsilane,
Tris (di-n-butylamino) -3-vinylphenylsilane.

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

Compound in which n in formula (1-V1) is 1:
Tris (dimethylamino) -4-isopropenylphenylsilane,
Tris (dimethylamino) -3-isopropenylphenylsilane,
Tris (diethylamino) -4-isopropenylphenylsilane,
Tris (diethylamino) -3-isopropenylphenylsilane,
Tris (di-n-propylamino) -4-isopropenylphenylsilane,
Tris (di-n-propylamino) -3-isopropenylphenylsilane,
Tris (di-n-butylamino) -4-isopropenylphenylsilane,
Tris (di-n-butylamino) -3-isopropenylphenylsilane.

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

Compound in which n in formula (1-V1) is 0:
Tris (dimethylamino) (1-methylene-2-propenyl) silane,
Tris (diethylamino) (1-methylene-2-propenyl) silane,
Tris (di-n-propylamino) (1-methylene-2-propenyl) silane,
Tris (di-n-butylamino) (1-methylene-2-propenyl) silane.

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

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

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

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

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

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

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

In the formula (2-V), 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.

（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。）

（式中、ｉ、ｊ、ｋは、それぞれ、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 (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)).

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

(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, a 1-methylene-2-propenyl group, a 2-methylene-3-butenyl group; a group in which R ²¹ is a phenyl group as 4- (1- Phenylvinyl) phenyl group.

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

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

（式中、Ｒ^２５及びＲ^２６は、それぞれ、ヒドロカルビル基、又は、トリヒドロカルビルシリル基、あるいは、Ｒ^２５とＲ^２６とが結合して、窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基、又は、Ｒ^２５とＲ^２６は１つの基であって、窒素原子に二重結合で結合する基を表す。） The substituted amino group for A ² is preferably a group represented by the following formula (2-A).

(In the formula, each of R ²⁵ and R ²⁶ has a hydrocarbyl group, a trihydrocarbyl silyl group, or R ²⁵ and R ²⁶ bonded to each other, and has a nitrogen atom and / or an oxygen atom as a hetero atom. The hydrocarbylene group which may be substituted, or R ²⁵ and R ²⁶ are one group and represent a group bonded to the nitrogen atom with a double bond.)

Examples of the hydrocarbyl group for R ²⁵ and R ²⁶ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group. Examples of the alkynyl group include an ethynyl group and a propargyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group.

The number of carbon atoms of the hydrocarbyl group of R ²⁵ and R ²⁶ is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.

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

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

The trihydrocarbylsilyl group of R ²⁵ and R ²⁶ is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably an alkyl group bonded to a silicon atom having 1 to 4 carbon atoms. A trialkylsilyl group which is an alkyl group, and more preferably a trimethylsilyl group.

The hydrocarbylene group optionally having a nitrogen atom and / or oxygen atom to which R ²⁵ and R ²⁶ are bonded as a hetero atom includes a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and an oxygen atom. And hydrocarbylene groups. Examples of the hydrocarbylene group include an alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. As the hydrocarbylene group having a nitrogen atom, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH—N A group represented by ═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified. Examples of the hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom to which R ²⁵ and R ²⁶ are bonded as a hetero atom is preferably 2 to 20, more preferably 2 to 7. Yes, more preferably 4-6.

The hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom to which R ²⁵ and R ²⁶ are bonded as a hetero atom is preferably a hydrocarbylene group, more preferably an alkylene group, A polymethylene group is preferred.

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

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

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

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

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

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

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

The group represented by the formula (2-A) is preferably a group in which R ²⁵ and R ²⁶ are hydrocarbyl groups, a group in which R ²⁵ and R ²⁶ are trihydrocarbylsilyl groups, and R ²⁵ and R ²⁶ are bonded. Group which is a hydrocarbylene group. More preferably, R ²⁵ and R ²⁶ are a group that is a linear alkyl group, R ²⁵ and R ²⁶ are a group that is a trialkylsilyl group, and a group that is a polymethylene group to which R ²⁵ and R ²⁶ are bonded.

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

Examples of the nitrogen-containing heterocyclic group represented by A ² include a nitrogen-containing aliphatic heterocyclic group and a nitrogen-containing aromatic heterocyclic group. In the present specification, a nitrogen-containing aliphatic heterocyclic group represents a group obtained by removing one hydrogen atom from a carbon atom of a heterocyclic ring of a compound having a nitrogen-containing aliphatic heterocyclic ring. Represents an aliphatic heterocycle having a nitrogen atom as a heteroatom. The nitrogen-containing aromatic heterocyclic group represents a group obtained by removing one hydrogen atom from a carbon atom of a heterocyclic ring of a compound having a nitrogen-containing aromatic heterocyclic ring, and the nitrogen-containing aromatic heterocyclic ring constitutes a ring. An aromatic heterocyclic ring having a nitrogen atom as a hetero atom is represented.

The nitrogen-containing aliphatic heterocyclic group represented by A ² includes a group having only a nitrogen atom as a hetero atom constituting a ring, a group having a nitrogen atom and an oxygen atom as a hetero atom constituting a ring, and a hetero atom constituting a ring. Examples thereof include a group having a nitrogen atom and a sulfur atom.

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

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

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

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

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

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

The nitrogen-containing aliphatic heterocyclic group represented by A ² is preferably a group having only a nitrogen atom as a hetero atom constituting the ring. The number of carbon atoms in the nitrogen-containing aliphatic heterocyclic group is preferably 4-10.

The nitrogen-containing aromatic heterocyclic group represented by A ² includes a group having only a nitrogen atom as a hetero atom constituting the ring, a group having a nitrogen atom and an oxygen atom as a hetero atom constituting the ring, and a hetero atom constituting the ring. Examples thereof include a group having a nitrogen atom and a sulfur atom.

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

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

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

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

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

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

The nitrogen-containing aromatic heterocyclic group for A ² is preferably a nitrogen-containing aromatic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring, more preferably a group having an imidazole ring or a pyridine ring. And a group having a quinoline ring, more preferably a group having a pyridine ring.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

1- (4-N, N-dimethylaminophenyl) -1-phenylethylene,
1- (4-N, N-diethylaminophenyl) -1-phenylethylene,
1- (4-N, N-dipropylaminophenyl) -1-phenylethylene,
1- (4-N, N-diisopropylaminophenyl) -1-phenylethylene,
1- (4-N, N-dibutylaminophenyl) -1-phenylethylene,
1- (4-N, N-diisobutylaminophenyl) -1-phenylethylene,
1- (4-N, N-di (tert-butyl) aminophenyl) -1-phenylethylene, 1- (4-N, N-diphenylaminophenyl) -1-phenylethylene,
1- (4- (1-aziridinyl) phenyl) -1-phenylethylene,
1- (4- (1-pyrrolidinyl) phenyl) -1-phenylethylene,
1- (4- (1-piperidinyl) phenyl) -1-phenylethylene,
1- (4-hexamethyleneiminophenyl) -1-phenylethylene,
1- (4-morpholinophenyl) -1-phenylethylene,
1- (4- (N, N-bis (trimethylsilyl) amino) phenyl) -1-phenylethylene,
1- (4- (N, N-bis (tert-butyldimethylsilyl) amino) phenyl) -1-phenylethylene,
1- (4- (N, N-bis (triisopropylsilyl) amino) phenyl) -1-phenylethylene,
1- (3-N, N-dimethylaminophenyl) -1-phenylethylene,
1- (3-N, N-diethylaminophenyl) -1-phenylethylene,
1- (3-N, N-dipropylaminophenyl) -1-phenylethylene,
1- (3-N, N-diisopropylaminophenyl) -1-phenylethylene,
1- (3-N, N-dibutylaminophenyl) -1-phenylethylene,
1- (3-N, N-diisobutylaminophenyl) -1-phenylethylene,
1- (3-N, N-di (tert-butyl) aminophenyl) -1-phenylethylene, 1- (3-N, N-diphenylaminophenyl) -1-phenylethylene,
1- (3- (1-aziridinyl) phenyl) -1-phenylethylene,
1- (3- (1-pyrrolidinyl) phenyl) -1-phenylethylene,
1- (3- (1-piperidinyl) phenyl) -1-phenylethylene,
1- (3-hexamethyleneiminophenyl) -1-phenylethylene,
1- (3-morpholinophenyl) -1-phenylethylene,
1- (3- (N, N-bis (trimethylsilyl) amino) phenyl) -1-phenylethylene,
1- (3- (N, N-bis (tert-butyldimethylsilyl) amino) phenyl) -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) aminomethyl) phenyl) -1-phenylethylene,
1- (4- (N, N-bis (triisopropylsilyl) aminomethyl) 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-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) aminomethyl) phenyl) -1-phenylethylene,
1- (3- (N, N-bis (triisopropylsilyl) aminomethyl) 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 hydrogen atom, and m is 0. As the compounds wherein A ² is a nitrogen-containing aliphatic heterocyclic group, the following compounds can be exemplified.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the formula (3), ^examples of the alkyl group represented by R ³¹ , R ³² , and R ³³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Can give. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group.

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

At least one of R ³¹ , R ³² , and R ³³ is an alkoxy group, and in order to improve fuel economy, preferably at least two of R ³¹ , R ³² , and R ³³ are alkoxy groups, and more Preferably, three of R ³¹ , R ³² and R ³³ are alkoxy groups.

（式中、Ｒ^３４及びＲ^３５は、それぞれ、水素原子、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビル基、あるいは、Ｒ^３４とＲ^３５とが結合して、窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基、又は、Ｒ^３４とＲ^３５は１つの基であって、窒素原子に二重結合で結合する基を表す。） In formula (3), A ³ represents a substituted amino group. The substituted amino group for A ³ is preferably a group represented by the following formula (3-A).

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

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

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

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

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

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

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

Examples of the group to which R ³⁴ and R ³⁵ are bonded include a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and a hydrocarbylene group having an oxygen atom. Examples of the hydrocarbylene group include alkylene groups such as trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group. As the hydrocarbylene group having a nitrogen atom, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH—N A group represented by ═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified. Examples of the hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the group to which R ³⁴ and R ³⁵ are bonded is preferably 2 to 20, and more preferably 2 to 12.

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

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

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

p is an integer of 1 to 10, preferably 2 to 4, and more preferably 3.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

From the viewpoint that fuel economy and fracture strength can be improved in a well-balanced manner, the total amount of monomer units based on the monomer components used in the polymerization is defined as 100% by mass. The content of the monomer unit based on the compound represented by formula (2) and the monomer unit based on the compound represented by formula (2) is preferably 99.9% by mass or more, more preferably 99.95. It is at least mass%, more preferably 100 mass%.

The Mooney viscosity (ML _{1 + 4} ) of the conjugated diene polymer is preferably 10 or more, more preferably 20 or more, in order to increase the fracture strength. Moreover, in order to improve performance, Preferably it is 200 or less, More preferably, it is 150 or less, More preferably, it is 60 or less. The Mooney viscosity (ML _{1 + 4} ) is measured at 100 ° C. according to JIS K 6300 (1994).

The vinyl bond amount of the conjugated diene polymer is such that the content of monomer units based on the conjugated diene is 100 mol%, preferably 70 mol% or less, from the viewpoint that the fuel economy and the fracture resistance can be improved in a balanced manner. More preferably, it is 50 mol% or less, More preferably, it is 40 mol% or less, Preferably it is 20 mol% or more, More preferably, it is 30 mol% or more. The vinyl bond amount is determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the vinyl group absorption peak, by infrared spectroscopy.

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

As a suitable production method of the conjugated diene polymer, a production method having the following step A and step B can be mentioned.
(Step A): In a hydrocarbon solvent, a monomer component containing a conjugated diene, a compound represented by the above formula (1) and a compound represented by the above formula (2) is polymerized with an alkali metal catalyst. A polymer unit having a monomer unit based on a conjugated diene, a monomer unit based on a compound represented by the above formula (1), and a monomer unit based on a compound represented by the above formula (2) A step of obtaining a polymer having an alkali metal derived from an alkali metal catalyst at one end.
(Step B): A step of reacting the polymer obtained in Step A with an alkoxysilane compound.

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

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

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

The amount of the compound represented by the formula (1) is preferably 0.01% by mass or more in order to improve fuel efficiency by setting the total amount of the monomer components used in the polymerization to 100% by mass. Yes, more preferably 0.02% by mass or more, still more preferably 0.05% by mass or more. In order to increase economy and fracture strength, 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% in order to improve the fuel efficiency and the fracture resistance by setting the total amount of the monomer components used in the polymerization to 100% by mass. 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 fracture strength, 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. It is.

In the polymerization reaction, the total amount of the conjugated diene, the compound represented by the formula (1) and the compound represented by the formula (2) is 100 masses of the total amount of the monomer components used in the polymerization. % In order to increase the fracture resistance, it is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and further preferably 100% by mass.

Polymerization reaction is an agent that adjusts the vinyl bond amount of monomer units based on conjugated dienes, and a monomer based on monomer units other than conjugated dienes and monomers other than conjugated dienes in conjugated diene polymer chains. You may carry out in presence of the agent which adjusts distribution of a body unit (Hereinafter, it describes generically as a "regulator."). Examples of such agents include ether compounds, tertiary amines, and phosphine compounds. Examples of the ether compound include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and diethylene glycol diethyl ether. And aliphatic diethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, quinoline and the like. Examples of the phosphine compound include trimethylphosphine, triethylphosphine, triphenylphosphine, and the like. One or more of these are used.

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

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

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

In the above method for producing a conjugated diene polymer, a coupling agent is added to the hydrocarbon solution of the conjugated diene polymer from the start of polymerization of the monomer using an alkali metal catalyst to the termination of polymerization as necessary. Also good. An example of the coupling agent is a compound represented by the following formula (4).

R ⁴¹ _a ML _4-a (4)
Wherein R ⁴¹ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aryl group, M represents a silicon atom or a tin atom, L represents a halogen atom or a hydrocarbyloxy group, and a is an integer of 0 to 4 Represents.)

As the coupling agent represented by the above formula (4), silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxysilane, Examples thereof include methyltrimethoxysilane, dimethoxydimethylsilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, and diethoxydiethylsilane.
It is preferable that said a represents the integer of 0-2.

The amount of coupling agent added 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 enhance the performance of the conjugated diene polymer. is there. In order to improve fuel efficiency, the amount is preferably 0.4 mol or less, more preferably 0.3 mol or less.

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

The conjugated diene polymer can be used as a rubber component, and other rubber components and additives such as silica can be blended to obtain the rubber composition according to the present invention.

The content of the conjugated diene polymer in 100% by mass of the rubber component is 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. If the amount is less than 5% by mass, the effect of improving fuel economy tends to be difficult to obtain. Further, the content of the conjugated diene polymer is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less, and particularly preferably 30% by mass or less. When it exceeds 90% by mass, the fracture strength decreases and the cost tends to increase.

The rubber component that can be used in addition to the conjugated diene polymer is not limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR). ), Chloroprene rubber (CR), butyl rubber (IIR) and the like. These rubber components may be used alone or in combination of two or more. Of these, NR and BR are preferable because they exhibit a good balance between low fuel consumption and fracture strength.
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 25% by mass or more, and further preferably 45% 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 90% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less. When it exceeds 90 mass%, there exists a tendency for performance 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. If it is less than 5% by mass, sufficient fracture strength tends not to be 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 according to the present invention contains a structure silica (straight chain silica) in which several silicas are linked and have a chain structure. By using the structure silica in combination with the conjugated diene polymer according to the present invention, the fuel economy and the fracture resistance can be improved in a well-balanced manner.

In the structure silica used in the present invention, particles adjacent to one particle have three or more particles (hereinafter referred to as branched particles Z). The structure of the particle in contact with the branched particle Z is called a branched structure. The branched particle Z is a particle Z of the particles in FIG. 1, which is a schematic explanatory view of the branched particle, and is in contact with three or more other particles. In addition, as structure silica, what has a branched structure (for example, FIG. 2) and what does not have are mentioned, However, Since the structured silica which does not have a branched structure will aggregate immediately, it does not exist substantially.

The average length (W ¹ in FIG. 2) of the ZZ between the branched particles including the branched particles Z of the structure silica is 30 nm or more, preferably 40 nm or more. If it is less than 30 nm, the performance tends not to be sufficiently improved. W ¹ is 400 nm or less, preferably 200 nm or less, more preferably 100 nm or less, and still more preferably 60 nm or less. If it exceeds 400 nm, the hysteresis loss increases excessively due to the increase of stress in the low extension region, and thus the fuel efficiency tends to deteriorate.

The average primary particle diameter of the structure silica (D, see FIG. 2 which is a schematic explanatory diagram of the structure silica containing branched particles) is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more. If it is less than 1 nm, the specific surface area increases and the stress that the interface between rubber and silica increases even in the low extension region, that is, the hysteresis loss increases too much, and the fuel efficiency tends to deteriorate. Further, D is preferably 1000 nm or less, more preferably 800 nm or less, still more preferably 100 nm or less, and particularly preferably 20 nm or less. If it exceeds 1000 nm, the performance tends not to be sufficiently improved.

The average aspect ratio (W ¹ / D) of ZZ between branched particles including the branched particles Z of structure silica is preferably 3 or more, more preferably 4 or more. If it is less than 3, there is a tendency that the performance cannot be sufficiently improved. W ¹ / D is preferably 100 or less, more preferably 30 or less, and still more preferably 6 or less. When W ¹ / D exceeds 100, the stress increases in the low extension region, and the hysteresis loss increases excessively, so that the fuel efficiency tends to deteriorate.

In the present invention, D, W ¹ and W ¹ / D of silica can be measured by observation with a transmission electron microscope of silica dispersed in a vulcanized rubber composition. For example, in FIG. 2, W ¹ / D is 5 when the particle is a true sphere.

The content of the structure silica is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 5 mass parts, there exists a tendency for the effect which mix | blended structure silica is not fully acquired. The content of the structure silica is 150 parts by mass or less, preferably 120 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 80 parts by mass or less, and particularly preferably 40 parts by mass or less. When it exceeds 150 parts by mass, the structural viscosity derived from silica of the rubber composition becomes too high, and the performance tends to deteriorate.

The content of the structure silica in the total 100% by mass of the structure silica and the carbon black is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and preferably 90% by mass or less. More preferably, it is 60 mass% or less. If it is in the said range, low-fuel-consumption property and fracture strength can be improved with a high degree of balance.

You may mix | blend the particulate silica conventionally mix | blended with the rubber for tires with structure silica (for example, Ultrasil VN3 by Degussa).

The rubber composition according to the present invention may contain additives other than the chemicals described above. 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 Examples thereof include fillers such as clay, aluminum hydroxide and mica; silane coupling agents; extension oils; processing aids; anti-aging agents;

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 more preferably 50 to 150 m ² / g. Moreover, the dibutyl phthalate (DBP) absorption amount of carbon black is preferably 5 to 300 ml / 100 g, and more preferably 10 to 120 ml / 100 g. The nitrogen adsorption specific surface area is measured according to ASTM D4820-93, and the DBP absorption is measured according to ASTM D2414-93. As a commercial item, Mitsubishi Chemical Corporation trade name Dia Black N220, Tokai Carbon Co., Ltd. trade name Seast 6, Seast 7HM, Seast KH, Degussa Corporation trade name CK3, 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 10 parts by mass or more, and still more preferably 15 parts by mass or more, in order to increase the fracture resistance. Moreover, in order to improve fuel-consumption property, More preferably, it is 45 mass parts or less, More preferably, it is 40 mass parts or less.

The content of the reinforcing agent is preferably 10 to 180 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, further preferably 30 parts by mass or more, and particularly preferably 50 parts by mass or more in order to increase the fracture resistance. Moreover, in order to improve low fuel consumption, More preferably, it is 150 mass parts or less, More preferably, it is 120 mass parts or less, Most preferably, it is 70 mass parts or less.

Moreover, as mass ratio (content of structure silica: content of carbon black) of content of the structure silica used as a reinforcing agent, and content of carbon black, it is 0.1: 1-10: 1. preferable. The mass ratio is more preferably 0.5: 1 to 2: 1 in order to enhance fuel efficiency and enhance reinforcement.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ- Aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxy Cyril) Pills) tetrasulfide, .gamma.-trimethoxysilylpropyl dimethylthiocarbamoyl tetrasulfide, and the like .gamma.-trimethoxysilylpropyl benzothiazyl tetrasulfide. One or more of these are used. As commercial products, trade names Si69, Si75, etc., manufactured by Degussa Corporation can be used.

The content of the silane coupling agent is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and further preferably 5 to 10 parts by mass with respect to 100 parts by mass of silica.

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 according to 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.

In particular, it is preferable to knead the silica sol with a rubber component containing the conjugated diene polymer in a rubber kneading apparatus from the viewpoint that the rubber composition according to the present invention in which the structure silica is formed can be easily produced. ,In particular,
(I) A rubber component containing the conjugated diene polymer, silica sol, and carbon black, silane coupling agent, zinc oxide, stearic acid, softening agent, anti-aging agent, wax, etc. A base kneading step of kneading for 3 to 10 minutes at a temperature of 90 ° C. (preferably 90 to 170 ° C.);
(II) a final kneading step of kneading the kneaded material obtained by the base kneading step, the vulcanizing agent, and the vulcanization accelerator at 30 to 100 ° C. (preferably 40 to 85 ° C.) for 3 to 10 minutes;
(III) A production method including a vulcanization step of vulcanizing the unvulcanized rubber composition obtained by the finish kneading step at 150 to 190 ° C. (preferably 160 to 180 ° C.) for 5 to 30 minutes is more preferable.

The preferable content of silica sol (in terms of silica) is the same as that of the above-described structure silica.

In the kneading step for forming the structure silica (base kneading step, etc.), if each component is kneaded in toluene, which is a good solvent for rubber, W ^{1 of} the structure silica tends to become excessively long. It is preferable to knead without using.

In this specification, silica sol refers to a colloidal solution in which silica is dispersed in a solvent. The silica sol is not particularly limited, but a colloidal solution in which elongated silica is dispersed in a solvent is preferable because a structure silica can be suitably formed. A colloidal solution in which elongated silica is dispersed in an organic solvent (organo Silica sol) is more preferable. Here, the elongated silica means a silica (secondary particle) having a chain shape in which a plurality of primary particles such as a spherical shape and a granular shape are connected. It may be linear or branched.

The solvent for dispersing silica is not particularly limited, but alcohols such as methanol and isopropanol are preferable, and isopropanol is more preferable.

The average particle diameter of the primary particles constituting the silica (secondary particles) contained in the silica sol is preferably 1 to 100 nm, more preferably 5 to 80 nm.
The average particle size of the primary particles is a value obtained by measuring the particle size (average diameter) of 50 primary particles by visual observation in a photograph taken with a transmission electron microscope JEM2100FX manufactured by JEOL Ltd. did.

In addition, when the silica (secondary particles) has an elongated shape, the average diameter of the primary particles is an average value of thicknesses (diameters) measured at arbitrary 50 locations of the silica (secondary particles) in the electron micrograph. In the case where the silica (secondary particles) has a bead shape with a constriction, it can be obtained as an average value of the diameters of 50 bead beads in an electron micrograph. When each rosary has a major axis and a minor axis, that is, when each rosary is elongated, the minor axis is measured.

The average particle diameter of silica (secondary particles) contained in the silica sol is preferably 20 to 300 nm, more preferably 30 to 150 nm. The average particle diameter of silica (secondary particles) can be measured by a dynamic light scattering method, and specifically, can be measured by the following method.
The average particle diameter of silica (secondary particles) was measured with a laser particle analysis system ELS-8000 (cumulant analysis) manufactured by Otsuka Electronics Co., Ltd. The measurement conditions are a temperature of 25 ° C., an angle between incident light and a detector of 90 °, and an integration count of 100. The refractive index of water (1.333) is input as the refractive index of the dispersion solvent. The measurement concentration was usually about 5 × 10 ⁻³ mass%.

The silica (secondary particles) is, for example, a method described in claim 2 of International Publication No. WO 00/15552 and the disclosure of the specification related thereto, Japanese Patent No. 2803134, Japanese Patent No. 2926915. It can be produced according to the method described in claim 2 of the publication and the disclosure part of the specification relating thereto.

Specific examples of the silica (secondary particles) that can be used in the present invention include “Snowtex-OUP” (average secondary particle size: 40 to 100 nm) manufactured by Nissan Chemical Industries, Ltd. "Tex-UP" (average secondary particle size: 40 to 100 nm), "Snowtex PS-M" (average secondary particle size: 80 to 150 nm), "Snowtex PS-MO" (average secondary particle size) : 80-150 nm), "Snowtex PS-S" (average secondary particle size: 80-120 nm), "Snowtex PS-SO" (average secondary particle size: 80-120 nm), "IPA-ST -UP "(average secondary particle size: 40 to 100 nm)," Quarton PL-7 "(average secondary particle size: 130 nm) manufactured by Fuso Chemical Industry Co., Ltd., and the like. Among these, IPA-ST-UP is preferable because it can form the structure silica suitably.

The rubber composition according to the present invention has a good balance between low fuel consumption and fracture strength.

The rubber composition according to the present invention is used for a base tread of a tire.

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, a rubber composition blended with various additives as necessary is extruded according to the shape of the base tread of the tire at an unvulcanized stage, and molded by a normal method on a tire molding machine, Bonding together with other tire members forms 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 polymer 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, 2.58 g of a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene, tetrahydrofuran 6.1 ml and ethylene glycol diethyl ether 4.1 ml were 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 15.04 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 is continuously fed into the polymerization reactor, 1,3-butadiene, 3- (1-pyrrolidinyl) ethylstyrene, 4 A copolymerization reaction of-(1-pyrrolidinyl) ethylstyrene and bis (diethylamino) methylvinylsilane was performed for 3 hours. The supply amount of 1,3-butadiene in the entire polymerization reaction was 912 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 polymer 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 polymer 1 was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

<Preparation of polymer 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 ), 547 g of 1,3-butadiene, 6.1 ml of tetrahydrofuran, and 4.7 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, an n-butyllithium n-hexane solution (content of n-butyllithium 15.38 mmol) was 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 the reaction was carried out for 3 hours while 1,3-butadiene was continuously fed into the polymerization reactor. The supply amount of 1,3-butadiene in the entire polymerization reaction was 821 g.

Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 12.80 mmol of [3- (diethylamino) propyl] trimethoxysilane was added and stirred for 15 minutes. 20 ml of a hexane solution containing 0.8 ml of methanol in the polymer solution was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.

To the polymer solution, 8.0 g of 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM), 4.0 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) is added, and then the polymer solution is evaporated at room temperature for 24 hours. The polymer 2 was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

<Preparation of polymer 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, 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. .

Copolymerization of 1,3-butadiene and bis (diethylamino) methylvinylsilane while the stirring speed is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and 1,3-butadiene is continuously fed into the polymerization reactor. The reaction was carried out for 3 hours. The supply amount of 1,3-butadiene in the entire polymerization reaction was 912 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 polymer 3.

<Preparation of polymer 4>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 137 g of 1,3-butadiene, 0.53 g of a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene, tetrahydrofuran 1.52 ml and 1.18 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, an n-butyllithium n-hexane solution (content of n-butyllithium 3.73 mmol) was 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 is continuously fed into the polymerization reactor, 1,3-butadiene, 3- (1-pyrrolidinyl) ethylstyrene, and , 4- (1-pyrrolidinyl) ethylstyrene was copolymerized for 2 hours. The supply amount of 1,3-butadiene in the entire polymerization reaction was 205 g. In the total amount of monomers charged and supplied to the polymerization reactor, the charged amount of the mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene was 0.12% by mass.

20 ml of hexane solution containing 0.8 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 8 was added to the polymer solution. 0.0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) 4.0 g was added, and then the polymer solution was evaporated at room temperature for 24 hours. And dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 4.

<Preparation of polymer 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, 1.41 g of 4-vinylpyridine, 6.1 ml of tetrahydrofuran, and 4.0 ml of ethylene glycol diethyl ether are placed in the polymerization reactor. I put it in. Next, 2.88 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 17.84 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, 4-vinylpyridine, and bis (diethylamino) were continuously fed into the polymerization reactor. The copolymerization reaction of methyl vinyl silane was performed for 3 hours. The supply amount of 1,3-butadiene in the entire polymerization reaction was 912 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 polymer solution was stirred at a stirring speed of 130 rpm, and 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 polymer 5 was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

<Preparation of polymer 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, 1.41 g of 4-vinylpyridine, 6.1 ml of tetrahydrofuran, and 4.0 ml of ethylene glycol diethyl ether are placed in the polymerization reactor. I put it in. Next, an n-butyllithium n-hexane solution (a content of n-butyllithium of 18.52 mmol) was charged into the polymerization reactor 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 was continuously fed into the polymerization reactor, the copolymerization reaction of 1,3-butadiene and 4-vinylpyridine was conducted. I went for 3 hours. The supply amount of 1,3-butadiene in the entire polymerization reaction was 912 g. Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of 4-vinylpyridine charged was 0.07% by mass.

20 ml of hexane solution containing 0.8 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) 8 was added to the polymer solution. 0.0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) 4.0 g was added, and then the polymer solution was evaporated at room temperature for 24 hours. And dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 6.

The obtained polymers 1 to 6 were analyzed by the following method. The results are shown in Table 1.

<Mooney viscosity (ML _{1 + 4} )>
The Mooney viscosity of the polymer was measured at 100 ° C. according to JIS K 6300 (1994).

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

<Molecular weight distribution (Mw / Mn)>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method under the following conditions (1) to (8), and the molecular weight distribution (Mw / Mn) was determined.
(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.
Natural rubber (NR): RSS # 3
Butadiene rubber (BR): Ubepol BR150B manufactured by Ube Industries, Ltd.
Polymers 1 to 6: 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 1: Organosilica sol IPA-ST-UP manufactured by Nissan Chemical Industries, Ltd. (elongated isopropanol-dispersed silica sol (average particle diameter of silica (secondary particles) measured by dynamic light scattering method: 40 to 100 nm)) Silica content: 15% by mass) (The amounts shown in Table 2 indicate the amount of silica in the organosilica sol.)
Silica 2: Ultrasil VN3 manufactured by Degussa (particle size silica, N ₂ SA: 175 m ² / g)
Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa
Anti-aging agent: Antigen 3C manufactured by Sumitomo Chemical Co., Ltd.
Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Stearic acid: Beads manufactured by NOF Corporation Zinc stearate zinc oxide: Zinc flower No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powdered sulfur vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd .: Sumitomo Chemical Co., Ltd. Soxinol CZ

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

The obtained sheet-like vulcanized rubber composition and test tire were used for evaluation by the above test method. Table 2 shows the test results and the average of these two evaluation values.

<Evaluation items and test methods>
(Average primary particle diameter, average length and average aspect ratio of silica)
A sample was cut out from the tread of the test tire, and the silica dispersed in the sample was observed with a transmission electron microscope. The average primary particle diameter (D) of silica and the average length of ZZ between the branched particles including the branched particles Z were measured. (W ¹ in FIG. 2), the average length of the inter-branched particles ZZ not including the branched particles Z (W ² in FIG. ² ), the average aspect ratio of the ZZ between the branched particles including the branched particles Z (W ¹ / D), the average aspect ratio (W ² / D) of ZZ between the branched particles not including the branched particles Z was calculated. The numerical value was an average value obtained by measuring 50 locations.

(Tan δ)
A strip-shaped test piece having a width of 1 mm or 2 mm and a length of 40 mm was punched out from the sheet-like vulcanized rubber composition and subjected to the test. The measurement is performed by measuring the loss tangent (tan δ (70 ° C.)) of the test piece at a temperature of 70 ° C. under the conditions of a strain of 1% and a frequency of 10 Hz using a viscoelasticity measuring device (manufactured by Ueshima Seisakusho Co., Ltd.). The reciprocal of tan δ in Example 10 was taken as 100 and displayed as an index. The larger the index, the better the fuel efficiency.

<Destructive strength>
The sheet-like vulcanized rubber composition was subjected to a tensile test using a No. 3 dumbbell according to JIS K 6251, and the breaking strength (TB) and elongation at break (EB) (%) were measured. The numerical value of TB × EB / 2 was used as the fracture resistance, and the index was expressed as an index with the fracture resistance of Comparative Example 10 as 100. The larger the index, the better the fracture strength.

As shown in Table 2, the rubber composition of the example in which the specific conjugated diene polymer (polymers 1 and 5) and the specific silica were blended was more resistant to breakage than the rubber composition of the comparative example. The strength was good and the fuel efficiency was synergistically improved, and these performances were obtained at a high level and well-balanced.

Z branch particles

Claims (8)

Containing a rubber component and silica,
In 100% by mass of the rubber component, a monomer unit based on a conjugated diene, a monomer unit based on a compound represented by the following formula (1), and a single amount based on a compound represented by the following formula (2) The content of the conjugated diene polymer obtained by reacting the alkoxysilane compound with one end of the copolymer having a body unit is 5% by mass or more,
The silica is intended when the particles adjacent to one particle has three or more particle branched particles Z, the average length W ¹ of branch intergranular Z-Z including the branch particles Z of 30~400nm Yes,
A pneumatic tire comprising a base tread composed of a rubber composition having a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

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

(In the formula, V ² represents a hydrocarbyl group having a polymerizable carbon-carbon double bond, and A ² represents a substituted amino group or a nitrogen-containing heterocyclic group.) A copolymer having monomer units based on a conjugated diene, monomer units based on a compound represented by the following formula (1), and monomer units based on a compound represented by the following formula (2) A pneumatic tire comprising, at one end, a base tread composed of a rubber composition obtained by kneading a conjugated diene polymer obtained by reacting an alkoxysilane compound and silica sol.

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

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

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

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

(Wherein X ¹ , X ² and X ³ each independently represents a substituted amino group or a hydrocarbyl group which may have a substituent, and at least one of X ¹ , X ² and X ³ is A substituted amino group.) The pneumatic tire according to claim 4, wherein R ^{11 in the} formula (1-V1) is a hydrogen atom, and n is 0. Groups represented by V ² in the formula (2) The pneumatic tire according to claim 1 is a group represented by the following formula (2-V1).

(Wherein R ²¹ represents a hydrogen atom or a hydrocarbyl group, m is 0 or 1, and R ²² represents a hydrocarbylene group.) The pneumatic tire according to any one of claims 1 to 6 substituted amino group of A ² in the formula (2) is a group represented by the following formula (2-A).

(In the formula, each of R ²⁵ and R ²⁶ has a hydrocarbyl group, a trihydrocarbyl silyl group, or R ²⁵ and R ²⁶ bonded to each other, and has a nitrogen atom and / or an oxygen atom as a hetero atom. The hydrocarbylene group which may be substituted, or R ²⁵ and R ²⁶ are one group and represent a group bonded to the nitrogen atom with a double bond.) The vinyl bond amount of the conjugated diene polymer is 20 mol% or more and 70 mol% or less, where the content of monomer units based on the conjugated diene is 100 mol%. Pneumatic tire.

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