JP6006054B2 - Rubber composition and pneumatic tire - Google Patents

Description

The present invention relates to a rubber composition and a pneumatic tire produced using the rubber composition.

As a rubber composition for an automobile tire, a rubber composition containing a conjugated diene polymer such as polybutadiene or butadiene-styrene copolymer and a filler such as carbon black or silica is used. In recent years, due to increasing interest in environmental issues, there has been a strong demand for lower fuel consumption for automobiles, and rubber compositions used for automobile tires are also required to have excellent fuel efficiency. .

As a method for improving fuel economy, for example, Patent Document 1 proposes a method using a diene rubber (modified rubber) modified with an organosilicon compound containing an amino group and an alkoxy group. However, in recent years, further improvement in fuel economy has been demanded due to an increase in interest in environmental problems. In addition, the performance required for rubber compositions for automobile tires includes wet grip performance and wear resistance, but these performances generally have a contradiction to low fuel consumption, and each performance is It was difficult to obtain a high dimension and good balance.

JP 2000-344955 A

An object of the present invention is to solve the above-mentioned problems and to provide a rubber composition that can improve fuel economy, wet grip performance, and wear resistance in a well-balanced manner, and a pneumatic tire using the same.

（式（Ｉ）中、ｉは０又は１であり、Ｒ^１は炭素原子数１〜１００のヒドロカルビレン基を表し、Ｒ^２及びＲ^３は、置換基を有してもよいヒドロカルビル基、又は、トリヒドロカルビルシリル基を表すか、あるいは、Ｒ^２とＲ^３とが結合して、ケイ素原子、窒素原子及び酸素原子からなる原子群から選択される少なくとも１種の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を表し、Ｍはアルカリ金属原子を表す。）

（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。） In the present invention, a polymerization initiator represented by the following formula (I) is used to polymerize a conjugated diene, a compound represented by the following formula (1), and a compound represented by the following formula (2). The present invention relates to a rubber composition containing the resulting conjugated diene polymer (A) and silica, wherein the silica content is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

(In Formula (I), i is 0 or 1, R ¹ represents a hydrocarbylene group having 1 to 100 carbon atoms, R ² and R ³ are hydrocarbyl groups which may have a substituent, Alternatively, it represents a trihydrocarbylsilyl group, or R ² and R ³ are bonded to each other and have at least one atom selected from the group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a hetero atom. Represents an optionally hydrocarbylene group, and M represents an alkali metal atom.)

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.)

（式（Ｉａ）中、Ｒ^４は共役ジエン化合物由来の構造単位及び／又は芳香族ビニル化合物由来の構造単位からなるヒドロカルビレン基を表し、ｊは１〜１０の整数を表す。） R ^{1 in the} formula (I) is preferably a group represented by the following formula (Ia).

(In formula (Ia), R ⁴ represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, and j represents an integer of 1 to 10.)

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１〜５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 content of the monomer unit based on the compound represented by the formula (1) per 100 mass% of the conjugated diene polymer (A) is 0.01 to 3 mass%, and is represented by the formula (2). The content of the monomer unit based on the compound is preferably 0.01 to 3% by mass.

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

According to the present invention, since it is a rubber composition in which the conjugated diene polymer (A) and silica are blended, it is possible to provide a pneumatic tire with improved fuel economy, wet grip performance and wear resistance in a well-balanced manner.

（式（Ｉ）中、ｉは０又は１であり、Ｒ^１は炭素原子数１〜１００のヒドロカルビレン基を表し、Ｒ^２及びＲ^３は、置換基を有してもよいヒドロカルビル基、又は、トリヒドロカルビルシリル基を表すか、あるいは、Ｒ^２とＲ^３とが結合して、ケイ素原子、窒素原子及び酸素原子からなる原子群から選択される少なくとも１種の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を表し、Ｍはアルカリ金属原子を表す。）

（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 (A) according to the present invention uses a polymerization initiator represented by the following formula (I), a conjugated diene, a compound represented by the following formula (1), and the following formula (2). It is obtained by polymerizing a compound represented by

(In Formula (I), i is 0 or 1, R ¹ represents a hydrocarbylene group having 1 to 100 carbon atoms, R ² and R ³ are hydrocarbyl groups which may have a substituent, Alternatively, it represents a trihydrocarbylsilyl group, or R ² and R ³ are bonded to each other and have at least one atom selected from the group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a hetero atom. Represents an optionally hydrocarbylene group, and M represents an alkali metal atom.)

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.

I in the formula (I) is 0 or 1, preferably 1.

R ¹ in the formula (I) is a hydrocarbylene group having 1 to 100 carbon atoms, preferably a hydrocarbylene group having 6 to 100 carbon atoms, more preferably 7 to 80 carbon atoms. It is a hydrocarbylene group. When the number of carbon atoms in R ¹ exceeds 100, the molecular weight of the polymerization initiator increases, and the economy and operability during polymerization may be reduced.
As the polymerization initiator represented by formula (I), the number of carbon atoms of R ¹ may be used in combination plural kinds of different compounds.

（式（Ｉａ）中、Ｒ^４は共役ジエン化合物由来の構造単位及び／又は芳香族ビニル化合物由来の構造単位からなるヒドロカルビレン基を表し、ｊは１〜１０の整数を表す。） R ¹ in the formula (I) is preferably a group represented by the following formula (Ia).

(In formula (Ia), R ⁴ represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, and j represents an integer of 1 to 10.)

In formula (Ia), R ⁴ represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, preferably a hydrocarbylene group composed of a structural unit derived from isoprene. And more preferably a hydrocarbylene group consisting of 1 to 10 structural units derived from isoprene.

The number of structural units derived from the conjugated diene compound and / or aromatic vinyl compound in R ⁴ is preferably 1 to 10 units, and more preferably 1 to 5 units.

In the formula (Ia), j is an integer of 1 to 10, preferably an integer of 2 to 4.

R ¹ includes a group in which 1 to 10 structural units derived from isoprene and a methylene group are bonded, a group in which 1 to 10 structural units derived from isoprene and an ethylene group are bonded, and a structural unit 1 to 1 derived from isoprene. Examples thereof include a group in which 10 units and a trimethylene group are bonded, and a group in which 1 to 10 structural units derived from isoprene and a trimethylene group are bonded is preferable.

R ² and R ^{3 in} formula (I) represent a hydrocarbyl group or trihydrocarbylsilyl group which may have a substituent, or R ² and R ³ are bonded to each other to form a silicon atom, It represents a hydrocarbylene group that may have at least one atom selected from the group consisting of a nitrogen atom and an oxygen atom as a hetero atom.

The hydrocarbyl group which may have a substituent is a hydrocarbyl group or a substituted hydrocarbyl group. Examples of the substituent in the substituted hydrocarbyl group include a substituted amino group and a hydrocarbyloxy group. Hydrocarbyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and n-octyl. Group, a chain alkyl group such as n-dodecyl group; a cyclic alkyl group such as cyclopentyl group and cyclohexyl group; and an aryl group such as phenyl group and benzyl group, preferably a chain alkyl group, more preferably Is a chain alkyl group having 1 to 4 carbon atoms. Examples of the substituted hydrocarbyl group in which the substituent is a substituted amino group include an N, N-dimethylaminomethyl group, a 2-N, N-dimethylaminoethyl group, and a 3-N, N-dimethylaminopropyl group. Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include a methoxymethyl group, a methoxyethyl group, and an ethoxymethyl group. In these, a hydrocarbyl group is preferable, a C1-C4 chain alkyl group is more preferable, and a methyl group or an ethyl group is still more preferable.

Examples of the trihydrocarbylsilyl group include a trimethylsilyl group and a tert-butyl-dimethylsilyl group, and a trimethylsilyl group is preferable.

The hydrocarbylene group which may have at least one atom selected from the atomic group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a heteroatom is a hydrocarbylene group, or a heteroatom is a silicon atom, nitrogen It is a heteroatom-containing hydrocarbylene group which is at least one atom selected from an atomic group consisting of an atom and an oxygen atom. As the heteroatom-containing hydrocarbylene group in which the heteroatom is at least one atom selected from the group consisting of a silicon atom, a nitrogen atom, and an oxygen atom, the heteroatom-containing hydrocarbylene group in which the heteroatom is a silicon atom, Examples thereof include a heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom and a heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom. Examples of the hydrocarbylene group include a tetramethylene group, a pentamethylene group, a hexamethylene group, a pentan-2-ene-1,5-diyl group, and a 2,2,4-trimethylhexane-1,6-diyl group. Alkylene group; Alkenediyl group such as pentane-2-ene-1,5-diyl group can be mentioned, preferably an alkylene group, more preferably an alkylene group having 4 to 7 carbon atoms. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is a silicon atom include a group represented by —Si (CH ₃ ) ₂ —CH ₂ —CH ₂ —Si (CH ₃ ) ₂ —. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom include a group represented by —CH═N—CH═CH— and a group represented by —CH═N—CH ₂ —CH ₂ —. be able to. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom include a group represented by —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —. In these, a hydrocarbylene group is preferable, a C4-C7 alkylene group is more preferable, and a tetramethylene group, a pentamethylene group, and a hexamethylene group are still more preferable.

R ² and R ³ are preferably hydrocarbyl groups, or R ² and R ³ are preferably bonded to form a hydrocarbylene group, which is a linear alkyl group having 1 to 4 carbon atoms, or a bond It is more preferably an alkylene group having 4 to 7 carbon atoms, and further preferably a methyl group or an ethyl group.

In formula (I), M represents an alkali metal atom. Examples of the alkali metal atom include Li, Na, K, and Cs, and Li is preferable.

Among the polymerization initiators represented by the formula (I), examples of the compound in which i is 1 include compounds obtained by polymerizing 1 to 5 structural units derived from isoprene on an aminoalkyl lithium compound. Examples of the aminoalkyllithium compound include 3- (N, N-dimethylamino) -1-propyllithium, 3- (N, N-diethylamino) -1-propyllithium, 3- (N, N-di-n- Butylamino) -1-propyllithium, 4- (N, N-dimethylamino) -1-butyllithium, 4- (N, N-diethylamino) -1-butyllithium, 4- (N, N-di-n) N, N-dialkylaminoalkyllithium such as -propylamino) -1-butyllithium, 3- (N, N-di-n-butylamino) -1-butyllithium; 3- (1-pyrrolidino) -1- Propyllithium, 3- (1-piperidino) -1-propyllithium, 3- (1-hexamethyleneimino) -1-propyllithium, 3- [1- (1,2,3,6-tetrahydro) Non-heteroatom-containing cyclic aminoalkyllithium compounds such as lysino)]-1-propyllithium; 3- (1-morpholino) -1-propyllithium, 3- (1-imidazolyl) -1-propyllithium, 3- (4 , 5-dihydro-1-imidazolyl) -1-propyllithium, 3- (2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl) -1-propyllithium, etc. Heteroatom-containing cyclic aminoalkyllithium compounds can be mentioned, N, N-dialkylaminoalkyllithium is preferred, 3- (N, N-dimethylamino) -1-propyllithium or 3- (N, N-diethylamino) -1-Propyllithium is more preferred.

Among the polymerization initiators represented by the formula (I), compounds in which i is 0 include lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, and lithium dimethylamide. , Lithium diethylamide, lithium dipropylamide, lithium dibutylamide, lithium dihexylamide, lithium diheptylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiperazide, lithium ethylpropylamide, lithium Examples thereof include ethyl butyramide, lithium methyl butyramide, lithium ethyl benzylamide, and lithium methyl phenethyl amide.

Among the polymerization initiators represented by the formula (I), a compound in which i is 0 may be preliminarily prepared from a secondary amine and a hydrocarbyl lithium compound and used for the polymerization reaction, or generated in a polymerization system. Also good. Here, examples of the secondary amine include dimethylamine, diethylamine, dibutylamine, dioctylamine, dicyclohexylamine, diisobutylamine and the like, as well as azacycloheptane (ie, hexamethyleneimine), 2- (2-ethylhexyl) pyrrolidine, 3 -(2-propyl) pyrrolidine, 3,5-bis (2-ethylhexyl) piperidine, 4-phenylpiperidine, 7-decyl-1-azacyclotridecane, 3,3-dimethyl-1-azacyclotetradecane, 4- Dodecyl-1-azacyclooctane, 4- (2-phenylbutyl) -1-azacyclooctane, 3-ethyl-5-cyclohexyl-1-azacycloheptane, 4-hexyl-1-azacycloheptane, 9-isoamyl -1-Azacycloheptadecane, 2-methyl-1-a Cycloheptadec-9-ene, 3-isobutyl-1-azacyclododecane, 2-methyl-7-tert-butyl-1-azacyclododecane, 5-nonyl-1-azacyclododecane, 8- (4-methylphenyl) -5-pentyl-3-azabicyclo [5.4.0] undecane, 1-butyl-6-azabicyclo [3.2.1] octane, 8-ethyl-3-azabicyclo [3.2.1] octane, -Propyl-3-azabicyclo [3.2.2] nonane, 3- (t-butyl) -7-azabicyclo [4.3.0] nonane, 1,5,5-trimethyl-3-azabicyclo [4.4 .0] cyclic amines such as decane.

As the polymerization initiator represented by the formula (I), a compound in which i is 1 is preferable, and a compound obtained by polymerizing 1 to 5 structural units derived from isoprene on N, N-aminoalkyllithium is more preferable. More preferred is a compound obtained by polymerizing 1 to 5 structural units derived from isoprene to-(N, N-dimethylamino) -1-propyllithium or 3- (N, N-diethylamino) -1-propyllithium.

The amount of the polymerization initiator represented by the formula (I) is preferably 0.01 to 15 mmol, more preferably 0.1 to 10 mmol, per 100 g of monomer components used in the polymerization.

In the present invention, if necessary, another polymerization initiator such as n-butyl lithium may be used in combination.

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 has been 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 ( Group represented by 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), a meta-phenylene-methylene group (a formula (1b where q = 1). ), A para-phenylene-ethylene group (a group represented by the formula (1a) where q = 2), and a meta-phenylene-ethylene group (a formula (1b) where q = 2). Represented 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.

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-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 preferably, it 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 has been 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 ( Group represented by 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). And 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 para-phenylene-ethylene group (a group represented by formula (2a) where s = 2), a meta-phenylene-ethylene group (a formula (2b) where s = 2). Represented group.).

（式中、ｒは０〜５の整数を表し、ｒが１〜５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１〜５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). In the formula, r is an integer of 0 to 5, preferably an integer of 0 to 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 aliphatic heterocycle having a nitrogen atom as a heteroatom. The nitrogen-containing aromatic heterocyclic group represents a group obtained by removing one hydrogen atom from a carbon atom of a heterocyclic ring of a compound having a nitrogen-containing aromatic heterocyclic ring, and the nitrogen-containing aromatic heterocyclic ring constitutes a ring. An aromatic heterocyclic ring having a nitrogen atom as a hetero atom is represented.

The nitrogen-containing aliphatic heterocyclic group 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 (A) in order to improve fuel efficiency. Yes, more preferably 0.02% by mass or more, still more preferably 0.05% by mass or more. In order to improve economy and wear resistance, the content is preferably 3% 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 preferably 0.01% per 100% by mass of the conjugated diene polymer (A) in order to improve fuel economy and wear resistance. It is at least mass%, more preferably at least 0.02 mass%, still more preferably at least 0.05 mass%. In order to improve economy and wear resistance, the content is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

The conjugated diene polymer (A) according to the present invention may have a structural unit (vinyl aromatic hydrocarbon unit) based on a vinyl aromatic hydrocarbon in order to improve wear resistance. Examples of the vinyl aromatic hydrocarbon include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene. Styrene is preferable.

The content of the vinyl aromatic hydrocarbon unit is 0% by mass or more (the content of the conjugated diene unit is 100% by mass or less), where the total amount of the conjugated diene unit and the vinyl aromatic hydrocarbon unit is 100% by mass. The content is preferably 10% by mass or more (the content of the conjugated diene unit is 90% by mass or less), and more preferably 15% by mass or more (the content of the conjugated diene unit is 85% by mass or less). In order to improve fuel economy, the content of vinyl aromatic hydrocarbon units is preferably 50% by mass or less (the content of conjugated diene units is 50% by mass or more), more preferably 45% by mass or less. (The content of the conjugated diene unit is 55% by mass or more).

When the conjugated diene polymer (A) has a constituent unit based on the above-mentioned vinyl aromatic hydrocarbon, the vinyl bond amount is preferably set to 100 mol% of the conjugated diene unit content in order to improve fuel efficiency. Is 80 mol% or less, more preferably 70 mol% or less. Moreover, in order to improve wet grip property, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more, Most preferably, it is 40 mol% or more. The vinyl bond amount is determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

The weight average molecular weight Mw of the conjugated diene polymer (A) is preferably 10 to 400 kg / mol, and more preferably 100 to 300 kg / mol in order to improve fuel efficiency. The weight average molecular weight Mw is determined by a gel permeation chromatograph (GPC) method.

As a suitable production method of the conjugated diene polymer (A), a conjugated diene, a compound represented by the formula (1), a compound represented by the formula (1) and a formula (I) are represented by a polymerization initiator represented by the formula (I) in a hydrocarbon solvent. The method of polymerizing the monomer component containing the compound represented by 2) can be mention | raise | lifted.

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.

In a hydrocarbon solvent, a monomer component containing a conjugated diene, a compound represented by formula (1) and a compound represented by formula (2) is polymerized by a polymerization initiator represented by formula (I). , A monomer unit based on a conjugated diene, a monomer unit based on a compound represented by the formula (1), and a monomer unit based on a compound represented by the formula (2), wherein the starting terminal is represented by the formula ( A polymer (conjugated diene polymer (A)) modified with a polymerization initiator represented by I) is produced. Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. One or more of these are used. 1,3-butadiene and isoprene are preferred.

The amount of the compound represented by the formula (1) is preferably 0.01% by mass or more in order to improve the fuel efficiency by setting the total amount of the monomer components used in the polymerization to 100% by mass. More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve economic efficiency and wear resistance, it is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. is there.

The amount of the compound represented by the formula (2) is preferably 0.01% by mass in order to increase the fuel efficiency and wear resistance, with the total amount of the monomer components used in the polymerization being 100% by mass. % Or more, more preferably 0.02 mass% or more, still more preferably 0.05 mass% or more. In order to improve economic efficiency and wear resistance, it is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. is there.

Polymerization may be carried out by combining a conjugated diene, a compound represented by the formula (1) and a compound represented by the formula (2) with a vinyl aromatic hydrocarbon. Examples of the vinyl aromatic hydrocarbon include styrene, α -Methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and the like can be mentioned. Styrene is preferable.

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

In the polymerization reaction, the total amount of the conjugated diene, the compound represented by the formula (1), the compound represented by the formula (2) and the vinyl aromatic hydrocarbon is 100. In order to increase the strength, it is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and still more preferably 100% by mass.

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

The polymerization temperature 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 production method of the conjugated diene polymer (A), if necessary, the carbonization of the conjugated diene polymer from the start of polymerization of the monomer by the polymerization initiator represented by formula (I) to the termination of polymerization is performed. A coupling agent may be added to the hydrogen solution. An example of the coupling agent is a compound represented by the following formula (3).

R ³¹ _a ZL _4-a (3)
(Wherein R ³¹ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aryl group, Z 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 (A) 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, or (2) a hydrocarbon solution of a conjugated diene polymer. It can be recovered from a hydrocarbon solution of a conjugated diene polymer by a method of adding steam. 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 (A) 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 (A) in 100% by mass of the rubber component is preferably 10% by mass or more, more preferably 20% by mass or more. If the amount is less than 10% by mass, the effect of improving fuel economy tends to be difficult to obtain. The content of the conjugated diene polymer (A) is preferably 90% by mass or less, more preferably 80% by mass or less. When it exceeds 90% by mass, the wear resistance is lowered and the cost tends to be high.

The rubber composition of the present invention preferably uses another rubber component (hereinafter also referred to as a conjugated diene polymer (B)) together with the conjugated diene polymer (A). The conjugated diene polymer (B) is not particularly limited as long as it is a rubber component other than the conjugated diene polymer (A). For example, natural rubber (NR) and diene synthetic rubber can be used. Examples of the diene synthetic rubber include isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), and butyl rubber (IIR). These may be used alone or in combination of two or more. Among these, NR, BR, and SBR are preferable, and BR and SBR are more preferable as the conjugated diene polymer (B) because it shows low fuel consumption, wet grip performance, and wear resistance.
These rubber components are not particularly limited, and those generally used in the tire industry can be used.

The content of the conjugated diene polymer (B) in 100% by mass of the rubber component is preferably 10% by mass or more, more preferably 20% by mass or more. When the content is less than 10% by mass, the content of the conjugated diene polymer (A) increases, and the wear resistance tends to decrease. The content of the conjugated diene polymer (B) is preferably 90% by mass or less, more preferably 80% by mass or less. When it exceeds 90% by mass, the content of the conjugated diene polymer (A) decreases, and there is a tendency that the fuel efficiency cannot be sufficiently improved.

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, trade names made by Degussa, Ultrasil VN3-G, trade names made by Tosoh Silica, Inc., trade names VN3, AQ, ER, RS-150, trade names made by Rhodia, Zeosil 1115MP, 1165MP, etc. can be used. .

The content of silica is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component. The content is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, in order to improve fuel efficiency. Moreover, in order to improve abrasion resistance and intensity | strength, Preferably it is 120 mass parts or less, More preferably, it is 100 mass parts or less.

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 thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethylthiuram Thiuram vulcanization accelerators such as disulfide; 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, N, N'-diisopropyl-2-benzothiazole sulfenamide; diphenylguanidine, diortolylguanidine, orthotolylbiguanidine, etc. No It can be mentioned blurring based vulcanization accelerator. The content of the vulcanization accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the rubber component.

Examples of the carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. Carbon blacks include channel carbon blacks such as EPC, MPC and CC; furnace carbon blacks such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF; FT and MT Thermal carbon black such as acetylene carbon black is exemplified. One or more of these can be used.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 5 to 200 m ² / g, and the dibutyl phthalate (DBP) absorption amount of carbon black is preferably 5 to 300 ml / 100 g. . The nitrogen adsorption specific surface area is measured according to ASTM D4820-93, and the DBP absorption is measured according to ASTM D2414-93. As a commercial item, Mitsubishi Chemical Corporation trade name Dia Black N339, Tokai Carbon Co., Ltd. trade name Seast 6, Seast 7HM, Seast KH, Degussa Corporation trade name CK3, Special Black 4A, etc. can be used.

The content of carbon black is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the rubber component. Further, the content is more preferably 2 parts by mass or more, and still more preferably 3 parts by mass or more, in order to increase wear resistance and strength. Moreover, in order to improve low fuel consumption, More preferably, it is 40 mass parts or less, More preferably, it is 30 mass parts or less.

The content of the reinforcing agent is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the rubber component. Further, the content is more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, in order to increase wear resistance and strength. Moreover, in order to improve low fuel consumption, More preferably, it is 120 mass parts or less, More preferably, it is 100 mass parts or less.

The mass ratio of the silica content and the carbon black content used as the reinforcing agent (silica content: carbon black content) is preferably 2: 1 to 50: 1. The mass ratio is more preferably 5: 1 to 20: 1 in order to increase fuel efficiency and enhance reinforcement.

Examples of the 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 a commercial item, Degussa company name Si69, Si75, etc. 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 good balance between low fuel consumption, wet grip performance and wear resistance.

The rubber composition of the present invention is used for tires, shoe soles, flooring materials, vibration-proof materials, and the like, and is preferably used for tires (particularly tire treads).

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, a rubber composition containing various additives as necessary is extruded according to the shape of a tire tread, etc. 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.

<Synthesis of a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene>
In a 100 ml container sufficiently purged with nitrogen, cyclohexane 50 ml, pyrrolidine (manufactured by Kanto Chemical Co., Ltd.) 4.1 ml (3.6 g), divinylbenzene (Sigma-Aldrich p-Divinylbenzene) 8.9 ml (6.5 g) Then, 0.7 ml of 1.6 M n-butyllithium hexane solution was added at 0 ° C. and stirred. After 1 hour, isopropanol was added to stop the reaction, extraction and purification were performed to obtain a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene.

<Synthesis of bis (diethylamino) methylvinylsilane>
To a 2 L three-necked flask thoroughly purged with nitrogen, 1000 mL of tetrahydrofuran and 13 g of sodium hydride (manufactured by Kanto Chemical Co., Ltd.) are added, and 36.5 g of diethylamine (manufactured by Kanto Chemical Co., Ltd.) is added while stirring on an ice water bath. Slowly dripped. After stirring for 30 minutes, 36 g of methylvinyldichlorosilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 30 minutes and stirred for 2 hours. The resulting solution was concentrated, filtered, and purified by distillation under reduced pressure to obtain bis (diethylamino) methylvinylsilane.

<Synthesis of initiator (1)>
In a 200 ml container made of brown glass sufficiently purged with nitrogen, 127.6 ml of dehydrated cyclohexane and 15.7 g of diamylamine were added. After cooling to 0 ° C., 62.5 ml of n-butyllithium solution was slowly added over 1 hour.

<Synthesis of copolymer (1)>
The inside of the stainless polymerization reactor with an internal volume of 30 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 15.3 kg of n-hexane, 828 g of 1,3-butadiene, 258 g of styrene, 3.2 g of a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene, 9.1 ml of tetrahydrofuran, 7.1 ml of ethylene glycol diethyl ether was put into the polymerization reactor, and the inside of the polymerization vessel was brought to 40 ° C. Next, 3.8 g of bis (diethylamino) methylvinylsilane and 24 mmol of initiator (1) were charged into the polymerization reactor to initiate the polymerization reaction. The temperature in the polymerization reactor was raised to 65 ° C., and a copolymerization reaction was carried out for 3 hours while continuously supplying 1,30 g of 1,3-butadiene and 390 g of styrene into the polymerization reactor. Further, 60 ml of a hexane solution containing 3 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 5 g of 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymer solution. 3 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) was added, and the polymer solution was evaporated at room temperature for 24 hours. It was dried under reduced pressure for a time to obtain a copolymer (1).

<Synthesis of copolymer (2)>
Initiator (1) 24 mmol was added to initiator (2) (FMC Co., Ltd. AI-200CE2 (3- (N, N-dimethylamino) -1-propyllithium with 2 units of structural units derived from isoprene). The compound (2) was obtained using the same method as the copolymer (1) except that the compound was changed to 24 mmol.

<Synthesis of copolymer (3)>
Except for changing 3.2 g of a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene to 0.5 g and 3.8 g of bis (diethylamino) methylvinylsilane to 0.6 g, A copolymer (3) was obtained using the same method as for the polymer (2).

<Synthesis of copolymer (4)>
A copolymer except that 3.2 g of a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene was changed to 50 g and 3.8 g of bis (diethylamino) methylvinylsilane was changed to 0.6 g. A copolymer (4) was obtained using the same method as (2).

<Synthesis of copolymer (5)>
The inside of the stainless polymerization reactor with an internal volume of 30 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 15.3 kg of cyclohexane, 960 g of 1,3-butadiene, 3.2 g of a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene, 9.1 ml of tetrahydrofuran, ethylene glycol diethyl ether 7 0.1 ml was put into the polymerization reactor, and the inside of the polymerization vessel was brought to 40 ° C. Next, 3.8 g of bis (diethylamino) methylvinylsilane and 32 mmol of initiator (2) were charged into the polymerization reactor to initiate the polymerization reaction. The temperature in the polymerization reactor was raised to 65 ° C., and 1420 g of 1,3-butadiene was continuously fed into the polymerization reactor to carry out the copolymerization reaction for 3 hours. Further, 60 ml of a hexane solution containing 3 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 5 g of 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymer solution. 3 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) was added, and the polymer solution was evaporated at room temperature for 24 hours. It was dried under reduced pressure for a time to obtain a copolymer (5).

<Synthesis of copolymer (6)>
A copolymer (6) was obtained using the same method as the copolymer (1) except that 24 mmol of the initiator (1) was changed to 24 mmol of butyllithium solution.

<Synthesis of copolymer (7)>
A copolymer (7) was obtained using the same method as the copolymer (2) except that 3.8 g of bis (diethylamino) methylvinylsilane was changed to 0 g.

<Synthesis of copolymer (8)>
The copolymer (8) was prepared in the same manner as the copolymer (2) except that 3.2 g of a mixture of 3- (1-pyrrolidinyl) ethylstyrene and 4- (1-pyrrolidinyl) ethylstyrene was changed to 0 g. )

<Synthesis of copolymer (9)>
The inside of the stainless polymerization reactor with an internal volume of 30 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 15.3 kg of cyclohexane, 960 g of 1,3-butadiene, 9.1 ml of tetrahydrofuran, and 7.1 ml of ethylene glycol diethyl ether were charged into the polymerization reactor, and the inside of the polymerization vessel was brought to 40 ° C. Next, 32 mmol of butyl lithium solution was charged into the polymerization reactor to initiate the polymerization reaction. The temperature in the polymerization reactor was raised to 65 ° C., and 1420 g of 1,3-butadiene was continuously fed into the polymerization reactor to carry out the copolymerization reaction for 3 hours. Further, 60 ml of a hexane solution containing 3 ml of methanol was added to the polymer solution, and the polymer solution was stirred for 5 minutes. Next, 5 g of 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM) was added to the polymer solution. 3 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) was added, and the polymer solution was evaporated at room temperature for 24 hours. It was dried under reduced pressure for a time to obtain a copolymer (9).

The obtained copolymers (1) to (9) were analyzed by the following method. The results are shown in Table 1.

<Measurement of weight average molecular weight Mw>
The weight average molecular weight Mw of the copolymer is determined by gel permeation chromatography (GPC) (GPC-8000 series, manufactured by Tosoh Corporation), detector: differential refractometer, column: TSKGEL SUPERMULTIPORE HZ-M manufactured by Tosoh Corporation. It calculated | required as a standard polystyrene conversion value based on the measured value.

<Structural identification of copolymer>
The amount of styrene (content of styrene units) and the amount of vinyl (vinyl bond amount) in the copolymer were measured using an apparatus of JNM-ECA series manufactured by JEOL Ltd. The measurement was performed after dissolving 0.1 g of the copolymer in 15 ml of toluene, slowly pouring it into 30 ml of methanol and reprecipitating it under reduced pressure.
In addition, the content of the monomer unit based on the compound represented by the formula (1) and the content of the monomer unit based on the compound represented by the formula (2) are as follows. After mixing and precipitating the copolymer, the amount of the compound contained in the solution layer (the amount of the compound not taken into the copolymer) is obtained by gas chromatography and calculated from the difference from the amount of the compound added. did.

Below, various chemical | medical agents used by the Example and the comparative example are demonstrated.
Copolymers (1) to (9): Synthetic silica by the above method: Ultrasil VN3-G (N ₂ SA: 175 m ² / g) manufactured by Degussa
Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa
Carbon black: Dia Black N339 manufactured by Mitsubishi Chemical Corporation (N ₂ SA: 96 m ² / g, DBP absorption: 124 ml / 100 g)
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Anti-aging agent: Antigen 3C manufactured by Sumitomo Chemical Co., Ltd.
Stearic acid: Beads manufactured by NOF Corporation Zinc stearate Zinc oxide: Zinc flower No. 1 manufactured by Mitsui Kinzoku Mining Co., Ltd. Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. 1: Soxinol CZ manufactured by Sumitomo Chemical Co., Ltd.
Vulcanization accelerator 2: Soxinol D manufactured by Sumitomo Chemical Co., Ltd.

(Examples and Comparative Examples)
In accordance with the contents shown in Tables 2 and 3, materials other than sulfur and a vulcanization accelerator were kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer manufactured by Kobe Steel, Ltd., and mixed. A kneaded paste was obtained. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes under the condition of 80 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized with a 0.5 mm thick mold at 170 ° C. for 20 minutes to obtain a vulcanized rubber composition. Further, the obtained unvulcanized rubber composition is molded into a tread shape and bonded together with other tire members on a tire molding machine to form an unvulcanized tire, which is vulcanized at 170 ° C. for 12 minutes, and tested. Tires (size: 195 / 65R15) were manufactured.

<Evaluation items and test methods>
In the following evaluation, the reference comparative example in Table 2 was set as Comparative Example 2, and the reference comparative example in Table 3 was set as Comparative Example 4.

<Tan δ>
Using a spectrometer manufactured by Ueshima Seisakusho, tan δ of the vulcanized rubber composition was measured at a dynamic strain amplitude of 1%, a frequency of 10 Hz, and a temperature of 50 ° C. The reciprocal value of tan δ was expressed as an index with the reference comparative example being 100. Larger values indicate lower rolling resistance and better fuel efficiency.

<Rolling resistance>
Using a rolling resistance tester, the rolling resistance when the test tire was run at a rim (15 × 6JJ), internal pressure (230 kPa), load (3.43 kN), speed (80 km / h) was measured, and the standard The index is expressed as an index when the comparative example is 100. Larger values indicate lower rolling resistance and better fuel efficiency.

<Wet grip performance>
Each test tire was mounted on all wheels of a vehicle (domestic FF2000cc), and a braking distance from an initial speed of 100 km / h was determined on a wet asphalt road surface. The result is expressed as an index. The larger the value, the better the wet skid performance (wet grip performance). The index was calculated by the following formula.
(Wet grip performance index) = (braking distance of reference comparative example) / (braking distance of each formulation) × 100

<Abrasion resistance>
Using a LAT tester (Laboratory Abrasion and Skid Tester), the volume loss of each vulcanized rubber composition was measured under the conditions of a load of 50 N, a speed of 20 km / h, and a slip angle of 5 °. The numerical values (wear resistance index) in Tables 2 and 3 are relative values when the volume loss amount of the reference comparative example is 100. The larger the value, the better the wear resistance.

As shown in Tables 2 and 3, conjugated diene polymer (A) (copolymers (1) to (5)), conjugated diene polymer (B) (copolymers (6) to (9)). Further, in the examples in which silica and silica were blended, the fuel economy, wet grip performance and wear resistance were improved in a well-balanced manner as compared with the rubber composition of the comparative example. In addition, the rubber composition of Table 2 having a high silica content tended to have a greater improvement effect due to the blending of the conjugated diene polymer (A) as compared with the rubber composition of Table 3.

Claims (7)

Monomer unit based on Conjugate diene monomer unit based on a compound represented by the following formula (1), and having a monomer unit based on a compound represented by the following formula (2), starting Containing a conjugated diene polymer (A) having a terminal modified with a polymerization initiator represented by the following formula (I), and silica;
The rubber composition whose content of the said silica with respect to 100 mass parts of rubber components is 5-150 mass parts.

(In Formula (I), i is 0 or 1, R ¹ represents a hydrocarbylene group having 1 to 100 carbon atoms, R ² and R ³ are hydrocarbyl groups which may have a substituent, Alternatively, it represents a trihydrocarbylsilyl group, or R ² and R ³ are bonded to each other and have at least one atom selected from the group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a hetero atom. Represents an optionally hydrocarbylene group, and M represents an alkali metal atom.)

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 according to claim ¹ , wherein R ^{1 in the} formula (I) is a group represented by the following formula (Ia).

(In formula (Ia), R ⁴ represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, and j represents an integer of 1 to 10.) The rubber composition according to claim 1 or 2, 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 in any one.

(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 content of the monomer unit based on the compound represented by the formula (1) per 100 mass% of the conjugated diene polymer (A) is 0.01 to 3 mass%, and is represented by the formula (2). The rubber composition according to any one of claims 1 to 4, wherein the content of the monomer unit based on the compound is 0.01 to 3% by mass. The rubber composition according to any one of claims 1 to 5, wherein the content of the conjugated diene polymer (A) is 10 to 90% by mass in 100% by mass of the rubber component. The pneumatic tire produced using the rubber composition in any one of Claims 1-6 .