JP6100630B2 - Sidewall rubber composition and 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 fracture strength and the flex crack resistance may deteriorate, or the hardness may decrease and the 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, fracture strength, flex crack resistance, steering stability 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, fracture strength, 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 provides a rubber composition for a sidewall capable of improving the fuel economy, fracture strength, bending crack resistance, steering stability and processability in a balanced manner, and a sidewall produced using the rubber composition. An object is to provide a pneumatic tire having the same.

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

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

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

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

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

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

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

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

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

According to the present invention, since it is a rubber composition for a side wall in which a conjugated diene polymer having a specific monomer unit and silica are blended, low fuel consumption, fracture strength, flex crack resistance, steering stability It is possible to provide a pneumatic tire with improved balance and workability.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the compound represented by formula (1) include the following compounds as compounds in which R ¹¹ is a vinyl group and ^{two of} X ¹ , X ² and X ³ are dialkylamino groups.
Compound in which m is 0:

Bis (dimethylamino) methyl (1-methylene-2-propenyl) silane,
Bis (diethylamino) methyl (1-methylene-2-propenyl) silane,
Bis (di-n-propylamino) methyl (1-methylene-2-propenyl) silane,
Bis (di-n-butylamino) methyl (1-methylene-2-propenyl) silane,
Bis (dimethylamino) ethyl (1-methylene-2-propenyl) silane,
Bis (diethylamino) ethyl (1-methylene-2-propenyl) silane,
Bis (di-n-propylamino) ethyl (1-methylene-2-propenyl) silane,
Bis (di-n-butylamino) ethyl (1-methylene-2-propenyl) silane.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The content of the monomer unit based on the compound represented by the formula (1) is preferably 0.01% by mass or more per 100% by mass of the conjugated diene polymer in order to improve fuel efficiency. Preferably it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve economy, fracture strength, flex crack resistance and steering stability, it is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0%. .5% by mass or less.

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, fracture strength, flex crack resistance, and steering stability. 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, fracture strength, flex crack resistance and steering stability, it is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0%. .5% by mass or less.

From the viewpoint that fuel economy, fracture strength, flex crack resistance, handling stability and processability can be improved in a balanced manner, the total amount of the structural units based on the monomer components used in the polymerization is set to 100% by mass, resulting in a conjugated diene. The content of the structural unit based on the structural unit based on the compound represented by Formula (1) and the structural unit based on the compound represented by Formula (2) is preferably 99.9% by mass or more, 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 increase the fracture strength, the flex crack resistance and the steering stability. Moreover, in order to improve workability, Preferably it is 200 or less, More preferably, it is 150 or less. The Mooney viscosity (ML _{1 + 4} ) is measured at 100 ° C. according to JIS K 6300 (1994).

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

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

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

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

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

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

The amount of the compound represented by the formula (1) is preferably 0.01% by mass or more in order to improve the fuel efficiency by setting the total amount of the monomer components used in the polymerization to 100% by mass. More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve economy, fracture strength, flex crack resistance and steering stability, 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, fracture strength, flex crack resistance, and handling stability by setting the total amount of the 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, fracture strength, flex crack resistance and steering stability, 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. %, In order to enhance the fracture strength, flex crack resistance and steering stability, it is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and further preferably 100% by mass. .

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

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

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

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

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

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

The conjugated diene polymer can be obtained by a known recovery method, for example, (1) a method of adding a coagulant to a hydrocarbon solution of 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 fracture strength, resistance to flex cracking, and steering stability tend to decrease and the cost tends to increase.

The rubber component that can be used in addition to the conjugated diene polymer is not limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR). ), Chloroprene rubber (CR), butyl rubber (IIR) and the like. These rubber components may be used alone or in combination of two or more. Of these, NR and BR are preferred because they exhibit a good balance between low fuel consumption, breaking strength, flex crack resistance, steering stability and processability.
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. If it is less than 1% by mass, sufficient fracture strength, flex crack resistance and steering stability tend not to 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 a commercial product of silica, the product name Ultrasil VN3-G manufactured by Degussa, the product name VN3, AQ, ER, RS-150 manufactured by Tosoh Silica Co., Ltd., and the product names Zeosil 1115MP, 1165MP manufactured by Rhodia can be used. .

The content of silica is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component. The content is preferably 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 fracture strength, bending crack resistance, steering stability, and workability, it is preferably 100 parts by mass or less, more preferably 40 parts by mass or less.

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 Examples thereof include fillers such as clay, aluminum hydroxide and mica; silane coupling agents; extension oils; processing aids; anti-aging agents;

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

Examples of the vulcanization accelerator include 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and thiazole vulcanization accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethylthiuram. Thiuram vulcanization accelerators such as disulfides; N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N -Sulfenamide vulcanization accelerators such as oxyethylene-2-benzothiazole sulfenamide and N, N'-diisopropyl-2-benzothiazole sulfenamide; diphenylguanidine, diortolylguanidine, orthotolylbiguanidine What guanidine-based vulcanization accelerator and the like. The content of the vulcanization accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 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 improve the fracture strength, the flex crack resistance and the steering stability. 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 improve the fracture strength, the flex crack resistance and the steering stability. 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 silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ- Aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxy Cyril) Pills) tetrasulfide, .gamma.-trimethoxysilylpropyl dimethylthiocarbamoyl tetrasulfide, and the like .gamma.-trimethoxysilylpropyl benzothiazyl tetrasulfide. One or more of these are used. As commercial products, trade names Si69, Si75, etc., manufactured by Degussa Corporation can be used.

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

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

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

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

The rubber composition of the present invention has a high level of well-balanced fuel economy, fracture strength, flex crack resistance, steering stability and processability.

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>
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, 0.64 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 3.98 mmol) were charged into the polymerization reactor to initiate the polymerization reaction. .

While stirring speed was 130 rpm, polymerization reactor internal temperature was 65 ° C., and 1,3-butadiene was continuously fed into the polymerization reactor, 1,3-butadiene, bis (diethylamino) methylvinylsilane, 3- (1 -Pyrrolidinyl) ethyl styrene and 4- (1-pyrrolidinyl) ethyl styrene were copolymerized for 2 hours. The supply amount of 1,3-butadiene was 205 g. Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of the mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene was 0.12% by mass, bis (diethylamino) methyl The amount of vinylsilane charged was 0.14% by mass.

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

<Preparation of polymer 2>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 1,3-butadiene 137 g, 1.81 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, 3.81 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

While stirring speed is 130 rpm, polymerization reactor internal temperature is 65 ° C. and 1,3-butadiene 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 / supplied to the polymerization reactor, the charged amount of the mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene was 0.40% by mass.

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

<Preparation of polymer 3>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 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, 3.73 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

While stirring speed is 130 rpm, polymerization reactor internal temperature is 65 ° C. and 1,3-butadiene 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.

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

<Preparation of polymer 4>
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 6.1 ml of tetrahydrofuran, and 4.0 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, 5.43 g of bis (diethylamino) methylvinylsilane and n-hexane solution of n-butyllithium (content of n-butyllithium 14.72 mmol) were charged into the polymerization reactor to initiate the polymerization reaction. .

Copolymerization of 1,3-butadiene and bis (diethylamino) methylvinylsilane while the stirring speed is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and 1,3-butadiene is continuously fed into the polymerization reactor. The reaction was carried out for 3 hours. The supply amount of 1,3-butadiene was 912 g. In the total amount of monomers charged / supplied to the polymerization reactor, the charged amount of bis (diethylamino) methylvinylsilane was 0.27% 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 (modified BR having a modified main chain).

<Preparation of polymer 5>
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, industrial hexane (density 680 kg / m ³ ) 2.55 kg, 1,3-butadiene 137 g, 4-N, N-dimethylaminomethylstyrene 0.43 g, tetrahydrofuran 1.52 ml, ethylene glycol diethyl ether 1.18 ml Was charged into the polymerization reactor. Next, 0.64 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 3.59 mmol) were charged into the polymerization reactor to initiate the polymerization reaction. .

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, bis (diethylamino) methylvinylsilane, and 4- The copolymerization reaction of N, N-dimethylaminomethylstyrene was performed for 2 hours. The supply amount of 1,3-butadiene was 205 g. Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of 4-N, N-dimethylaminomethylstyrene charged was 0.10% by mass, and the amount of bis (diethylamino) methylvinylsilane charged was 0.14% by mass. there were.

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

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

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

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

<Preparation of polymer 7>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, industrial hexane (density 680 kg / m ³ ) 2.55 kg, 1,3-butadiene 137 g, 4-N, N-bis (trimethylsilyl) aminostyrene 0.70 g, tetrahydrofuran 1.52 ml, ethylene glycol diethyl ether 1 .18 ml was charged into the polymerization reactor. Next, 0.64 g of bis (diethylamino) methylvinylsilane and an n-hexane solution of n-butyllithium (content of n-butyllithium 3.66 mmol) were put 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, bis (diethylamino) methylvinylsilane, and 4- The copolymerization reaction of N, N-bis (trimethylsilyl) aminostyrene was performed for 2 hours. The supply amount of 1,3-butadiene was 205 g. Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of 4-N, N-bis (trimethylsilyl) aminostyrene charged was 0.16% by mass, and the amount of bis (diethylamino) methylvinylsilane charged was 0.14%. %Met.

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

<Preparation of polymer 8>
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 137 g of 1,3-butadiene, 1.52 ml of tetrahydrofuran, 1.18 ml of ethylene glycol diethyl ether, 4-N, N-bis (trimethylsilyl) aminostyrene 0 .70 g was charged into the polymerization reactor. Next, 3.81 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

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

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

The obtained polymers 1 to 8 were analyzed by the following method. The results are shown in Table 1.

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

<Amount of vinyl (unit: mol%)>
The amount of vinyl 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 8: Synthetic carbon black prepared 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: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa
Anti-aging agent: Antigen 3C manufactured by Sumitomo Chemical Co., Ltd.
Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Stearic acid: Beads manufactured by NOF Corporation Zinc stearate zinc oxide: Zinc flower No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powdered sulfur vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd. 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 was molded into a sidewall shape, and bonded together with other tire members on a tire molding machine to form an unvulcanized tire, and vulcanized at 170 ° C. for 12 minutes, A test tire (size: 195 / 65R15) was produced.

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

<Evaluation items and test methods>
<Mooney viscosity>
In accordance with JIS K 6300: 1994, the Mooney viscosity of the unvulcanized rubber composition was measured at 100 ° C., and Comparative Example 1 was taken as 100 and indicated by the following formula. The larger the index, the smaller the Mooney viscosity and the better the workability.
(Mooney viscosity index) = (Mooney viscosity of Comparative Example 1) / (Mooney viscosity of each formulation) × 100

<Rolling resistance>
Using a viscoelastic spectrometer VES manufactured by Iwamoto Seisakusho, tan δ of the vulcanized rubber composition was measured at an initial strain of 10%, a dynamic strain of 2%, a frequency of 10 Hz, and a temperature of 70 ° C. The index was expressed by the following formula. The larger the index, the smaller the rolling resistance and the better the fuel efficiency.
(Rolling resistance index) = (tan δ of Comparative Example 1) / (tan δ of each formulation) × 100

<Destructive strength>
The vulcanized rubber composition was subjected to a tensile test using a No. 3 dumbbell according to JIS K 6251, and the breaking strength (TB) and the elongation at break (EB) (%) were measured. (TB × EB / 2) was taken as 100, and indexed by the following formula. The larger the index, the better the breaking strength.
(Destructive strength index) = (Destructive strength of each formulation) / (Destructive strength of Comparative Example 1) × 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. At that time, relative evaluation was made with 10 points being the perfect score and the steering stability of Comparative Example 1 being 6 points. The larger the value, the better the steering stability.

<Bending crack resistance index>
Using a vulcanized rubber composition, a sample was prepared based on JIS K6260 “vulcanized rubber and thermoplastic rubber-dematcher bending crack test method”, a flex crack growth test was performed, and 70% elongation was repeated 1 million times. After bending, the length of the generated crack was measured. And the measured value (length) of the comparative example 1 was set to 100, and it displayed 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 1) / (Measured value of each formulation) × 100

As shown in Table 2, Examples in which conjugated diene polymers having specific monomer units (Polymers 1, 5, 7) and silica were blended were compared with the rubber composition of Comparative Example, All the performances of low fuel consumption, breaking strength, flex crack resistance, handling stability and workability were improved, and these performances were obtained in a high level and well-balanced.

Claims (6)

Containing a rubber component and silica,
In 100% by mass of the rubber component, a monomer unit based on 1,3-butadiene, a monomer unit based on a compound represented by the following formula (1), and a compound represented by the following formula (2) The content of the modified butadiene polymer having a monomer unit based thereon is 5% by mass or more, the content of natural rubber is 5 to 90% by mass, the content of butadiene rubber is 1 to 40% by mass,
In the modified butadiene polymer, the total amount of structural units based on the monomer components used in the polymerization is 100% by mass, the structural units based on 1,3-butadiene, and the structural units based on the compound represented by the formula (1) And the total content of the structural unit based on the compound represented by Formula (2) is 99.9 mass% or more,
A rubber composition for a sidewall, wherein the silica content is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

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

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

(In the formula, r represents an integer of 0 to 5, and when r is an integer of 1 to 5, (CH ₂ ) _r is a substituent on the benzene ring, and (CH ₂ ) _r is bonded to A. , R is 0, (CH ₂ ) _r represents a bond between the benzene ring and A.) The vinyl bond content of the modified butadiene polymer is 20 mol% or more and 70 mol% or less, with the content of the structural unit based on 1,3-butadiene being 100 mol%. Rubber composition for sidewall. The rubber composition for a sidewall according to any one of claims 1 to 4 , wherein a content of carbon black is 10 to 50 parts by mass with respect to 100 parts by mass of the rubber component. The pneumatic tire which has a side wall produced using the rubber composition for side walls in any one of Claims 1-5 .