JP6154260B2 - Pneumatic tire - Google Patents

Description

The present invention relates to a rubber composition for a sidewall and a pneumatic tire having a sidewall manufactured using the rubber composition.

Conventionally, the fuel consumption of automobiles has been reduced by reducing the rolling resistance of tires (improving rolling resistance characteristics). For example, a tire tread has a two-layer structure (an inner surface layer (base tread) and a surface layer (cap tread)), and a rubber composition having excellent low heat generation (low fuel consumption) is used for the base tread. . However, in recent years, the demand for lower fuel consumption has become stronger, and more excellent fuel efficiency is required not only for tires with a high occupation ratio but also for members other than treads (for example, sidewalls). Yes.

In the rubber composition for the sidewall, unlike the rubber composition for the cap tread, carbon black having a large particle diameter has been conventionally used, and even if the carbon black is changed to silica, the effect of improving the fuel efficiency is so great. Absent. Further, if the blending amount of the filler is reduced to improve fuel efficiency, the strength may decrease and the flex crack resistance may deteriorate, or the hardness may decrease and steering stability may deteriorate.

In addition, when silica is blended in a rubber composition, there are disadvantages in processability (kneading processability) such as an increase in unvulcanized rubber viscosity (Mooney viscosity). As a method for improving processability, a method of adding oil such as aroma oil is known. However, when oil is added, there is a tendency that rolling resistance is increased and fuel economy is deteriorated, or hardness is lowered and steering stability is deteriorated. Therefore, a method for improving the fuel economy, steering stability, flex crack resistance and workability in a well-balanced manner is desired.

Patent Document 1 discloses a rubber composition in which silica having different particle diameters is blended to improve fuel efficiency. Patent Documents 2 to 5 propose improving the grip performance and the like using a resin (resin) such as an indene resin. However, these rubber compositions still have room for improvement in terms of improving fuel economy, flex crack resistance, handling stability and processability in a well-balanced manner.

JP 2008-101127 A JP 2006-124601 A JP 2004-137463 A JP 2009-7454 A JP 2001-240704 A

The present invention solves the above-mentioned problems and can improve the fuel economy, handling stability, bending crack resistance and processability in a well-balanced manner, and a rubber composition for a sidewall having the sidewall produced using the rubber composition. The object is to provide a tire.

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

（式中、Ｖ^２は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ａ^２は置換アミノ基、又は、含窒素複素環基を表す。） The present invention contains a rubber component, silica, and a silane coupling agent represented by the following formula (I), and in 100% by mass of the rubber component, a monomer unit based on a conjugated diene is represented by the following formula (1). ) And a conjugation obtained by reacting an alkoxysilane compound with one end of a copolymer having a monomer unit based on the compound represented by formula (2) and a monomer unit based on the compound represented by the following formula (2). The content of the diene polymer is 5% by mass or more, the content of the silica with respect to 100 parts by mass of the rubber component is 5 to 150 parts by mass, and the content of the silane coupling agent with respect to 100 parts by mass of the silica The present invention relates to a pneumatic tire including a sidewall made of a rubber composition having a weight of 0.1 to 70 parts by mass.
_{(C p H 2p + 1 O} ) 3 Si-C q H 2q -S-CO-C k H 2k + 1 (I)
(In the formula, p is an integer of 1 to 3, q is an integer of 1 to 5, and k is an integer of 5 to 12.)

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

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

（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, a conjugated diene polymer having a specific monomer unit and having a terminal modified with a specific compound, silica, and a silane coupling agent represented by the formula (I) Since it is a rubber composition for a sidewall, it is possible to provide a pneumatic tire with improved fuel economy, handling stability, flex crack resistance and processability in a well-balanced manner.

The conjugated diene polymer according to the present invention includes a monomer unit based on a conjugated diene, a monomer unit based on a compound represented by the following formula (1), and a compound represented by the following formula (2). It is obtained by reacting an alkoxysilane compound with one end of a copolymer having a monomer unit based thereon. The conjugated diene polymer has a structure in which the main chain is modified with a compound represented by the following formula (1) and a compound represented by the following formula (2), and the terminal is modified with an alkoxysilane compound. It has a structure, and a synergistic improvement effect is obtained by the compound represented by the following formula (1), the compound represented by the following formula (2) and the alkoxysilane compound.

(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).

(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)).

(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.

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.

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.

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).

(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.

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 2.

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-ethylene group (a group represented by the formula (2-Ra) where i = 2), meta-phenylene- An ethylene group (a group represented by the formula (2-Rb) where j = 2); 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.

The group represented by the formula (2-V) is preferably a group represented by the following formula (2-V1).

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

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

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

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

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) amino) methylphenyl) -1-phenylethylene,
1- (4- (N, N-bis (triisopropylsilyl) amino) methylphenyl) -1-phenylethylene.

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

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

Examples of the alkoxysilane compound having a substituted amino group include compounds represented by the following formula (3).

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

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

^Examples of the alkyl group for R ³¹ , R ³² , and R ³³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group.

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

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

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. which may have hydrocarbylene group, or, R ³⁴ and R ^35, form one group represents a group which bonds to a nitrogen atom with a double bond.

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. Preferably it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve economic efficiency, steering stability, resistance to flex cracking, and workability, 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 about 100% by mass of the conjugated diene polymer, in order to improve fuel economy, handling stability, flex crack resistance, and workability. Preferably it is 0.01 mass% or more, More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve economic efficiency, steering stability, resistance to flex cracking, and workability, 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.

Based on conjugated dienes, with the total amount of monomer units based on the monomer components used in the polymerization being 100% by mass from the viewpoint of improving fuel economy, handling stability, flex crack resistance and processability in a well-balanced manner. The content of the monomer unit, the monomer unit based on the compound represented by formula (1), and the monomer unit based on the compound represented by formula (2) is preferably 99.9% by mass. As mentioned above, More preferably, it is 99.95 mass% or more, More preferably, it is 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 improve the steering stability and the flex crack resistance in a well-balanced manner. Moreover, in order to improve workability, Preferably it is 200 or less, More preferably, it is 150 or less. The Mooney viscosity (ML _{1 + 4} ) is measured at 100 ° C. according to JIS K 6300 (1994).

The vinyl bond amount of the conjugated diene polymer is preferably 80 mol% or less, more preferably 70 mol% or less, and still more preferably from the viewpoint of improving fuel economy, with the content of the conjugated diene unit being 100 mol%. 50 mol% or less, more preferably 40 mol% or less, and preferably 10 mol% or more, more preferably 15 mol% or more, and more preferably 15 mol% or more from the viewpoint that steering stability and flex crack resistance can be improved in a balanced manner. 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 absorption peak of the vinyl group, by infrared spectroscopy.

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

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

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

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

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

The amount of the compound represented by the formula (1) is preferably 0.01% by mass or more in order to improve the fuel efficiency by setting the total amount of the monomer components used in the polymerization to 100% by mass. More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve economy, steering stability, flex crack resistance and workability, 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. Is 0.5 mass% or less.

The amount of the compound represented by the formula (2) is used in order to improve the fuel efficiency, steering stability, flex crack resistance and processability by setting the total amount of monomer components used in the polymerization to 100% by mass. Preferably, it is 0.01 mass% or more, More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve economy, steering stability, flex crack resistance and workability, 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. Is 0.5 mass% or less.

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. % Is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and still more preferably 100 in order to improve fuel economy, steering stability, flex crack resistance and workability. % By mass.

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

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

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

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

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

R ⁴¹ _a ML _4-a (4)
Wherein R ⁴¹ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aryl group, M represents a silicon atom or a tin atom, L represents a halogen atom or a hydrocarbyloxy group, and a represents an integer of 0 to 2. Represents.)

As the coupling agent represented by the above formula (4), silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxysilane, Examples thereof include methyltrimethoxysilane, dimethoxydimethylsilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, and diethoxydiethylsilane.

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

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

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

The content of the conjugated diene polymer in 100% by mass of the rubber component is 5% by mass or more, preferably 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 40% by mass or less, more preferably 30% by mass or less. If it exceeds 40% by mass, the handling stability, the bending crack resistance and the workability tend to be lowered, and the cost tends to be high.

The rubber component that can be used in addition to the conjugated diene polymer is not limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR). ), Chloroprene rubber (CR), butyl rubber (IIR) and the like. These rubber components may be used alone or in combination of two or more. Among these, NR and BR are preferable because they exhibit low fuel consumption, steering stability, bending crack resistance, and workability in a well-balanced manner.
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 50% 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. When it exceeds 90 mass%, workability tends to deteriorate.

The content of BR in 100% by mass of the rubber component is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. When it is less than 1% by mass, there is a tendency that sufficient steering stability and bending crack resistance cannot be obtained. The BR content is preferably 40% by mass or less, more preferably 30% by mass or less. When it exceeds 40 mass%, workability tends to deteriorate.

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

The content of silica is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component. The content is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, in order to improve fuel efficiency. Moreover, in order to improve steering stability, bending crack resistance, and workability, it is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 40 parts by mass or less.

The rubber composition of the present invention uses a silane coupling agent represented by the following formula (I) as a silane coupling agent. By blending the silane coupling agent represented by the following formula (I) together with the conjugated diene polymer and silica, the silica can be dispersed well, resulting in low fuel consumption, steering stability, flex crack resistance and workability. (Especially, low fuel consumption) can be remarkably improved.
_{(C p H 2p + 1 O} ) 3 Si-C q H 2q -S-CO-C k H 2k + 1 (I)
(In the formula, p is an integer of 1 to 3, q is an integer of 1 to 5, and k is an integer of 5 to 12.)

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

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

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

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

Content of the silane coupling agent represented by the said formula (I) is 0.1-70 mass parts with respect to 100 mass parts of silica. The content is preferably 2 parts by mass or more, more preferably 4 parts by mass or more. If it is less than 2 parts by mass, it will be difficult to sufficiently disperse silica, and fuel efficiency may be deteriorated. Moreover, this content becomes like this. Preferably it is 20 mass parts or less, More preferably, it is 16 mass parts or less, More preferably, it is 12 mass parts or less. When it exceeds 20 parts by mass, there is a tendency that an effect commensurate with the increase in cost cannot be obtained.

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

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

Examples of the vulcanization accelerator include 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and thiazole vulcanization accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethylthiuram. Thiuram vulcanization accelerators such as disulfides; N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N -Sulfenamide vulcanization accelerators such as oxyethylene-2-benzothiazole sulfenamide and N, N'-diisopropyl-2-benzothiazole sulfenamide; diphenylguanidine, diortolylguanidine, orthotolylbiguanidine What guanidine-based vulcanization accelerator and the like. The content of the vulcanization accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 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, more preferably 10 to 80 m ² / g, and the dibutyl phthalate (DBP) absorption of carbon black is The amount is preferably 5 to 300 ml / 100 g, 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 brand name Diablack N550, Tokai Carbon Co., Ltd. brand name Seast FM, Seast SO, 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 strength of the rubber. Moreover, in order to improve low-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 150 parts by mass with respect to 100 parts by mass of the rubber component. Further, the content is more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, in order to increase the strength of the rubber. Moreover, in order to improve low fuel consumption, More preferably, it is 120 mass parts or less, More preferably, it is 100 mass parts or less.

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

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

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

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

The rubber composition of the present invention has high fuel economy, handling stability, flex crack resistance, and processability at a high level and in a well-balanced manner.

The rubber composition of the present invention is used for tire sidewalls.

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, a rubber composition containing various additives as required is extruded according to the shape of the sidewall 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 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 amount of 1,3-butadiene supplied 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 reaction of 1,3-butadiene and bis (diethylamino) methylvinylsilane while stirring speed is 130 rpm, polymerization reactor temperature is 65 ° C. and 1,3-butadiene is continuously fed into the polymerization reactor. For 3 hours. The supply amount of 1,3-butadiene 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 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. .

1,3-butadiene, 4-vinylpyridine, and bis (diethylamino) methyl, while stirring speed was 130 rpm, polymerization reactor temperature was 65 ° C., and 1,3-butadiene was continuously fed into the polymerization reactor. Vinylsilane copolymerization was carried out for 3 hours. The supply amount of 1,3-butadiene 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 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.
NR: RSS # 3
BR: Ubepol BR150B manufactured by Ube Industries, Ltd.
Polymers 1 to 6: Carbon black synthesized by the above method: Diablack N550 manufactured by Mitsubishi Chemical Corporation (N ₂ SA: 42 m ² / g, DBP absorption: 115 ml / 100 g)
Silica: Ultrasil VN3 manufactured by Degussa (N ₂ SA: 175 m ² / g)
Silane coupling agent 1: NXT manufactured by GE Toshiba Silicone Co. (compound with p = 2, q = 3, k = 7 in the silane coupling agent represented by the above formula (I))
Silane coupling agent 2: 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: Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd. 1: Sumitomo Chemical ( Soxinol CZ manufactured by
Vulcanization accelerator 2: Soxinol D manufactured by Sumitomo Chemical Co., Ltd.

(Examples and Comparative Examples)
According to the composition shown in Table 2, materials other than sulfur and vulcanization accelerator were kneaded for 3 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 at 50 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized at 170 ° C. for 12 minutes to obtain a vulcanized rubber composition. Further, the obtained unvulcanized rubber composition is molded into a sidewall shape, bonded to another tire member on a tire molding machine, molded into an unvulcanized tire, and vulcanized at 170 ° C. for 12 minutes. A test tire (tire size: 195 / 65R15) was produced.

Using the obtained unvulcanized rubber composition, vulcanized rubber composition, and test tire, the following evaluation was performed. Each test result is shown in Table 2.

<Evaluation items and test methods>
<Mooney viscosity>
The Mooney viscosity of a predetermined unvulcanized rubber composition was measured at 130 ° C. according to JIS K 6300 (1994). The measurement results were displayed as an index according to the following calculation formula, with Comparative Example 8 taken as 100. The larger the index, the smaller the Mooney viscosity and the better the workability.
(Mooney viscosity index) = (Mooney viscosity of Comparative Example 8) / (Mooney viscosity of each formulation) × 100

<Rolling resistance>
Using a viscoelastic spectrometer VES manufactured by Iwamoto Seisakusho, tan δ of each vulcanized rubber composition was measured under conditions of initial strain 10%, dynamic strain 2%, frequency 10 Hz, and temperature 70 ° C. Then, tan δ of Comparative Example 8 was set to 100, and indexed by the following calculation formula. The larger the index, the lower the rolling resistance and the better the fuel efficiency.
(Rolling resistance index) = (tan δ of Comparative Example 8) / (tan δ of each formulation) × 100

<Steering stability>
The test tires were mounted on all wheels of a vehicle (domestic FF2000cc) and the vehicle was run on the test course, and the driving stability was evaluated by sensory evaluation of the driver. The results are shown as an index with the handling stability of Comparative Example 8 as 100. The larger the index, the better the steering stability.

<Bending crack resistance>
Using a vulcanized rubber composition, a sample was prepared based on JIS K 6260 “Vulcanized Rubber and Thermoplastic Rubber—Dematcher Flex Crack Test Method”, a flex crack growth test was performed, and 70% elongation was repeated 1 million times. After bending the sample, the length of the crack that occurred was measured. And the measured value (length) of the comparative example 8 was set to 100, and it represented by the index | exponent by the following formula. The larger the index, the more the crack growth is suppressed and the better the flex crack resistance.
(Bending crack resistance index) = (Measured value of Comparative Example 8) / (Measured value of each formulation) × 100

As shown in Table 2, a conjugated diene polymer (polymers 1 and 5) having a specific monomer unit and having a terminal modified with a specific compound, and a silane represented by the formula (I) The rubber composition of the Example which mix | blended the coupling agent compared with the rubber composition of a comparative example, all of low-fuel-consumption property, steering stability, bending crack resistance, and workability (especially low-fuel-consumption property). The performance improved synergistically, and these performances were obtained in a high level and well-balanced.

Claims (8)

Containing a rubber component, silica, and a silane coupling agent represented by the following formula (I),
In 100% by mass of the rubber component, a monomer unit based on a conjugated diene, a monomer unit based on a compound represented by the following formula (1), and a single amount based on a compound represented by the following formula (2) The content of the conjugated diene polymer obtained by reacting the alkoxysilane compound with one end of the copolymer having a body unit is 5% by mass or more,
The content of the silica with respect to 100 parts by mass of the rubber component is 5 to 150 parts by mass, and the content of the silane coupling agent with respect to 100 parts by mass of the silica is 0.1 to 70 parts by mass. Pneumatic tires with side walls.
_{(C p H 2p + 1 O} ) 3 Si-C q H 2q -S-CO-C k H 2k + 1 (I)
(In the formula, p is an integer of 1 to 3, q is an integer of 1 to 5, and k is an integer of 5 to 12.)

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

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

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

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

(Wherein X ¹ , X ² and X ³ each independently represents a substituted amino group or a hydrocarbyl group which may have a substituent, and at least one of X ¹ , X ² and X ³ is A substituted amino group.) The pneumatic tire according to claim 3, wherein R ^{11 in the} formula (1-V1) is a hydrogen atom, and n is 0. Groups represented by V ² in the formula (2) 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 5 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 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. The pneumatic tire according to any one of claims 1 to 7, wherein the rubber component further contains natural rubber and / or butadiene rubber.