JP6046423B2 - Diene copolymer, rubber composition, and pneumatic tire - Google Patents

Description

The present invention relates to a diene copolymer, a rubber composition, and a pneumatic tire.

In recent years, from the standpoint of saving resources and protecting the environment, it has been required to improve fuel efficiency by improving rolling resistance of tires, and also to improve wet grip performance to improve safety during driving.

Hysteresis loss is required to improve fuel economy, and wet skid resistance is required to improve wet grip performance. However, low hysteresis loss and high wet skid resistance are contradictory, and it is difficult to improve the fuel economy and wet grip performance in a balanced manner.

As a method for improving fuel economy and wet grip performance in a well-balanced manner, there is a method using silica as a filler. However, silica has a room for improvement in that it is highly self-aggregating and difficult to disperse. In Patent Document 1, a styrene butadiene rubber terminal-modified with a specific compound containing a nitrogen atom and a silicon atom and an aliphatic carboxylic acid zinc salt are blended, and a rubber composition excellent in fuel efficiency and wet grip performance is obtained. Although a method for obtaining an object is described, provision of other methods is also sought.

JP 2010-111754 A

An object of the present invention is to solve the above-mentioned problems and to provide a diene copolymer capable of providing a rubber composition and a pneumatic tire having improved fuel economy, wet grip performance and wear resistance in a well-balanced manner. And

As a result of intensive studies and studies to solve the above problems, the present inventors have used a polymerization initiator having a specific amino group, a conjugated diene compound, a specific aromatic compound, and a specific silicon compound (silicon-containing). Rubber composition comprising a diene copolymer obtained by reacting a specific compound with an active end of a diene copolymer obtained by copolymerizing a vinyl compound) and having a weight average molecular weight Mw within a specific range By producing a pneumatic tire using an object, it has been found that fuel economy, wet grip performance and wear resistance are improved in a well-balanced manner, and the present invention has been made.

（式中、ｄ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は１〜２０の整数を表し、Ｒ^１１及びＲ^１３はそれぞれ独立に、炭素原子数１〜１０のヒドロカルビル基を表し、Ｒ^１２は炭素原子数１〜１０のヒドロカルビレン基を表し、Ｒ^１１、Ｒ^１２及びＲ^１３の少なくとも１つが下記一般式（ＩＩ−１）で表される基を有する。Ｒ^１１とＲ^１３は互いに結合していてもよい。）

（式中、ｋは０又は１であり、Ｒ^１４はヒドロカルビレン基を表し、Ｒ^１５、Ｒ^１６及びＲ^１７はそれぞれ独立に、置換アミノ基、ヒドロカルビルオキシ基、又は置換基を有していてもよいヒドロカルビル基を表す。）

（式中、Ｒ^２１は、水素原子、炭素原子数が１〜１０のヒドロカルビル基又は炭素原子数が１〜６の置換ヒドロカルビル基を表す。ｎは、１〜１０の整数を表し、Ａ^１は、酸素原子又は−ＮＲ^２２−基（Ｒ^２２は、水素原子又は炭素原子数が１〜１０のヒドロカルビル基を表す。）を表し、Ａ^２は、窒素原子及び／又は酸素原子を有する官能基を表す。）

（式中、ｐは０又は１の整数を表し、Ｔは、炭素原子数が１〜２０のヒドロカルビレン基又は炭素原子数が１〜２０の置換ヒドロカルビレン基を表し、Ａ^３は窒素原子を有する官能基を表す。）

（式中、ｍは１〜１１の整数を表し、Ａ^４は窒素原子を有する官能基を表す。） That is, this invention is represented by the conjugated diene compound, the compound represented by the following general formula (II), and the following general formula (III) using the polymerization initiator represented by the following general formula (I). A compound having a compound represented by the following general formula (IV) and a group represented by the following general formula (V) at the active terminal of a diene copolymer obtained by copolymerizing a monomer containing a silicon compound And at least one compound selected from the group consisting of compounds having a group represented by the following general formula (VI), and having a weight average molecular weight Mw of 1.0 × 10 ^{5 to} 2.5 × 10. ⁶ is a diene copolymer.

(In the formula, d is 0 or 1, R ¹ represents a hydrocarbylene group having 1 to 100 carbon atoms, and R ² and R ³ are hydrocarbyl groups which may have a substituent, or tri A hydrocarbylsilyl group, or R ² and R ³ may be 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 heteroatom. Represents a good hydrocarbylene group, and M represents an alkali metal atom.)

(Wherein, r represents an integer of 1 to 20, R ¹¹ and R ¹³ each independently represent a hydrocarbyl group having 1 to 10 carbon atoms, and R ¹² represents a hydrocarbylene group having 1 to 10 carbon atoms. And at least one of R ¹¹ , R ¹² and R ¹³ has a group represented by the following general formula (II-1): R ¹¹ and R ¹³ may be bonded to each other.

(In the formula, k is 0 or 1, R ¹⁴ represents a hydrocarbylene group, and R ¹⁵ , R ^16, and R ¹⁷ each independently have a substituted amino group, a hydrocarbyloxy group, or a substituent. Represents an optional hydrocarbyl group.)

(In the formula, R ²¹ represents a hydrogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, or a substituted hydrocarbyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 10, and A ¹ represents , An oxygen atom or a —NR ²² — group (R ²² represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms), and A ² represents a functional group having a nitrogen atom and / or an oxygen atom. Represents.)

(In the formula, p represents an integer of 0 or 1, T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms, and A ³ represents nitrogen. Represents a functional group having an atom.)

(In the formula, m represents an integer of 1 to 11, and A ⁴ represents a functional group having a nitrogen atom.)

（式中、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、ｚは１〜１０の整数を表す。） R ¹ in the general formula (I) is preferably a group represented by the following general formula (Ia).

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

The monomer preferably contains styrene.

The content of the compound represented by the general formula (II) in the diene copolymer is preferably 0.05 to 10% by mass. The content of the silicon compound represented by the general formula (III) in the diene copolymer is preferably 0.05 to 10% by mass.

The present invention also relates to a rubber composition containing 5% by mass or more of the diene copolymer in 100% by mass of the rubber component. The rubber composition preferably contains 5 to 150 parts by mass of silica with respect to 100 parts by mass of the rubber component.
The rubber composition is preferably used as a tire rubber composition.

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

According to the present invention, an active terminal of a diene copolymer obtained by copolymerizing a conjugated diene compound, a specific aromatic compound, and a specific silicon compound using a polymerization initiator having a specific amino group. The diene copolymer obtained by reacting a specific compound and having a weight average molecular weight Mw within a specific range is low in rubber compositions and pneumatic tires using the diene copolymer. The fuel economy, wet grip performance and wear resistance can be improved in a well-balanced manner.

（式中、ｄ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は１〜２０の整数を表し、Ｒ^１１及びＲ^１３はそれぞれ独立に、炭素原子数１〜１０のヒドロカルビル基を表し、Ｒ^１２は炭素原子数１〜１０のヒドロカルビレン基を表し、Ｒ^１１、Ｒ^１２及びＲ^１３の少なくとも１つが下記一般式（ＩＩ−１）で表される基を有する。Ｒ^１１とＲ^１３は互いに結合していてもよい。）

（式中、ｋは０又は１であり、Ｒ^１４はヒドロカルビレン基を表し、Ｒ^１５、Ｒ^１６及びＲ^１７はそれぞれ独立に、置換アミノ基、ヒドロカルビルオキシ基、又は置換基を有していてもよいヒドロカルビル基を表す。）

（式中、Ｒ^２１は、水素原子、炭素原子数が１〜１０のヒドロカルビル基又は炭素原子数が１〜６の置換ヒドロカルビル基を表す。ｎは、１〜１０の整数を表し、Ａ^１は、酸素原子又は−ＮＲ^２２−基（Ｒ^２２は、水素原子又は炭素原子数が１〜１０のヒドロカルビル基を表す。）を表し、Ａ^２は、窒素原子及び／又は酸素原子を有する官能基を表す。）

（式中、ｐは０又は１の整数を表し、Ｔは、炭素原子数が１〜２０のヒドロカルビレン基又は炭素原子数が１〜２０の置換ヒドロカルビレン基を表し、Ａ^３は窒素原子を有する官能基を表す。）

（式中、ｍは１〜１１の整数を表し、Ａ^４は窒素原子を有する官能基を表す。） The diene copolymer of the present invention is prepared by using a polymerization initiator represented by the following general formula (I), a conjugated diene compound, a compound represented by the following general formula (II), and the following general formula (III). A compound represented by the following general formula (IV), represented by the following general formula (V) at the active end of a diene copolymer obtained by copolymerizing a monomer containing a silicon compound represented by: It is obtained by reacting at least one compound selected from the group consisting of a compound having a group and a compound having a group represented by the following general formula (VI), and has a weight average molecular weight Mw of 1.0 × 10 ⁵ to 2 .5 × 10 ⁶ .

(In the formula, d is 0 or 1, R ¹ represents a hydrocarbylene group having 1 to 100 carbon atoms, and R ² and R ³ are hydrocarbyl groups which may have a substituent, or tri A hydrocarbylsilyl group, or R ² and R ³ may be 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 heteroatom. Represents a good hydrocarbylene group, and M represents an alkali metal atom.)

(Wherein, r represents an integer of 1 to 20, R ¹¹ and R ¹³ each independently represent a hydrocarbyl group having 1 to 10 carbon atoms, and R ¹² represents a hydrocarbylene group having 1 to 10 carbon atoms. And at least one of R ¹¹ , R ¹² and R ¹³ has a group represented by the following general formula (II-1): R ¹¹ and R ¹³ may be bonded to each other.

(In the formula, k is 0 or 1, R ¹⁴ represents a hydrocarbylene group, and R ¹⁵ , R ^16, and R ¹⁷ each independently have a substituted amino group, a hydrocarbyloxy group, or a substituent. Represents an optional hydrocarbyl group.)

(In the formula, R ²¹ represents a hydrogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, or a substituted hydrocarbyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 10, and A ¹ represents , An oxygen atom or a —NR ²² — group (R ²² represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms), and A ² represents a functional group having a nitrogen atom and / or an oxygen atom. Represents.)

(In the formula, p represents an integer of 0 or 1, T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms, and A ³ represents nitrogen. Represents a functional group having an atom.)

(In the formula, m represents an integer of 1 to 11, and A ⁴ represents a functional group having a nitrogen atom.)

By using the diene copolymer together with silica, the interaction between the polymerization initiator contained in the diene copolymer and silica, and the interaction between the compound represented by the general formula (II) and silica. The dispersibility of the silica is improved by the action, the interaction between the silicon compound represented by the general formula (III) and silica, and the interaction between the terminal modifier and silica. Movement is restrained. As a result, it is possible to obtain a pneumatic tire with reduced hysteresis loss, improved fuel efficiency, improved wet grip performance, and improved wear resistance.
In addition, since the diene copolymer is modified with a combination of specific compounds, the improvement effect is synergistically improved, and fuel efficiency, wet grip performance, and wear resistance can be greatly improved.

In the present specification, the hydrocarbyl group represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon. The hydrocarbylene group represents a divalent group obtained by removing two hydrogen atoms from a hydrocarbon. The hydrocarbyloxy group represents a monovalent group having a structure in which a hydrogen atom of a hydroxy group is replaced with a hydrocarbyl group. A substituted amino group is a group having a structure in which at least one hydrogen atom of an amino group is replaced by a monovalent atom other than a hydrogen atom or a monovalent group, or two hydrogen atoms of an amino group are divalent groups Represents a group having a structure replaced by The hydrocarbyl group having a substituent (hereinafter sometimes referred to as a substituted hydrocarbyl group) represents a monovalent group having a structure in which at least one hydrogen atom of the hydrocarbyl group is replaced with a substituent. A hydrocarbylene group having a heteroatom (hereinafter sometimes referred to as a heteroatom-containing hydrocarbylene group) is a carbon atom and / or hydrogen other than the carbon atom from which the hydrogen atom of the hydrocarbylene group is removed. A divalent group having a structure in which an atom is replaced with a group having a hetero atom (an atom other than a carbon atom or a hydrogen atom) is represented.

（式中、ｄ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。） (Polymerization initiator)
In the present invention, a compound represented by the following general formula (I) is used as a polymerization initiator.

(In the formula, d is 0 or 1, R ¹ represents a hydrocarbylene group having 1 to 100 carbon atoms, and R ² and R ³ are hydrocarbyl groups which may have a substituent, or tri A hydrocarbylsilyl group, or R ² and R ³ may be 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 heteroatom. Represents a good hydrocarbylene group, and M represents an alkali metal atom.)

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

R ¹ in the general 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. Of the 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 the general formula (I), the number of carbon atoms of R ¹ may be used in combination plural kinds of different compounds.

（式中、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、ｚは１〜１０の整数を表す。） R ¹ in the general formula (I) is preferably a group represented by the following general formula (Ia).

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

In general 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. More preferably, it is 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 general formula (Ia), z is an integer of 1-10, Preferably it is an integer of 2-4.

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 the general formula (I) represent a hydrocarbyl group or trihydrocarbylsilyl group which may have a substituent, or R ² and R ³ are bonded to form a silicon atom. , A hydrocarbylene group optionally having, as a hetero atom, an atom selected from the group consisting of a nitrogen atom and an oxygen 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 further 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 general 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 general formula (I), examples of the compound in which d is 1 include compounds obtained by polymerizing isoprene units 1 to 5 units 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-dialkylaminoalkyl lithium such as -propylamino) -1-butyllithium and 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 general formula (I), compounds in which d is 0 include lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, and lithium dimethyl. Amide, lithium diethylamide, lithium dipropylamide, lithium dibutylamide, lithium dihexylamide, lithium diheptylamide, lithium dioctylamide, lytimidi-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiperazide, lithium ethylpropylamide, Examples include lithium ethyl butyramide, lithium methyl butyramide, lithium ethyl benzylamide, lithium methyl phenethyl amide and the like.

Among the polymerization initiators represented by the general formula (I), a compound in which d is 0 may be preliminarily prepared from a secondary amine and a hydrocarbyl lithium compound and used for the polymerization reaction, or may be generated in a polymerization system. May be. 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 general formula (I), a compound in which d is 1 is preferable, and a compound obtained by polymerizing 1 to 5 units of isoprene units on N, N-aminoalkyllithium is more preferable. A compound obtained by polymerizing 1 to 5 units of isoprene units on N, N-dimethylamino) -1-propyllithium or 3- (N, N-diethylamino) -1-propyllithium is more preferable.

In the above copolymer, the content of the structural unit derived from the polymerization initiator represented by the general formula (I) is from the viewpoint of improving the fuel economy, wet grip performance and wear resistance in a balanced manner. Preferably, it is 0.0001 mmol / g polymer or more, more preferably 0.001 mmol / g polymer or more, preferably 0.15 mmol / g polymer or less, more preferably 0.1 mmol / g polymer or less. It is.

(Monomer)
In the present invention, a conjugated diene compound, a compound represented by the general formula (II), and a silicon compound represented by the general formula (III) are used as monomers.

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. These may be one type or two or more types. From the viewpoint of availability, 1,3-butadiene and isoprene are preferable.

In the general formula (II), the hydrocarbyl group represented by R ¹¹ and R ¹³ has 1 to 10 carbon atoms. If the number of carbon atoms exceeds 10, the cost tends to increase. The number of carbon atoms is preferably 1-8, more preferably 1-6, from the viewpoint that the resulting diene copolymer has a high effect of improving fuel economy, wet grip performance and wear resistance.

Examples of the hydrocarbyl group represented by R ¹¹ and R ¹³ include a monovalent aliphatic hydrocarbon group such as an alkyl group and a monovalent aromatic hydrocarbon group such as an aryl group. R ¹¹ and R ¹³ are preferably alkyl groups, and methyl groups, ethyl groups, and n-propyl groups are preferred because the resulting diene copolymer has high fuel economy, wet grip performance, and high wear resistance improvement effect. , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group are more preferable.

Examples of the group to which R ¹¹ and R ¹³ are bonded include the same groups as the hydrocarbylene group represented by R ¹² described later. The group to which R ¹¹ and R ¹³ are bonded is preferably an alkylene group, and more preferably an ethylene group.

The hydrocarbylene group represented by R ¹² has 1 to 10 carbon atoms. If the number of carbon atoms exceeds 10, the cost tends to increase. The number of carbon atoms is preferably 1-8, more preferably 1-6, from the viewpoint that the resulting diene copolymer has a high effect of improving fuel economy, wet grip performance and wear resistance.
In addition, the carbon atom number of R < ¹¹ >, R < ¹² > and R < ¹³ > includes the carbon atom number 8 of the group represented by the general formula (II-1).

Examples of the hydrocarbylene group represented by R ¹² include a divalent aliphatic hydrocarbon group such as an alkylene group and a divalent aromatic hydrocarbon group such as an arylene group. R ¹² is preferably an alkylene group, and methylene group, ethylene group, n-propylene group, isopropylene, from the viewpoint that the resulting diene copolymer is highly effective in improving fuel economy, wet grip performance and abrasion resistance. Groups are more preferred. When r is 2 or more, each R ¹² may be the same or different.

r represents an integer of 1 to 20. If r exceeds 20, the cost increases. r is preferably 10 or less, more preferably 5 or less.

At least one of R ¹¹ , R ¹² and R ¹³ has a group represented by the general formula (II-1). One of R ¹¹ , R ¹² and R ¹³ is represented by the above general formula (II-1) because the resulting diene copolymer has a high effect of improving fuel economy, wet grip performance and wear resistance. It is preferable to have a group.

The compound represented by the general formula (II) can be synthesized by a known method. For example, it can be obtained by reacting a halogenated alkylstyrene with a polyalkylene glycol monoalkyl ether in the presence of a strong base. Specifically, using N, N-dimethylformamide as a solvent, a halogenated alkylstyrene (for example, 4-chloromethylstyrene) and a polyalkylene glycol monoalkyl ether (triethylene glycol monoalkyl ether) in the presence of sodium hydride. And butyl ether).
It can also be obtained by acetalizing vinylbenzaldehyde (for example, 4-vinylbenzaldehyde) by a known method.

Examples of the compound represented by the general formula (II) include 4-vinylbenzaldehyde dimethyl acetal, 4-vinylbenzaldehyde diethyl acetal, 4-vinylbenzaldehyde di-n-propyl acetal, 4-vinylbenzaldehyde diisopropyl acetal, the following formula Examples thereof include compounds represented by (1) to (4). Especially, the compound represented by following formula (1)-(4) is preferable from the point that the improvement effect of fuel-consumption property, wet grip performance, and abrasion resistance is high, and following formula (1), (4) The compound represented by the following formula (1) is still more preferable. In addition, the compound represented with the said general formula (II) may be used independently, and may combine 2 or more types.

The content of the compound represented by the general formula (II) in the diene copolymer is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 10% by mass. % Or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less. If it is less than 0.05% by mass, it is difficult to obtain the effect of improving fuel economy, wet grip performance and wear resistance, while if it exceeds 10% by mass, the cost tends to be high.
In addition, content of the compound represented by the said general formula (II) in the said diene type copolymer can be measured by the method of the Example mentioned later.

（式中、ｋは０又は１であり、Ｒ^１４はヒドロカルビレン基を表し、Ｒ^１５、Ｒ^１６及びＲ^１７はそれぞれ独立に、置換アミノ基、ヒドロカルビルオキシ基、又は置換基を有していてもよいヒドロカルビル基を表す。） In the present invention, a silicon compound represented by the following general formula (III) is used as a monomer.

(In the formula, k is 0 or 1, R ¹⁴ represents a hydrocarbylene group, and R ¹⁵ , R ^16, and R ¹⁷ each independently have a substituted amino group, a hydrocarbyloxy group, or a substituent. Represents an optional hydrocarbyl group.)

K in the general formula (III) is 0 or 1, and is preferably 0 from the viewpoint of high effects of improving fuel economy, wet grip performance and wear resistance.

Examples of the hydrocarbylene group for R ¹⁴ include an alkylene group, an alkenediyl 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. Examples of the alkenediyl group include a vinylene group and an ethylene-1,1-diyl group. Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the group in which an arylene group and an alkylene group are bonded include a group in which a phenylene group and a methylene group are bonded, and a group in which a phenylene group and an ethylene group are bonded.

R ¹⁴ is preferably an arylene group, more preferably a phenylene group.

R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a substituted amino group, a hydrocarbyloxy group, or an optionally substituted hydrocarbyl group. From the viewpoint of high effect of improving fuel economy, wet grip performance and wear resistance, preferably at least one of R ¹⁵ , R ¹⁶ and R ¹⁷ is a substituted amino group, more preferably R ¹⁵ , R ^16. And two of R ¹⁷ are substituted amino groups.

（式中、Ｒ^１８及びＲ^１９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^１８とＲ^１９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を表す。） The substituted amino group in the general formula (III) is preferably a group represented by the following general formula (IIIa).

(Wherein R ¹⁸ and R ¹⁹ represent a hydrocarbyl group or a trihydrocarbylsilyl group which may have a substituent, or R ¹⁸ and R ¹⁹ are bonded to each other to form a nitrogen atom and / or (This represents a hydrocarbylene group which may have an oxygen atom as a hetero atom.)

The hydrocarbyl group which may have a substituent in the general formula (IIIa) is a hydrocarbyl group or a substituted hydrocarbyl group. Examples of the substituted hydrocarbyl group include a substituted hydrocarbyl group in which the substituent is 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. A chain alkyl group such as a group; a cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group; and an aryl group such as a phenyl group, a benzyl group, and a naphthyl group. A chain alkyl group is preferred, and a methyl group or an ethyl group is preferred. More preferred. Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, ethoxymethyl group, and methoxyethyl group; aryloxyalkyl groups such as a phenoxymethyl group.

Examples of the trihydrocarbylsilyl group in the general formula (IIIa) include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.

The hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom as a hetero atom in the general formula (IIIa) is a hetero atom-containing hydrocarbyl group or a hetero atom-containing hydrocarbyl group in which the hetero atom is a nitrogen atom and / or an oxygen atom Carbylene group. The heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom and / or an oxygen atom includes a heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom, and a heteroatom-containing hydrocarbylene in which the heteroatom is an oxygen atom You can raise a group. Examples of the hydrocarbylene group include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, decamethylene group, dodecamethylene group, 2,2,4-trimethylhexane-1,6. An alkylene group such as a diyl group; and an alkenediyl group such as a pentane-2-ene-1,5-diyl group. 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 —.

R ¹⁸ and R ¹⁹ are alkyl groups, or R ¹⁸ and R ¹⁹ are preferably combined to form an alkylene group, more preferably an alkyl group, and a methyl group or an ethyl group. Is more preferable.

Of the substituted amino groups represented by the general formula (IIIa), R ¹⁸ and R ¹⁹ are hydrocarbyl groups, and include dimethylamino group, diethylamino group, ethylmethylamino group, di-n-propylamino group, diisopropylamino. A dialkylamino group such as a diphenylamino group; a dialkylamino group such as a diphenylamino group; a dialkylamino group such as a diphenylamino group; An amino group is preferable, and a dimethylamino group, a diethylamino group, and a di-n-butylamino group are more preferable. Examples of R ¹⁸ and R ^{19 which} are substituted hydrocarbyl groups having a hydrocarbyloxy group as a substituent include di (alkoxyalkyl) amino groups such as di (methoxymethyl) amino group and di (ethoxymethyl) amino group. Can do. Examples of R ¹⁸ and R ^{19 that} are trihydrocarbylsilyl groups include trialkylsilyl groups such as bis (trimethylsilyl) amino group, bis (tert-butyldimethylsilyl) amino group, and N-trimethylsilyl-N-methylamino group. An amino group can be mentioned.

Among the substituted amino groups represented by the general formula (IIIa), those in which R ¹⁸ and R ¹⁹ are bonded to form a hydrocarbylene group include a 1-trimethyleneimino group, a 1-pyrrolidino group, -1-alkyleneimino groups such as -piperidino group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-decamethyleneimino group, 1-dodecamethyleneimino group . Examples of the hetero atom-containing hydrocarbylene group in which the hetero atom is a nitrogen atom include a 1-imidazolyl group and a 4,5-dihydro-1-imidazolyl group. Examples of the hetero atom-containing hydrocarbylene group in which the hetero atom is an oxygen atom include a morpholino group.

The substituted amino group represented by the general formula (IIIa) is preferably a dialkylamino group or a 1-alkyleneimino group, more preferably a dialkylamino group, and further a dimethylamino group, a diethylamino group, or a di-n-butylamino group. preferable.

Examples of the hydrocarbyloxy group in the general formula (III) include alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group; An aryloxy group such as an oxy group can be mentioned.

The hydrocarbyl group which may have a substituent in the general formula (III) is a hydrocarbyl group or a substituted hydrocarbyl group. Examples of the substituted hydrocarbyl group include a substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group. Examples of the hydrocarbyl 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; a phenyl group, a 4-methyl-1-phenyl group, An aryl group such as a benzyl group can be mentioned. Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, and an ethoxyethyl group.

Among the silicon compounds represented by the general formula (III), one of R ¹⁵ , R ¹⁶ and R ¹⁷ is a substituted amino group and k is 0.
(Dimethylamino) dimethylvinylsilane, (ethylmethylamino) dimethylvinylsilane, (di-n-propylamino) dimethylvinylsilane, (diisopropylamino) dimethylvinylsilane, (dimethylamino) diethylvinylsilane, (ethylmethylamino) diethylvinylsilane, (di (N-propylamino) diethylvinylsilane, (dialkylamino) dialkylvinylsilanes such as (diisopropylamino) diethylvinylsilane; [bis (trimethylsilyl) amino] dimethylvinylsilane, [bis (t-butyldimethylsilyl) amino] dimethylvinylsilane, [bis [Bis (trialkyl) amino] diethylvinylsilane, [bis (t-butyldimethylsilyl) amino] diethylvinylsilane, etc. (Silyl) amino] dialkylvinylsilane; (dimethylamino) di (methoxymethyl) vinylsilane, (dimethylamino) di (methoxyethyl) vinylsilane, (dimethylamino) di (ethoxymethyl) vinylsilane, (dimethylamino) di (ethoxyethyl) vinylsilane (Dialkylamino) di (alkoxyalkyl) such as (diethylamino) di (methoxymethyl) vinylsilane, (diethylamino) di (methoxyethyl) vinylsilane, (diethylamino) di (ethoxymethyl) vinylsilane, (diethylamino) di (ethoxyethyl) vinylsilane ) Vinylsilane; pyrrolidinodimethylvinylsilane, piperidinodimethylvinylsilane, hexamethyleneiminodimethylvinylsilane, 4,5-dihydroimidazolyldimethylvinyl Silane, can be mentioned morpholino cyclic amino dialkylvinylsilane compounds such as dimethyl vinyl silane.

Among the silicon compounds represented by the general formula (III), one of R ¹⁵ , R ¹⁶ and R ¹⁷ is a substituted amino group and k 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-butyl) Amino) dimethyl-3-vinylphenylsilane, (dimethylamino) diethyl-4-vinylphenylsilane, (dimethylamino) diethyl-3-vinylphenylsilane, (diethylamino) diethyl-4-vinylphenylsilane, (diethylamino) diethyl- 3-vinyl pheny Silane, (di-n-propylamino) diethyl-4-vinylphenylsilane, (di-n-propylamino) diethyl-3-vinylphenylsilane, (di-n-butylamino) diethyl-4-vinylphenylsilane, Mention may be made of (dialkylamino) dialkylvinylphenylsilanes such as (di-n-butylamino) diethyl-3-vinylphenylsilane.

Among the silicon compounds represented by the general formula (III), two of R ¹⁵ , R ¹⁶ and R ¹⁷ are substituted amino groups and k is 0.
Bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (di-n-propylamino) methylvinylsilane, bis (di-n-butylamino) methylvinylsilane, bis (dimethylamino) ethylvinylsilane, bis (diethylamino) ) Bis (dialkylamino) alkylvinylsilanes such as ethylvinylsilane, bis (di-n-propylamino) ethylvinylsilane, bis (di-n-butylamino) ethylvinylsilane; bis [bis (trimethylsilyl) amino] methylvinylsilane, bis [ Bis (tert-butyldimethylsilyl) amino] methylvinylsilane, bis [bis (trimethylsilyl) amino] ethylvinylsilane, bis [bis (tert-butyldimethylsilyl) amino] ethylvinyl Bis [bis (trialkylsilyl) amino] alkyl vinyl silanes such as orchid; bis (dimethylamino) methoxymethyl vinyl silane, bis (dimethylamino) methoxyethyl vinyl silane, bis (dimethylamino) ethoxymethyl vinyl silane, bis (dimethylamino) ethoxyethyl Bis (dialkylamino) alkoxyalkylsilanes such as vinylsilane, bis (diethylamino) methoxymethylvinylsilane, bis (diethylamino) methoxyethylvinylsilane, bis (diethylamino) ethoxymethylvinylsilane, bis (dimethylamino) ethoxyethylvinylsilane; bis (pyrrolidino) methyl Vinylsilane, bis (piperidino) methylvinylsilane, bis (hexamethyleneimino) methylvinylsilane, bis (4,5- It can be mentioned hydro imidazolylmethyl) methyl vinyl silane, bis (morpholino) bis (cyclic amino such as methyl vinyl silane) alkyl vinyl silane compounds.

Of the silicon compounds represented by the general formula (III), two of R ¹⁵ , R ¹⁶ and R ¹⁷ are substituted amino groups and k 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) Til-3-vinylphenylsilane, bis (di-n-propylamino) ethyl-4-vinylphenylsilane, bis (di-n-propylamino) ethyl-3-vinylphenylsilane, bis (di-n-butylamino) And bis (dialkylamino) alkylvinylphenylsilane such as ethyl-4-vinylphenylsilane and bis (di-n-butylamino) ethyl-3-vinylphenylsilane.

Of the silicon compounds represented by the general formula (III), three of R ¹⁵ , R ¹⁶ and R ¹⁷ are substituted amino groups and k is 0.
Examples thereof include tris (dialkylamino) vinylsilane such as tris (dimethylamino) vinylsilane, tris (diethylamino) vinylsilane, tris (di-n-propylamino) vinylsilane, and tris (di-n-butylamino) vinylsilane.

Among the silicon compounds represented by the general formula (III), three of R ¹⁵ , R ¹⁶ and R ¹⁷ are substituted amino groups and k 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- And tris (dialkylamino) vinylphenylsilane such as butylamino) -3-vinylphenylsilane.

Among the silicon compounds represented by the general formula (III), R ¹⁵ , R ¹⁶ and R ¹⁷ are not substituted amino groups and k is 0.
Trialkoxyvinylsilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxyvinylsilane; dialkoxyalkylvinylsilanes such as methyldimethoxyvinylsilane and methyldiethoxyvinylsilane; di (tert-pentoxy) phenylvinylsilane, di (tert-butoxy) phenylvinylsilane Dialkoxyarylvinylsilanes; monoalkoxydialkylvinylsilanes such as dimethylmethoxyvinylsilane; monoalkoxydiarylvinylsilanes such as tert-butoxydiphenylvinylsilane, tert-pentoxydiphenylvinylsilane; tert-butoxymethylphenylvinylsilane, tert-butoxyethylphenylvinylsilane, etc. Monoalkoxyalkylary Vinylsilane; tris (beta-methoxyethoxy) substitution such as vinyl silane alkoxy vinyl silane compounds can be mentioned.

The silicon compound represented by the general formula (III) is more preferably a compound in which k in the general formula (III) is 0, and two of R ¹⁵ , R ¹⁶ and R ^{17 in} the general formula (III) are dialkyl. More preferred are compounds that are amino groups.

Particularly preferable compounds as the silicon compound represented by the general formula (III) are bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, and bis (di-n-butylamino) methylvinylsilane.

The content of the silicon compound represented by the general formula (III) in the diene copolymer is preferably 0.05% by mass or more, more preferably 0.2% by mass or more. Further, it is preferably 10% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. If it is less than 0.05% by mass, it is difficult to obtain the effect of improving fuel economy, wet grip performance and wear resistance, while if it exceeds 10% by mass, the cost tends to be high.
In addition, content of the silicon compound represented by the said general formula (III) in the said diene type copolymer can be measured by the method of the Example mentioned later.

In the production of the diene-based copolymer, in addition to the conjugated diene compound, the compound represented by the general formula (II), and the silicon compound represented by the general formula (III) as monomers, further polymerization is possible. Monomers may be used. Examples of the monomer include aromatic vinyl compounds, vinyl nitriles and unsaturated carboxylic acid esters. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene. Examples of the vinyl nitrile include acrylonitrile, and examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. In these, an aromatic vinyl compound is preferable and styrene is more preferable.

When the diene copolymer contains an aromatic vinyl compound, the content of the aromatic vinyl compound in the diene copolymer is preferably 5% by mass or more, more preferably 15% by mass or more. Moreover, Preferably it is 55 mass% or less, More preferably, it is 30 mass% or less. If it is less than 5% by mass, the wet grip performance tends to deteriorate, whereas if it exceeds 55% by mass, the fuel efficiency tends to deteriorate.
In addition, content of the aromatic vinyl compound in the said diene-type copolymer can be measured by the method of the Example mentioned later.

(Terminal modifier)
The diene copolymer of the present invention comprises a compound represented by general formula (IV), a compound having a group represented by general formula (V), and a compound having a group represented by general formula (VI). The terminal is modified with at least one compound selected from the group (terminal modifier (modifier for modifying the terminal)).

（式中、Ｒ^２１は、水素原子、炭素原子数が１〜１０のヒドロカルビル基又は炭素原子数が１〜６の置換ヒドロカルビル基を表す。ｎは、１〜１０の整数を表し、Ａ^１は、酸素原子又は−ＮＲ^２２−基（Ｒ^２２は、水素原子又は炭素原子数が１〜１０のヒドロカルビル基を表す。）を表し、Ａ^２は、窒素原子及び／又は酸素原子を有する官能基を表す。） Hereinafter, the compound represented by the following general formula (IV) will be described.

(In the formula, R ²¹ represents a hydrogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, or a substituted hydrocarbyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 10, and A ¹ represents , An oxygen atom or a —NR ²² — group (R ²² represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms), and A ² represents a functional group having a nitrogen atom and / or an oxygen atom. Represents.)

N of general formula (IV) represents the integer of 1-10. From the viewpoint of improving the fuel efficiency, wet grip performance and wear resistance in a well-balanced manner, it is preferably 2 or more, and preferably 4 or less from the viewpoint of improving economy during production. More preferably it is 3.

R ^{21 in the} general formula (IV) represents a hydrogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, or a substituted hydrocarbyl group having 1 to 6 carbon atoms.

Examples of the hydrocarbyl group of R ²¹ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and t-butyl group.

Examples of the substituted hydrocarbyl group represented by R ²¹ include a substituted hydrocarbyl group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom, a group having an oxygen atom, and a group having a silicon atom. it can. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl An alkoxyalkyl group such as a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group, and a group having a silicon atom group as a substituent includes a trialkylsilylalkyl group such as a trimethylsilylmethyl group; Examples thereof include a trialkylsilyloxyalkyl group such as a butyldimethylsilyloxymethyl group; a trialkoxysilylalkyl group such as a trimethoxysilylpropyl group.

The hydrocarbyl group of R ²¹ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, still more preferably It is a methyl group. The substituted hydrocarbyl group for R ²¹ is preferably an alkoxyalkyl group, more preferably an alkoxyalkyl group having 1 to 4 carbon atoms, and still more preferably a methoxymethyl group or an ethoxyethyl group. More preferably a methoxymethyl group.

R ²¹ is preferably a hydrogen atom, an alkyl group, or an alkoxyalkyl group, more preferably a hydrogen atom, a carbon atom, from the viewpoint of improving fuel economy, wet grip performance and wear resistance in a well-balanced manner and economy. An alkyl group having 1 to 4 carbon atoms and an alkoxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, and a methoxymethyl group, still more preferably a hydrogen atom and a methyl group. .

A ^{1 in the} general formula (IV) represents an oxygen atom or a —NR ²² — group, and R ²² represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms.

Examples of the hydrocarbyl group of R ²² include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, t-butyl groups, and other alkyl groups; phenyl groups, methylphenyl groups, and ethylphenyl groups. An aryl group such as a naphthyl group; and an aralkyl group such as a benzyl group.

The hydrocarbyl group for R ²² is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.

R ²² is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom, a methyl group or an ethyl group. And more preferably a hydrogen atom or a methyl group.

A ^{2 in the} general formula (IV) represents a functional group having a nitrogen atom and / or an oxygen atom. Examples of the functional group having a nitrogen atom include an amino group, isocyano group, cyano group, pyridyl group, piperidyl group, piperazinyl group, morpholino group and the like.

Examples of functional groups having an oxygen atom include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy; methoxymethyl, methoxyethyl And alkoxyalkyl groups such as ethoxymethyl group and ethoxyethyl group; alkoxyaryl groups such as methoxyphenyl group and ethoxyphenyl group; and alkylene oxide groups such as epoxy group and tetrahydrofuranyl group. Moreover, trialkyl silyloxy groups, such as a trimethyl silyloxy group, a triethyl silyloxy group, and t-butyldimethyl silyloxy group, can be mentioned. Moreover, a hydroxyl group can be mention | raise | lifted.

A ² is represented by the general formula (IIIa) described for the silicon compound represented by the general formula (III) from the viewpoint of low fuel consumption, wet grip performance, wear resistance, long-term stability and availability of the compound. Or a group represented by general formula (IIIa) is more preferred. More preferably, it is an acyclic group (acyclic amino group), and particularly preferably a dialkylamino group, a di (alkylene oxide) amino group, a di (alkyleneoxidealkyl) amino group, or a di (trialkylsilyl) amino group. It is.

Examples of the compound represented by the general formula (IV) include acrylamide compounds and methacrylamide compounds as compounds in which A ¹ is a secondary amino group.

As an acrylamide compound in which A ² is a group containing a nitrogen atom,
N- (2-dimethylaminoethyl) acrylamide,
N- (2-diethylaminoethyl) acrylamide,
N- (3-dimethylaminopropyl) acrylamide,
N- (3-diethylaminopropyl) acrylamide,
N- (4-dimethylaminobutyl) acrylamide,
N- (4-diethylaminobutyl) acrylamide,
N- (3-morpholinopropyl) acrylamide,
And N- (3-cyanopropyl) acrylamide.

As a methacrylamide compound in which A ² is a nitrogen atom-containing group,
N- (2-dimethylaminoethyl) methacrylamide,
N- (2-diethylaminoethyl) methacrylamide,
N- (3-dimethylaminopropyl) methacrylamide,
N- (3-diethylaminopropyl) methacrylamide,
N- (4-dimethylaminobutyl) methacrylamide,
N- (4-diethylaminobutyl) methacrylamide,
N- (3-morpholinopropyl) methacrylamide,
N- (3-cyanopropyl) methacrylamide and the like.

As an acrylamide compound in which A ² is an oxygen atom-containing group,
N- (3-methoxypropyl) acrylamide,
N- (3-ethoxypropyl) acrylamide,
N- (propoxymethyl) acrylamide,
N- (butoxymethyl) acrylamide,
N-glycidyl acrylamide,
Examples thereof include N-tetrahydrofurfuryl acrylamide.

As a methacrylamide compound in which A ² is an oxygen atom-containing group,
N- (3-methoxypropyl) methacrylamide,
N- (3-ethoxypropyl) methacrylamide,
N- (propoxymethyl) methacrylamide,
N- (butoxymethyl) methacrylamide,
N-glycidyl methacrylamide,
Examples thereof include N-tetrahydrofurfuryl methacrylamide.

As an acrylamide compound in which A ² is a group containing a nitrogen atom and an oxygen atom,
N- (3-di (glycidyl) aminopropyl) acrylamide,
N- (3-di (tetrahyhydrofurfuryl) aminopropyl) acrylamide and the like.

As the methacrylamide compound in which A ² is a group containing a nitrogen atom and an oxygen atom,
N- (3-di (glycidyl) aminopropyl) methacrylamide,
N- (3-di (tetrahyhydrofurfuryl) aminopropyl) methacrylamide and the like.

The compound represented by formula (IV), a compound A ¹ is an oxygen atom, may be mentioned acrylate compounds, methacrylate compounds, and the like.

As an acrylate compound in which A ² is a nitrogen atom-containing group,
2-dimethylaminoethyl acrylate,
2-diethylaminoethyl acrylate,
3-dimethylaminopropyl acrylate,
3-diethylaminopropyl acrylate,
4-dimethylaminobutyl acrylate,
Examples include 4-diethylaminobutyl acrylate.

As a methacrylate compound in which A ² is a nitrogen atom-containing group,
2-dimethylaminoethyl methacrylate,
2-diethylaminoethyl methacrylate,
3-dimethylaminopropyl methacrylate,
3-diethylaminopropyl methacrylate,
4-dimethylaminobutyl methacrylate,
Examples include 4-diethylaminobutyl methacrylate.

As an acrylate compound in which A ² is an oxygen atom-containing group,
2-ethoxyethyl acrylate,
2-propoxyethyl acrylate,
2-butoxyethyl acrylate,
3-methoxypropyl acrylate,
3-ethoxypropyl acrylate,
Glycidyl acrylate,
And tetrahydrofurfuryl acrylate.

As a methacrylate compound in which A ² is an oxygen atom-containing group,
2-ethoxyethyl methacrylate,
2-propoxyethyl methacrylate,
2-butoxyethyl methacrylate,
3-methoxypropyl methacrylate,
3-ethoxypropyl methacrylate,
Glycidyl methacrylate,
And tetrahydrofurfuryl methacrylate.

As the acrylate compound in which A ² is a group containing a nitrogen atom and an oxygen atom,
3-di (glycidyl) aminopropyl acrylate,
Examples include 3-di (tetrahydrofurfuryl) aminopropyl acrylate.

As a methacrylate compound in which A ² is a group containing a nitrogen atom and an oxygen atom,
3-di (glycidyl) aminopropyl methacrylate,
Examples include 3-di (tetrahydrofurfuryl) aminopropyl methacrylate.

The compound represented by the general formula (IV) is preferably a compound in which A ² is a group represented by the general formula (IIIa) from the viewpoint of improving the fuel economy, wet grip performance and wear resistance in a balanced manner. More preferably, A ¹ is an amino group, and A ² is a compound represented by the general formula (IIIa). More preferably, A ¹ is a secondary amino group (—NH—). And A ² is a compound represented by the general formula (IIIa).

The compound in which A ¹ is a secondary amino group and A ² is a group represented by the general formula (IIIa) is preferably N- (3-dialkylaminopropyl) acrylamide, N- (3-dialkylamino). Propyl) methacrylamide, more preferably N- (3-dimethylaminopropyl) acrylamide, N- (3-diethylaminopropyl) acrylamide, N- (3-dimethylaminopropyl) methacrylamide, N- (3-diethylamino) Propyl) methacrylamide.

（式中、ｐは０又は１の整数を表し、Ｔは、炭素原子数が１〜２０のヒドロカルビレン基又は炭素原子数が１〜２０の置換ヒドロカルビレン基を表し、Ａ^３は窒素原子を有する官能基を表す。） Hereinafter, the compound having a group represented by the following general formula (V) will be described.

(In the formula, p represents an integer of 0 or 1, T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms, and A ³ represents nitrogen. Represents a functional group having an atom.)

In general formula (V), p represents an integer of 0 or 1. T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms. A ³ represents a functional group having a nitrogen atom, and examples thereof include an amino group, an isocyano group, a cyano group, a pyridyl group, a piperidyl group, a pyrazinyl group, and a morpholino group.

As a compound having a group represented by the general formula (V), a compound having a group represented by the following general formula (Va) in which p in the general formula (V) is 0 and A ³ is an amino group. I can give you.

Examples of the compound having a group represented by the general formula (Va) include carboxylic acid amide compounds such as formamide, acetamide, and propionamide. Moreover, cyclic compounds, such as imidazolidinone and its derivative (s), and lactams, can be mentioned.

（式中、Ｒ^３１は、水素原子、炭素原子数が１〜１０のヒドロカルビル基、炭素原子数が１〜１０の置換ヒドロカルビル基、又は、窒素原子及び／若しくは酸素原子をヘテロ原子として有するヘテロ環基を表し、Ｒ^３２及びＲ^３３は、それぞれ独立に、窒素原子、酸素原子及びケイ素原子からなる原子群から選ばれる少なくとも１種の原子を有していてもよい炭素原子数が１〜１０の基を表し、Ｒ^３２及びＲ^３３は結合して窒素原子と共に環構造を形成していてもよく、Ｒ^３２及びＲ^３３は窒素に二重結合で結合する同一の基であってもよい。） Examples of the compound having a group represented by the general formula (Va) include a carboxylic acid amide compound represented by the following general formula (Va-1).

(In the formula, R ³¹ is a hydrogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, a substituted hydrocarbyl group having 1 to 10 carbon atoms, or a heterocycle having a nitrogen atom and / or an oxygen atom as a hetero atom. R ³² and R ³³ each independently represent a group having 1 to 10 carbon atoms which may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. R ³² and R ³³ may be bonded to form a ring structure together with the nitrogen atom, and R ³² and R ³³ may be the same group bonded to the nitrogen by a double bond.

As the hydrocarbyl group of R ³¹ , alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group; phenyl group, methylphenyl group, ethylphenyl group An aryl group such as a naphthyl group; and an aralkyl group such as a benzyl group.

Examples of the substituted hydrocarbyl group of R ³¹ include a substituted hydrocarbyl group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom and a group having an oxygen atom. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl And alkoxyalkyl groups such as methoxyethyl group, ethoxymethyl group, and ethoxyethyl group.

The heterocyclic group having a nitrogen atom and / or oxygen atom as a hetero atom of R ³¹ represents a heterocyclic compound residue containing a nitrogen atom and / or oxygen atom in the ring, and the group includes 2-pyridyl. Group, 3-pyridyl group, 4-pyridyl group, 2-furyl group and the like.

R ³¹ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, a substituted hydrocarbyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, More preferred are a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.

Examples of R ³² and R ^{33 in the} general formula (Va-1) include a hydrocarbyl group having 1 to 10 carbon atoms, a substituted hydrocarbyl group having 1 to 10 carbon atoms, and the like. Examples of the hydrocarbyl group for R ³² and R ³³ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group; phenyl group, methylphenyl group And aryl groups such as ethylphenyl group and naphthyl group; and aralkyl groups such as benzyl group.

Examples of the substituted hydrocarbyl group of R ³² and R ³³ include a substituted hydrocarbyl group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom and a group having an oxygen atom. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl And alkoxyalkyl groups such as methoxyethyl group, ethoxymethyl group, and ethoxyethyl group.

The group to which R ³² and R ³³ are bonded is a divalent group having 2 to 20 carbon atoms, which may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. Group. For example, an alkylene group such as a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; an oxydialkylene group such as an oxydiethylene group and an oxydipropylene group; and —CH ₂ CH ₂ —NH—CH ₂ — And a nitrogen-containing group such as a group represented by —CH ₂ CH ₂ —N═CH—.

As the same group bonded to the nitrogen of R ³² and R ^{33 by} a double bond, the number of carbon atoms that may have at least one atom selected from an atomic group consisting of a nitrogen atom and an oxygen atom is 2 to 2. 12 divalent groups. Examples thereof include an ethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene group, 1-methylethylidene group, 4-N, N-dimethylaminobenzylidene group.

R ³² and R ³³ are preferably a hydrocarbyl group, more preferably an alkyl group, still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or ethyl group. Group, n-propyl group and n-butyl group.

Examples of the carboxylic acid amide compound represented by the general formula (V) include formamide, N, N-dimethylformamide, N, N-diethylformamide, and the like; acetamide, N, N-dimethylacetamide, N, N-diethyl Acetamide, aminoacetamide, N, N-dimethyl-N ′, N′-dimethylaminoacetamide, N, N-dimethylaminoacetamide, N-ethylaminoacetamide, N, N-dimethyl-N′-ethylaminoacetamide, N, Acetamide compounds such as N-dimethylaminoacetamide and N-phenyldiacetamide;
Propionamide compounds such as propionamide and N, N-dimethylpropionamide; pyridylamide compounds such as 4-pyridylamide and N, N-dimethyl-4-pyridylamide;
Benzamide, N, N-dimethylbenzamide, N ′, N ′-(p-dimethylamino) benzamide, N ′, N ′-(p-diethylamino) benzamide, N, N-dimethyl-N ′, N ′-(p Benzamide compounds such as -dimethylamino) benzamide, N, N-dimethyl-N ', N'-(p-diethylamino) benzamide;
Acrylamide compounds such as N, N-dimethylacrylamide and N, N-diethylacrylamide;
Methacrylamide compounds such as N, N-dimethylmethacrylamide and N, N-diethylmethacrylamide;
Nicotinamide compounds such as N, N-dimethylnicotinamide, N, N-diethylnicotinamide, N, N-diethylisonicotinamide;
Phthalamide compounds such as N, N, N ′, N′-tetramethylphthalamide, N, N, N ′, N′-tetraethylphthalamide;
Examples thereof include phthalimide compounds such as N-methylphthalimide and N-ethylphthalimide.

（式中、ｈは０〜１０の整数を表し、Ｒ^３４及びＲ^３５は、それぞれ独立に、炭素原子数が１〜２０のヒドロカルビル基又は炭素原子数が１〜２０の置換ヒドロカルビル基を表す。）

（式中、ｉは０〜１０の整数を表し、Ｒ^３６は、炭素原子数が１〜２０のヒドロカルビル基又は炭素原子数が１〜２０の置換ヒドロカルビル基を表す。） Moreover, as a cyclic compound which has group represented by general formula (Va), the compound represented by the following general formula (Va-2) or the following general formula (Va-3) can be mention | raise | lifted.

(In the formula, h represents an integer of 0 to 10, and R ³⁴ and R ³⁵ each independently represent a hydrocarbyl group having 1 to 20 carbon atoms or a substituted hydrocarbyl group having 1 to 20 carbon atoms. )

(In the formula, i represents an integer of 0 to 10, and R ³⁶ represents a hydrocarbyl group having 1 to 20 carbon atoms or a substituted hydrocarbyl group having 1 to 20 carbon atoms.)

R ³⁴ , R ³⁵ and R ³⁶ in the general formula (Va-2) or the general formula (Va-3) are each independently a hydrocarbyl group having 1 to 20 carbon atoms or a substitution having 1 to 20 carbon atoms. Represents a hydrocarbyl group. Examples of the hydrocarbyl group of R ³⁴ , R ³⁵ and R ³⁶ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and t-butyl group; phenyl group, Examples thereof include aryl groups such as methylphenyl group, ethylphenyl group and naphthyl group; and aralkyl groups such as benzyl group.

The substituted hydrocarbyl group of R ³⁴ , R ³⁵ and R ^{36 is} a substituent having at least one group selected from the group consisting of a group having a nitrogen atom, a group having an oxygen atom and a group having a silicon atom as a substituent. Hydrocarbyl groups can be mentioned. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl Groups, methoxyethyl groups, ethoxymethyl groups, alkoxyalkyl groups such as ethoxyethyl groups; alkoxyaryl groups such as methoxyphenyl groups, ethoxyphenyl groups, and the like. , Trimethylsilylmethyl group, t-butyldimethylsilyloxymethyl group, trimethoxysilylpropyl group, and the like.

R ³⁴ and R ^{35 in the} general formula (Va-2) are preferably hydrocarbyl groups, more preferably alkyl groups, and still more preferably methyl groups.

R ^{36 in the} general formula (Va-3) is preferably a hydrocarbyl group, more preferably an alkyl group or an aryl group, still more preferably a methyl group or a phenyl group.

H and i in the general formula (Va-2) or the general formula (Va-3) each represents an integer of 0 to 10. From the viewpoint of improving the fuel efficiency, wet grip performance and wear resistance in a well-balanced manner, it is preferably 2 or more, and from the viewpoint of improving economy during production, it is preferably 7 or less.

Examples of the compound represented by the general formula (Va-2) include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di (n-propyl)- 1,3-hydrocarbyl-substituted-2-imidazolidinones such as 2-imidazolidinone, 1,3-di (t-butyl) -2-imidazolidinone, 1,3-diphenyl-2-imidazolidinone be able to. 1,3-substituted-2-imidazolidinone is preferred, 1,3-hydrocarbyl substituted-2-imidazolidinone is more preferred, and 1,3-dialkyl-2-imidazolidinone is more preferred. It is non. The 1,3-dialkyl-2-imidazolidinone is preferably 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di (n-propyl). ) -2-imidazolidinone, more preferably 1,3-dimethyl-2-imidazolidinone.

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

The compound represented by the general formula (Va-3) is preferably a 2-pyrrolidone compound or an ε-caprolactam compound, more preferably 1-hydrocarbyl-substituted-2-pyrrolidone, N-hydrocarbyl-substituted-ε-. Caprolactam, more preferably 1-alkyl-substituted-2-pyrrolidone, 1-aryl-substituted-2-pyrrolidone, N-alkyl-substituted-ε-caprolactam, N-aryl-substituted-ε-caprolactam, particularly preferably 1 -Phenyl-2-pyrrolidone, N-methyl-ε-caprolactam.

（式中、Ｔは、炭素原子数が１〜２０のヒドロカルビレン基又は炭素原子数が１〜２０の置換ヒドロカルビレン基を表す。） As a compound having a group represented by the general formula (V), a compound having a group represented by the following general formula (Vb) in which p in the general formula (V) is 1 and A ³ is an amino group. I can give you.

(In the formula, T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms.)

Examples of the compound having a group represented by the general formula (Vb) include a benzaldehyde compound, an acetophenone compound, and a benzophenone compound.

（式中、Ｒ^３７は、水素原子、炭素原子数が１〜１０のヒドロカルビル基、炭素原子数が１〜１０の置換ヒドロカルビル基、又は、窒素原子及び／若しくは酸素原子をヘテロ原子として有するヘテロ環基を表し、Ｒ^３８及びＲ^３９は、それぞれ独立に、窒素原子、酸素原子及びケイ素原子からなる原子群から選ばれる少なくとも１種の原子を有していてもよい炭素原子数が１〜１０の基を表し、Ｒ^３８及びＲ^３９は結合して窒素原子と共に環構造を形成していてもよく、Ｒ^３８及びＲ^３９は窒素に二重結合で結合する同一の基であってもよく、Ｔは、炭素原子数が１〜２０のヒドロカルビレン基又は炭素原子数が１〜２０の置換ヒドロカルビレン基を表す。） Examples of the compound having a group represented by the general formula (Vb) include compounds represented by the following general formula (Vb-1).

(In the formula, R ³⁷ represents a hydrogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, a substituted hydrocarbyl group having 1 to 10 carbon atoms, or a heterocycle having a nitrogen atom and / or an oxygen atom as a hetero atom. R ³⁸ and R ³⁹ each independently represent 1 to 10 carbon atoms which may have at least one kind of atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. R ³⁸ and R ³⁹ may be bonded to form a ring structure together with the nitrogen atom, R ³⁸ and R ³⁹ may be the same group bonded to the nitrogen by a double bond, and T Represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms.

Examples of the hydrocarbyl group for R ³⁷ include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, t-butyl groups, and other alkyl groups; phenyl groups, methylphenyl groups, and ethylphenyl groups. An aryl group such as a naphthyl group; and an aralkyl group such as a benzyl group.

Examples of the substituted hydrocarbyl group represented by R ³⁷ include a substituted hydrocarbyl group having at least one group selected from the group consisting of a group having a nitrogen atom and a group having an oxygen atom as a substituent. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl And alkoxyalkyl groups such as methoxyethyl group, ethoxymethyl group, and ethoxyethyl group.

The heterocyclic group having a nitrogen atom and / or oxygen atom as a hetero atom of R ³⁷ represents a heterocyclic compound residue containing a nitrogen atom and / or oxygen atom in the ring, and the group includes 2-pyridyl. Group, 3-pyridyl group, 4-pyridyl group, 2-furyl group and the like.

R ³⁷ is preferably a hydrogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, or a substituted hydrocarbyl group having 1 to 10 carbon atoms. The hydrocarbyl group having 1 to 10 carbon atoms is preferably an alkyl group or phenyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, or n-butyl. Group, a phenyl group. The substituted hydrocarbyl group having 1 to 10 carbon atoms is preferably an aryl group having a nitrogen atom group as a substituent, more preferably a dialkylaminophenyl group or a 4-morpholinophenyl group. .

Examples of R ³⁸ and R ^{39 in the} general formula (Vb-1) include a hydrocarbyl group having 1 to 10 carbon atoms and a substituted hydrocarbyl group having 1 to 10 carbon atoms.

Examples of the hydrocarbyl group of R ³⁸ and R ³⁹ include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group; a phenyl group, a methylphenyl group And aryl groups such as ethylphenyl group and naphthyl group; and aralkyl groups such as benzyl group.

Examples of the substituted hydrocarbyl group for R ³⁸ and R ³⁹ include a substituted hydrocarbyl group having at least one group selected from the group consisting of a group having a nitrogen atom and a group having an oxygen atom as a substituent. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl And alkoxyalkyl groups such as methoxyethyl group, ethoxymethyl group, and ethoxyethyl group.

The group to which R ³⁸ and R ³⁹ are bonded is a divalent group having 2 to 20 carbon atoms, which may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. Group. For example, an alkylene group such as a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; an oxydialkylene group such as an oxydiethylene group and an oxydipropylene group; and —CH ₂ CH ₂ —NH—CH ₂ — And a nitrogen-containing group such as a group represented by —CH ₂ CH ₂ —N═CH—.

As the same group bonded to the nitrogen of R ³⁸ and R ^{39 by} a double bond, the number of carbon atoms optionally having at least one atom selected from the group consisting of a nitrogen atom and an oxygen atom is 2 to 2. 12 divalent groups. Examples thereof include an ethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene group, 1-methylethylidene group, 4-N, N-dimethylaminobenzylidene group.

R ³⁸ and R ³⁹ are preferably a hydrocarbyl group, more preferably an alkyl group, still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or ethyl group. Group, n-propyl group and n-butyl group.

Examples of the hydrocarbylene group of T include alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group; phenylene group, methylphenylene group, ethylphenyllene group, naphthylene group, etc. An arylene group can be mentioned.

Examples of the substituted hydrocarbylene group for T include a substituted hydrocarbylene group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom and a group having an oxygen atom. Examples of the group having a nitrogen atom group as a substituent include dialkylaminoalkylene groups such as dimethylaminoethylene group and diethylaminoethylene group; dialkylaminoarylene groups such as dimethylaminophenylene group and diethylaminophenylene group; Examples of the group having an atom-containing group as a substituent include alkoxyalkylene groups such as a methoxymethylene group, a methoxyethylene group, an ethoxymethylene group, and an ethoxyethylene group.

T is preferably a hydrocarbylene group, more preferably an arylene group, and still more preferably a phenylene group.

Examples of the compound represented by the general formula (Vb-1) include dialkylamino-substituted benzaldehyde compounds such as 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 3,5-bis (dihexylamino) -benzaldehyde; 4′-aminoacetophenone Amino-substituted acetophenone compounds such as 4′-dimethylaminoacetophenone, dialkylamino-substituted acetophenone compounds such as 4′-diethylaminoacetophenone; Cyclic group-substituted acetophenone compounds; 4,4′-bis (dimethylamino) -benzophenone, 4,4′-bis (diethylamino) -benzophenone, 4-dimethylaminobenzopheno Dialkylamino-substituted benzophenone compounds such as 4-diethylaminobenzophenone, 3-dimethylaminobenzophenone and 3-diethylaminobenzophenone; heterocycles such as 4-morpholinobenzophenone, 4 ′-(imidazol-1-yl) -benzophenone and 4-pyrazolylbenzophenone Examples thereof include a group-substituted benzophenone compound.

（式中、ｊは１又は２の整数を表し、Ｙ^１はベンゼン環上の置換基であって、窒素原子を有する官能基を表し、Ｙ^１が複数ある場合、複数あるＹ^１は、同一でも異なっていてもよい。）

（式中、ｓは１又は２の整数を表し、ｔは０〜２の整数を表し、Ｙ^２及びＹ^３は、ベンゼン環上の置換基であって、窒素原子を有する官能基を表し、Ｙ^２が複数ある場合、複数あるＹ^２は、同一でも異なっていてもよく、Ｙ^３が複数ある場合、複数あるＹ^３は、同一でも異なっていてもよい。） The compound represented by the general formula (Vb-1) is preferably a substituted acetophenone compound or a substituted benzophenone compound, and is represented by the following general formula (Vb-1-1) or the following general formula (Vb-1-2). The compounds represented can be mentioned.

(Wherein, j represents an integer of 1 or 2, Y ¹ is a substituent on the benzene ring, represents a functional group having a nitrogen atom, if Y ¹ there are a plurality, Y ¹ there are a plurality of the same But it may be different.)

(In the formula, s represents an integer of 1 or 2, t represents an integer of 0 to 2, Y ² and Y ³ are substituents on the benzene ring and represent a functional group having a nitrogen atom, If the Y ² there is a plurality, a plurality of Y ² may be the same or different, if Y ³ is more, plural Y ³ may be the same or different.)

Y ¹ , Y ² and Y ³ in the general formula (Vb-1-1) or the general formula (Vb-1-2) represent a functional group having a nitrogen atom, and include an amino group, an isocyano group, a cyano group, and a pyridyl group. And piperidyl group, pyrazinyl group, pyrimidinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, morpholino group and the like. Preferred are a dialkylamino group, an imidazolyl group, and a morpholino group. Moreover, as an alkyl group of a dialkylamino group, a C1-C10 alkyl group is preferable.

The compound represented by the general formula (Vb-1) is more preferably a heterocyclic group-substituted acetophenone compound, a dialkylamino-substituted benzophenone compound, or a heterocyclic group-substituted benzophenone compound, and more preferably 4′-imidazole- 1-yl-acetophenone, 4-morpholinoacetophenone, 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4,4′-bis (dimethylamino) -benzophenone, 4,4′-bis (diethylamino) -benzophenone, 4-morpholino Benzophenone.

（式中、ｍは１〜１１の整数を表し、Ａ^４は窒素原子を有する官能基を表す。） Hereinafter, the compound having a group represented by the following general formula (VI) will be described.

(In the formula, m represents an integer of 1 to 11, and A ⁴ represents a functional group having a nitrogen atom.)

m represents an integer of 1 to 11. From the viewpoint of improving the fuel efficiency, wet grip performance and wear resistance in a well-balanced manner, it is preferably 1 or more, and from the viewpoint of improving economics during production, it is preferably 4 or less. A ⁴ is a functional group having a nitrogen atom, and examples thereof include an amino group, an isocyano group, a cyano group, a pyridyl group, a piperidyl group, a pyrazinyl group, and a morpholino group.

（式中、ｗは０〜１０の整数を表し、Ｒ^４１は炭素原子数が１〜５のヒドロカルビル基を表し、Ｒ^４２、Ｒ^４３、Ｒ^４４及びＲ^４５は、それぞれ独立に、水素原子、炭素原子数が１〜５のヒドロカルビル基、炭素原子数が１〜５の置換ヒドロカルビル基又は炭素原子数が１〜５のヒドロカルビルオキシ基を表し、Ｒ^４２及びＲ^４３が複数ある場合は、複数あるＲ^４２及び複数あるＲ^４３はそれぞれ同じであっても異なっていてもよく、Ｒ^４６及びＲ^４７は、それぞれ独立に、窒素原子、酸素原子及びケイ素原子からなる原子群から選ばれる少なくとも１種の原子を有していてもよい炭素原子数が１〜６の基を表し、Ｒ^４６及びＲ^４７は結合して窒素原子と共に環構造を形成していてもよく、Ｒ^４６及びＲ^４７は窒素に二重結合で結合する同一の基であってもよい。） Examples of the compound having a group represented by the general formula (VI) include compounds represented by the following general formula (VI-1).

(Wherein, w represents an integer of 0 to 10, R ⁴¹ represents a hydrocarbyl group having 1 to 5 carbon atoms, and R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ each independently represents a hydrogen atom, A hydrocarbyl group having 1 to 5 carbon atoms, a substituted hydrocarbyl group having 1 to 5 carbon atoms, or a hydrocarbyloxy group having 1 to 5 carbon atoms, and a plurality of R ⁴² and R ⁴³ are present. R ⁴² and a plurality of R ⁴³ may be the same or different, and R ⁴⁶ and R ⁴⁷ are each independently at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. represents an number of carbon atoms which may have a atom 1-6 groups, R ⁴⁶ and R ⁴⁷ may form a ring structure with a nitrogen atom bonded to, R ⁴⁶ and R ⁴⁷ is a nitrogen With double bond It may be the same group if.)

W of general formula (VI-1) represents the integer of 0-10. From the viewpoint of improving economy, it is preferably 3 or less, more preferably 0.

R ^{41 in the} general formula (VI-1) represents a hydrocarbyl group having 1 to 5 carbon atoms. Examples of the hydrocarbyl group of R ⁴¹ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and t-butyl group.

The hydrocarbyl group for R ⁴¹ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.

R ^{42 to} R ⁴⁵ in the general formula (VI-1) are each independently a hydrogen atom, a hydrocarbyl group having 1 to 5 carbon atoms, a substituted hydrocarbyl group having 1 to 5 carbon atoms, or 1 carbon atom. In the case where a plurality of R ⁴² and R ⁴³ are present, the plurality of R ⁴² and the plurality of R ⁴³ may be the same or different.

Examples of the hydrocarbyl group of R ^{42 to} R ⁴⁵ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and t-butyl group.

Examples of the substituted hydrocarbyl group of R ^{42 to} R ⁴⁵ include a substituted hydrocarbyl group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom and a group having an oxygen atom. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl And alkoxyalkyl groups such as a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group.

Examples of the hydrocarbyloxy group of R ^{42 to} R ⁴⁵ include alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a t-butoxy group. .

The hydrocarbyl group of R ^{42 to} R ⁴⁵ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.

The substituted hydrocarbyl group of R ^{42 to} R ⁴⁵ is preferably an alkoxyalkyl group, more preferably an alkoxyalkyl group having 1 to 4 carbon atoms, and still more preferably a methoxymethyl group or an ethoxyethyl group. .

The hydrocarbyloxy group of R ^{42 to} R ⁴⁵ is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms, and still more preferably a methoxy group or an ethoxy group.

From the viewpoint of improving fuel economy, wet grip performance and wear resistance in a well-balanced manner and economical efficiency, it is preferable that one of R ⁴⁴ and R ⁴⁵ is a hydrogen atom. More preferably, one of R ⁴⁴ and R ⁴⁵ is a hydrogen atom, and the other is an alkyl group or an alkoxy group. More preferably, one of R ⁴⁴ and R ⁴⁵ is a hydrogen atom, and the other is an alkoxy group. Particularly preferred are a methoxy group and an ethoxy group.

R ⁴⁶ and R ⁴⁷ in the general formula (VI-1) each independently have the number of carbon atoms that may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. 1 to 6 groups, R ⁴⁶ and R ⁴⁷ may be bonded to form a ring structure with the nitrogen atom, and R ⁴⁶ and R ⁴⁷ are the same group bonded to the nitrogen by a double bond; Also good.

Examples of R ⁴⁶ and R ^{47 in the} general formula (VI-1) include a hydrocarbyl group having 1 to 6 carbon atoms, a substituted hydrocarbyl group having 1 to 6 carbon atoms, and a substituted silyl group.

Examples of the hydrocarbyl group of R ⁴⁶ and R ⁴⁷ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, and isopentyl group. And alkyl groups such as n-hexyl group; cycloalkyl groups such as cyclohexyl group; phenyl groups and the like.

The substituted hydrocarbyl group of R ⁴⁶ and R ^{47 is} a substituted hydrocarbyl group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom, a group having an oxygen atom, and a group having a silicon atom. I can give you. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl Group, alkoxyalkyl group such as methoxyethyl group, ethoxymethyl group, ethoxyethyl group; alkylene oxide group such as epoxy group, tetrahydrofuranyl group; alkylene oxide alkyl group such as glycidyl group, tetrahydrofurfuryl group, etc. Examples of the group having a group having a silicon atom as a substituent include a trialkylsilylalkyl group such as a trimethylsilylmethyl group. In the present specification, the alkylene oxide group represents a monovalent group obtained by removing a hydrogen atom from a ring of a cyclic ether compound. The alkylene oxide alkyl group represents a group in which one or more hydrogen atoms of the alkyl group are substituted with an alkylene oxide group.

Examples of the substituted silyl group of R ⁴⁶ and R ⁴⁷ include a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group; a trialkoxysilyl group such as a trimethoxysilyl group.

The group to which R ⁴⁶ and R ⁴⁷ are bonded is a divalent divalent having 2 to 12 carbon atoms which may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. Group. For example, an alkylene group such as a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; an oxydialkylene group such as an oxydiethylene group and an oxydipropylene group; and —CH ₂ CH ₂ —NH—CH ₂ — And a nitrogen-containing group such as a group represented by —CH ₂ CH ₂ —N═CH—.

The group to which R ⁴⁶ and R ⁴⁷ are bonded is preferably a nitrogen-containing group, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—. Is more preferable.

As the same group bonded to the nitrogen of R ⁴⁶ and R ^{47 by} a double bond, the number of carbon atoms optionally having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom 2 to 12 divalent groups. Examples thereof include an ethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene group, 1-methylethylidene group, 4-N, N-dimethylaminobenzylidene group.

The hydrocarbyl group of R ⁴⁶ and R ⁴⁷ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group, an ethyl group, or an n-propyl group. , An n-butyl group, and more preferably a methyl group or an ethyl group. The substituted hydrocarbyl group for R ⁴⁶ and R ⁴⁷ is preferably an alkoxyalkyl group, an alkylene oxide group, or an alkylene oxide alkyl group. The substituted silyl group for R ⁴⁶ and R ⁴⁷ is preferably a trialkylsilyl group or a trialkoxysilyl group, more preferably a trialkylsilyl group, still more preferably a trimethylsilyl group or a triethylsilyl group. .

R ⁴⁶ and R ⁴⁷ are preferably an alkyl group, an alkoxyalkyl group, a substituted silyl group, or a nitrogen-containing group to which R ⁴⁶ and R ⁴⁷ are bonded, and more preferably an alkyl group having 1 to 4 carbon atoms. More preferred are a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and even more preferred are a methyl group and an ethyl group.

Examples of the amino group in which R ⁴⁶ and R ⁴⁷ are bonded to the nitrogen atom include an acyclic amino group and a cyclic amino group.
Examples of the acyclic amino group include dimethylamino group, diethylamino group, di (n-propyl) amino group, di (isopropyl) amino group, di (n-butyl) amino group, di (sec-butyl) amino group, di ( dialkylamino groups such as tert-butyl) amino group, di (neopentyl) amino group, ethylmethylamino group; di (methoxymethyl) amino group, di (methoxyethyl) amino group, di (ethoxymethyl) amino group, di ( And di (alkoxyalkyl) amino groups such as ethoxyethyl) amino group; and di (trialkylsilyl) amino groups such as di (trimethylsilyl) amino group and di (t-butyldimethylsilyl) amino group. In addition, di (alkylene oxide) amino groups such as di (epoxy) amino groups and di (tetrahydrofuranyl) amino groups; di (alkylene oxide alkyl) amino groups such as di (glycidyl) amino groups and di (tetrahydrofurfuryl) amino groups You can raise a group. Furthermore, an ethylideneamino group, 1-methylpropylideneamino group, 1,3-dimethylbutylideneamino group, 1-methylethylideneamino group, 4-N, N-dimethylaminobenzylideneamino group, and the like can also be mentioned.

Examples of the cyclic amino group include 1-pyrrolidinyl group, 1-piperidino group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-decamethyleneimino group, 1-dodecamethyleneimino. 1-polymethyleneimino groups such as groups can be mentioned. Examples of the cyclic amino group include 1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1-imidazolidinyl group, 1-piperazinyl group, morpholino group and the like.

The amino group in which R ⁴⁶ and R ⁴⁷ are bonded to the nitrogen atom is preferably an acyclic amino group from the viewpoint of low fuel consumption, wet grip performance, wear resistance, long-term stability and availability of the compound, A dialkylamino group is preferable, and a dimethylamino group and a diethylamino group are more preferable.

Examples of the compound represented by the general formula (VI-1) include N, N-dialkyl-substituted carboxylic acid amide dialkyl acetal compounds.

Examples of N, N-dialkyl-substituted carboxylic acid amide dialkyl acetal compounds include N, N-dimethylformamide dimethyl acetal, N, N-diethylformamide dimethyl acetal, N, N-di (n-propyl) formamide dimethyl acetal, N, N. -Dimethylformamide diethyl acetal, N, N-diethylformamide diethyl acetal, N, N-di (n-propyl) formamide diethyl acetal, N, N-dimethylformamide ethyl methyl acetal, N, N-diethylformamide ethyl methyl acetal, N N, N-dialkylformamide dialkyl acetals, such as N, N-di (n-propyl) formamidoethyl methyl acetal;

N, N-dimethylacetamide dimethyl acetal, N, N-diethylacetamide dimethyl acetal, N, N-di (n-propyl) acetamide dimethyl acetal, N, N-dimethylacetamide diethyl acetal, N, N-diethylacetamide diethyl acetal, N, N-di (n-propyl) acetamido diethyl acetal, N, N-dimethylacetamidoethyl methyl acetal, N, N-diethylacetamidoethyl methyl acetal, N, N-di (n-propyl) acetamidoethyl methyl acetal, etc. N, N-dialkylacetamido dialkyl acetal;

N, N-dimethylpropionamide dimethyl acetal, N, N-diethylpropionamide dimethyl acetal, N, N-di (n-propyl) propionamide dimethyl acetal, N, N-dimethylpropionamide diethyl acetal, N, N-diethyl Propionamide diethyl acetal, N, N-di (n-propyl) propionamide diethyl acetal, N, N-dimethylpropionamide ethyl methyl acetal, N, N-diethylpropionamide ethyl methyl acetal, N, N-di (n- N, N-dialkylpropionamide dialkyl acetals such as propyl) propionamidoethyl methyl acetal.

Among these, from the viewpoint of improving the fuel efficiency, wet grip performance and wear resistance in a balanced manner,
N, N-dialkylformamide dialkyl acetal,
More preferably,
N, N-dimethylformamide dimethyl acetal,
N, N-diethylformamide dimethyl acetal,
N, N-dimethylformamide diethyl acetal,
N, N-diethylformamide diethyl acetal.

(Weight average molecular weight Mw)
The weight average molecular weight Mw of the diene copolymer is 1.0 × 10 ^{5 to} 2.5 × 10 ⁶ . When Mw is less than 1.0 × 10 ^5, fuel economy tends to be poor, whereas when Mw exceeds 2.5 × 10 ⁶ , workability tends to be deteriorated. The lower limit of Mw is preferably 2.0 × 10 ⁵ or more, more preferably 3.0 × 10 ⁵ or more, and the upper limit is preferably 1.5 × 10 ⁶ or less, more preferably 1.0 × 10 ^6. It is as follows.
In addition, Mw can be adjusted suitably by methods, such as changing the quantity of the polymerization initiator used at the time of superposition | polymerization, and can be measured by the method of the below-mentioned Example.

The molecular weight distribution of the diene copolymer is preferably 1 to 5, more preferably 1 to 2, from the viewpoint of low fuel consumption. The molecular weight distribution is obtained by measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) method and dividing Mw by Mn.

When the diene copolymer contains an aromatic vinyl compound, the vinyl bond content of the diene copolymer is preferably 80% from the viewpoint of fuel efficiency, with the content of the conjugated diene unit being 100 mol%. The mol% or less, more preferably 70 mol% or less. Moreover, from a viewpoint of wet grip performance, 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.
When the diene copolymer does not contain an aromatic vinyl compound, the vinyl bond content of the diene copolymer is preferably 50% from the viewpoint of fuel efficiency, with the content of conjugated diene units being 100 mol%. The mol% or less, more preferably 40 mol% or less, still more preferably 20 mol% or less.
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.

<Method for producing diene copolymer>
The diene copolymer of the present invention is represented by a conjugated diene compound, a compound represented by the general formula (II), and a general formula (III) using a polymerization initiator represented by the general formula (I). Terminal modifier (a compound represented by the general formula (IV)) at the active terminal of a diene copolymer obtained by copolymerizing a silicon compound to be polymerized with another monomer that can be polymerized as necessary And at least one compound selected from the group consisting of a compound having a group represented by general formula (V) and a compound having a group represented by general formula (VI)), specifically, Can be produced by the following production method.

(Polymerization method)
The polymerization method of the diene copolymer is not particularly limited, and any of solution polymerization method, gas phase polymerization method and bulk polymerization method can be used, and the solution polymerization method is preferable from the viewpoint of easy handling. Moreover, any of a batch type and a continuous type may be sufficient as the superposition | polymerization form.

When the solution polymerization method is used, the monomer concentration in the solution (the total of the conjugated diene compound, the compound represented by the general formula (II), the silicon compound represented by the general formula (III), etc.) is , Preferably 5% by mass or more, more preferably 10% by mass or more. When the monomer concentration in the solution is less than 5% by mass, the amount of the obtained diene copolymer is small, and the cost tends to be high. The monomer concentration in the solution is preferably 50% by mass or less, more preferably 30% by mass or less. When the monomer concentration in the solution exceeds 50% by mass, the solution viscosity becomes so high that stirring becomes difficult and polymerization tends to be difficult.

(Method of anionic polymerization)
There is no restriction | limiting in particular as a method of manufacturing a diene copolymer by anionic polymerization using the polymerization initiator represented by general formula (I), A conventionally well-known method can be used. Specifically, the polymerization initiator represented by the general formula (I) is initiated in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound. A conjugated diene compound, a compound represented by the general formula (II), and a silicon compound represented by the general formula (III) can be polymerized if necessary in the presence of a randomizer. Any other monomer may be anionically polymerized.

(Hydrocarbon solvents in anionic polymerization)
The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans- Examples include 2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, and ethylbenzene.

(Randomizer in anionic polymerization)
The randomizer is a control of the microstructure of a conjugated diene moiety in a diene copolymer (for example, an increase in 1,2-bonds in butadiene, etc.) or a composition distribution of monomer units in a diene copolymer. It is a compound having an action such as control (for example, butadiene unit in butadiene-styrene copolymer, randomization of styrene unit, etc.). The randomizer is not particularly limited, and any known compound generally used as a conventional randomizer can be used. For example, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, bistetrahydrofurylpropane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-di Examples thereof include ethers such as piperidinoethane and tertiary amines. Further, potassium salts such as potassium-t-amylate and potassium-t-butoxide, and sodium salts such as sodium-t-amylate can also be used.

The amount of randomizer used varies depending on the type of randomizer used, but is preferably 0.01 molar equivalents or more, more preferably 0.05 molar equivalents or more per mole of the polymerization initiator. If the amount of randomizer used is less than 0.01 molar equivalent, the effect of addition tends to be small and it tends to be difficult to randomize. The amount of randomizer used is preferably 1000 molar equivalents or less, more preferably 500 molar equivalents or less per mole of the polymerization initiator. When the amount of the randomizer used exceeds 1000 molar equivalents, the monomer reaction rate changes greatly, and conversely, it tends to be difficult to randomize.

The amount of the monomer such as the conjugated diene compound, the compound represented by the general formula (II), and the silicon compound represented by the general formula (III) can be appropriately changed without departing from the gist of the present invention. it can.

In the production of the diene copolymer, the polymerization initiator represented by the general formula (I) may be supplied to the polymerization reactor before supplying the monomer to the polymerization reactor. The polymerization initiator represented by the general formula (I) may be supplied to the polymerization reactor after supplying the entire amount of the monomer to be used to the polymerization reactor, and a part of the monomer used for the polymerization is subjected to the polymerization reaction. The polymerization initiator represented by the general formula (I) may be supplied to the polymerization reactor after being supplied to the reactor. Moreover, the polymerization initiator represented by the general formula (I) may be supplied to the polymerization reactor at a time, or may be continuously supplied.
Regarding the supply of the monomer, the monomer may be supplied to the polymerization reactor at a time, may be supplied continuously, or may be supplied intermittently. Moreover, each monomer may be supplied separately to the polymerization reactor or may be supplied simultaneously.

The polymerization temperature in the production of the diene copolymer 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.

Examples of the modification method using a terminal modifier include a method of synthesizing a diene copolymer in which the starting terminal and the main chain are modified by anionic polymerization, and then bringing the diene copolymer into contact with the terminal modifier. As a result, the anion at the end of the diene copolymer reacts with the functional group of the terminal modifier. As a result, a diene copolymer having a modified starting end, main chain and terminating end can be obtained.
The reaction temperature of the modification reaction with the terminal modifier is usually 25 to 100 ° C, preferably 35 to 90 ° C, more preferably 50 to 80 ° C. The reaction time for the terminal reaction is usually 60 seconds to 5 hours, preferably 5 minutes to 1 hour, more preferably 15 minutes to 1 hour. The amount of the terminal modifier to be reacted is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the diene copolymer.

In the present invention, after performing a modification reaction with a terminal modifier, a known anti-aging agent or alcohol may be added as necessary to stop the polymerization reaction.
In addition, you may perform a hydrolysis process as needed, and, by this, in the unit derived from the silicon compound represented by general formula (III), at least one of R ¹⁵ , R ¹⁶ and R ¹⁷ is a hydroxyl group. can do.

<Rubber composition>
(Rubber component)
The diene copolymer can be used as a rubber component of a rubber composition. The content of the diene copolymer in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 50% by mass or more. If it is less than 5% by mass, there is a tendency that it is difficult to obtain an effect of improving fuel economy, wet grip performance and wear resistance. Further, the content of the diene copolymer is preferably 90% by mass or less, more preferably 80% by mass or less. When it exceeds 90 mass%, it tends to be expensive.

The diene copolymer may be used in combination with other rubber components. As another rubber component, it is preferable to use a diene rubber. As the diene rubber, 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), and acrylonitrile butadiene rubber. (NBR), chloroprene rubber (CR), butyl rubber (IIR) and the like. Of these, NR, BR, and SBR are preferable, and BR and SBR are more preferable, since low fuel consumption, wet grip performance, and wear resistance are exhibited in a well-balanced manner. These rubber components may be used alone or in combination of two or more.

The BR is not particularly limited, and those that are common in the tire industry can be used. When the rubber composition of the present invention contains BR, the content of BR in 100% by mass of the rubber component is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 95% by mass. Hereinafter, it is more preferably 90% by mass or less, and still more preferably 50% by mass or less. If it is in the said range, low-fuel-consumption property, wet grip performance, and abrasion resistance will be obtained with sufficient balance.

It does not specifically limit as SBR, A general thing can be used in the tire industry. When the rubber composition of the present invention contains SBR, the content of SBR in 100% by mass of the rubber component is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 50% by mass or more. Moreover, it is preferably 95% by mass or less, more preferably 90% by mass or less. If it is in the said range, low-fuel-consumption property, wet grip performance, and abrasion resistance will be obtained with sufficient balance.

(silica)
The rubber composition of the present invention preferably contains silica as a reinforcing agent. The above-mentioned diene copolymer promotes the dispersion of silica and can enhance the effects of improving fuel economy, wet grip performance and wear resistance. Silica that can be used is not particularly limited, and those commonly used in the tire industry can be used. Silica may be used alone or in combination of two or more.

The nitrogen adsorption specific surface area _(N 2 SA) of silica is preferably ^{50 m} 2 / g or more, more preferably ^{80 m} 2 / g or more, more preferably 150 meters ² / g or more, preferably 300 meters ² / g Hereinafter, more preferably 250 m ² / g or less, and still more preferably 200 m ² / g or less. Silica having a nitrogen adsorption specific surface area of less than 50 m ² / g has a small reinforcing effect and tends to decrease the wear resistance, and silica exceeding 300 m ² / g has poor dispersibility, increases hysteresis loss, and has low fuel consumption. Tends to decrease.
The _N 2 SA of silica is a value determined by the BET method in accordance with ASTM D3037-93.

The content of silica is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 50 parts by mass or more, and preferably 150 parts by mass or less, with respect to 100 parts by mass of the rubber component. Preferably it is 100 mass parts or less. If the silica content is less than 5 parts by mass, the wear resistance tends to be insufficient. On the other hand, if the silica content exceeds 150 parts by mass, the silica is difficult to disperse, and the workability and fuel efficiency are low. There is a tendency to get worse.

(Silane coupling agent)
In the present invention, it is preferable to use a silane coupling agent together with silica. The silane coupling agent is not particularly limited, and those conventionally used in the tire field can be used. For example, sulfide-based, mercapto-based, vinyl-based, amino-based, glycidoxy-based, nitro-based, chloro-based silane coupling Agents and the like. Among them, bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) disulfide, etc. A sulfide system can be preferably used.
Bis (3-triethoxysilylpropyl) tetrasulfide and 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide are particularly preferable from the viewpoint of reinforcing effect. These silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 4 parts by mass or more with respect to 100 parts by mass of silica. When the content of the silane coupling agent is less than 1 part by mass, the viscosity of the unvulcanized rubber composition tends to be high, and the processability tends to deteriorate. Further, the content of the silane coupling agent is preferably 20 parts by mass or less, more preferably 15 parts by mass or less with respect to 100 parts by mass of silica. When the content of the silane coupling agent exceeds 20 parts by mass, the blending effect of the silane coupling agent as much as the content cannot be obtained, and the cost tends to be high.

(Carbon black)
The rubber composition of the present invention preferably contains carbon black. Carbon black that can be used is not particularly limited, and those that are common in the tire industry can be used. Moreover, carbon black may be used independently and may be used in combination of 2 or more type.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 30 m ² / g or more, more preferably 70 m ² / g or more, preferably 250 m ² / g or less, more preferably 120 m ² / g or less. It is. Moreover, the dibutyl phthalate (DBP) absorption amount of carbon black is preferably 5 ml / 100 g or more, more preferably 80 ml / 100 g or more, preferably 300 ml / 100 g or less, more preferably 180 ml / 100 g or less. If the N ₂ SA or DBP absorption amount of the carbon black is less than the lower limit of the above range, the reinforcing effect tends to be small and the wear resistance tends to decrease. If the upper limit of the above range is exceeded, dispersibility is poor and hysteresis loss increases. There is a tendency for fuel efficiency to decrease. The nitrogen adsorption specific surface area is measured according to ASTM D4820-93, and the DBP absorption is measured according to ASTM D2414-93.

The content of carbon black is preferably 1 part by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 1 part by mass, sufficient reinforcement may not be obtained. The content of carbon black is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 10 parts by mass or less. If it exceeds 50 parts by mass, the fuel efficiency tends to deteriorate.

(Anti-aging agent)
The rubber composition of the present invention can contain an anti-aging agent. As the anti-aging agent, amine-based, phenol-based, and imidazole-based compounds, carbamic acid metal salts, waxes, and the like can be appropriately selected and used.

(Softener)
The rubber composition of the present invention can contain a softening agent. Examples of the softener include petroleum softeners, fatty oil softeners, fatty acids and the like. The content of the softening agent is preferably 100 parts by mass or less with respect to 100 parts by mass of the rubber component because there is little risk of reducing wet grip performance.

(Vulcanizing agent)
The rubber composition of the present invention can contain a vulcanizing agent. As the vulcanizing agent, an organic peroxide, a sulfur vulcanizing agent, or the like can be used. Of these, a sulfur-based vulcanizing agent is preferable and sulfur is more preferable from the viewpoint that the effects of the present invention can be obtained satisfactorily.

(Vulcanization accelerator)
The rubber composition of the present invention can contain a vulcanization accelerator. Examples of the vulcanization accelerator include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamic acid, aldehyde-amine, aldehyde-ammonia, imidazoline, and xanthate vulcanization accelerators. Can be given. These may be used alone or in combination of two or more.

(Vulcanization aid)
The rubber composition of the present invention can contain a vulcanization aid. As the vulcanization aid, stearic acid, zinc oxide (zinc white) or the like can be used.

(Other ingredients)
In the rubber composition of the present invention, various reinforcing agents, various oils, plasticizers, coupling agents, etc., various compounding agents and additives compounded for tires or general rubber compositions can be blended. . Moreover, the content of these compounding agents and additives can also be set to general amounts.

<Method for producing rubber composition>
The rubber composition of the present invention can be produced by a conventionally known production method, and the production method is not limited. For example, it can be produced by kneading each of the above components using a kneading machine such as a Banbury mixer or a kneading roll under ordinary methods and conditions.

By using the rubber composition of the present invention thus obtained, a pneumatic tire having improved fuel economy, wet grip performance and wear resistance in a well-balanced manner can be obtained. The rubber composition can be used for each member of a tire, and in particular, can be suitably used for a tread, a sidewall, and the like.

<Pneumatic tire>
The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, by extruding a rubber composition containing the above components in accordance with the shape of a tread or the like at an unvulcanized stage, and molding it with a tire molding machine by a normal method along with other tire members, Form an unvulcanized tire. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain a pneumatic tire.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

ｎ−ブチルリチウム：関東化学（株）製の１．６Ｍ ｎ−ブチルリチウムヘキサン溶液
２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール溶液：大内新興化学工業（株）製の「ノクラック２００」１ｇをメタノール１００ｍｌに溶解させて調整した。
メタノール：関東化学（株）製 Hereinafter, various chemicals used at the time of synthesis and polymerization will be described together. In addition, the chemical | medical agent refine | purified according to the usual method as needed.
DMF: manufactured by Kanto Chemical Co., Ltd. N, N-dimethylformamide sodium hydride: manufactured by Kanto Chemical Co., Ltd. diethylene glycol monobutyl ether: manufactured by Tokyo Chemical Industry Co., Ltd. 4-chloromethylstyrene: manufactured by Wako Pure Chemical Industries, Ltd. 4 -Vinyl benzaldehyde: Sigma-Aldrich p-toluenesulfonic acid: Kanto Chemical Co., Ltd. t-Butylcatechol: Kanto Chemical Co., Ltd. Sodium bicarbonate: Kanto Chemical Co., Ltd. Magnesium sulfate: Kanto Chemical Co., Ltd. Propylene glycol: manufactured by Kanto Chemical Co., Ltd .: THF: manufactured by Kanto Chemical Co., Ltd., tetrahydrofuran diethylamine: manufactured by Sigma-Aldrich, Inc. methylvinyldichlorosilane: manufactured by Shin-Etsu Chemical Co., Ltd., LS-190
Terminal modifier 1: N- (3-dimethylaminopropyl) acrylamide 1.6 g manufactured by Tokyo Chemical Industry Co., Ltd. was put into a 10 ml volumetric flask, and further n-hexane was added to make 10 ml.
n-Hexane: Anhydrous hexane terminal modifier manufactured by Kanto Chemical Co., Ltd. 2: 1.1 g of 1,3-dimethyl-2-imidazolidinone manufactured by Tokyo Chemical Industry Co., Ltd. was placed in a 10 ml volumetric flask, and further n-hexane. To make 10 ml.
Terminal modifier 3: Tokyo Chemical Industry Co., Ltd. N, N-dimethylformamide dimethyl acetal 1.2g was put into a 10 ml volumetric flask, and also n-hexane was added to make 10 ml.
Styrene: Kanto Chemical Co., Ltd. 1,3-Butadiene: Takachiho Trading Co., Ltd. Tetramethylethylenediamine: Kanto Chemical Co., Ltd. Initiator A: FMC AI-200CE2 (3- (N, N-dimethylamino) ) A compound in which 2 units of a structural unit derived from isoprene are bonded to 1-propyllithium (compound represented by the following formula)) (0.9M)

n-butyllithium: 1.6M n-butyllithium hexane solution manufactured by Kanto Chemical Co., Ltd. 2,6-di-tert-butyl-p-cresol solution: “NOCRACK 200” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. 1 g was prepared by dissolving in 100 ml of methanol.
Methanol: manufactured by Kanto Chemical Co., Inc.

<Synthesis of Compound Represented by General Formula (II)>
Synthesis of Compound 1 [4- (2,5,8-trioxadodecyl) styrene] (the following formula) 100 mL of DMF and 1.8 g of sodium hydride were added to a three-necked flask sufficiently substituted with nitrogen, and diethylene glycol mono hydrate at 0 ° C. While stirring, 12 g of butyl ether was added dropwise over 30 minutes. After stirring at room temperature for 1 hour, it was cooled again to 0 ° C., 7.5 g of 4-chloromethylstyrene was added dropwise, and the mixture was stirred as it was for 1 hour. Saturated aqueous ammonium chloride solution was added to the resulting solution, and the organic layer was extracted and concentrated with an evaporator to prepare 4- (2,5,8-trioxadodecyl) styrene, which was purified by a conventional method using a silica gel column.

Synthesis of Compound 2 [4- (2-1,3-dioxanyl) styrene] (Formula below) Toluene 100 mL, 4-vinylbenzaldehyde 5.3 g, propylene glycol 4.2 g, p -Toluenesulfonic acid 5 mg and t-butylcatechol 1 mg were added and refluxed at 110 ° C for 2 hours. Thereafter, the obtained solution was washed with an aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, filtered and concentrated to prepare 4- (2-1,3-dioxanyl) styrene, which was purified by distillation under reduced pressure.

<Synthesis of silicon compound represented by general formula (III)>
Synthesis of Compound 3 [bis (diethylamino) methylvinylsilane] 1000 mL of THF and 13 g of sodium hydride were added to a fully nitrogen-substituted 2 L three-necked flask, and 36.5 g of diethylamine was slowly added dropwise with stirring on an ice-water bath. After stirring for 30 minutes, 36 g of methylvinyldichlorosilane 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 synthesize bis (diethylamino) methylvinylsilane.
21.4 g of the obtained bis (diethylamino) methylvinylsilane was placed in a 100 ml volumetric flask under a nitrogen atmosphere, and anhydrous hexane was further added to make a total volume of 100 ml.

Compound 4 [bis (dimethylamino) methylvinylsilane]
15.8 g of bis (dimethylamino) methylvinylsilane manufactured by Shin-Etsu Chemical Co., Ltd. was placed in a 100 ml volumetric flask under a nitrogen atmosphere, and anhydrous hexane was further added to make a total volume of 100 ml.

<Analysis of copolymer>
The copolymer obtained as described below was analyzed by the following method.

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

(Structural identification of copolymer)
The structure of the copolymer was identified using a JNM-ECA series device manufactured by JEOL Ltd. From the measurement results, the styrene content, the contents of compounds 1 and 2, and the contents of compounds 3 and 4 were calculated.

<Synthesis of copolymer>
(Copolymer (1))
According to the recipe of Table 1, 1800 mL of n-hexane, 40 g of styrene, 130 g (2403.4 mmol) of 1,3-butadiene, 1.0 g (3.1 mmol) of Compound 1, and Compound 3 in a 3 L pressure vessel sufficiently substituted with nitrogen. 5 mmol, tetramethylethylenediamine 0.9 mmol, and initiator A 1.2 mmol were added, and the mixture was stirred at 50 ° C. for 3 hours. Thereafter, 1.0 ml (1 mmol) of the terminal modifier 1 was added and stirred for 1 hour. Further, 1 ml of 2,6-tert-butyl-p-cresol solution was added, and the reaction solution was taken out into a 10 L stainless steel cylindrical container containing 3 L of methanol. The obtained aggregate was dried under reduced pressure for 24 hours to obtain about 168 g of copolymer (1). As a result of analysis, Mw was 315000 and styrene content was 23.3 mass%.

(Copolymer (2) to (15))
Synthesis was performed in the same manner as for the copolymer (1) using the recipe in Table 1. The copolymer (7) was stirred at 50 ° C. for 4 hours after adding 1,3-butadiene or the like.
The yield and characteristics of the obtained copolymer are shown in Table 1.

<Examples and Comparative Examples>
Below, various chemical | medical agents used by the Example and the comparative example are demonstrated.
Copolymers (1) to (15): Synthetic silica by the above method: Ultrasil VN3 (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 Co., Ltd. (1): Soxinol CZ manufactured by Sumitomo Chemical Co., Ltd.
Vulcanization accelerator (2): Soxinol D manufactured by Sumitomo Chemical Co., Ltd.

According to the blending content shown in Table 2, materials other than sulfur and vulcanization accelerator were kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer manufactured by Kobe Steel Co., Ltd. Obtained. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes under the condition of 80 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized with a 0.5 mm thick mold at 170 ° C. for 20 minutes to obtain a 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>
<Low fuel consumption index>
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., and displayed as an index when Comparative Example 5 was taken as 100. . The larger the fuel efficiency index is, the smaller the rolling resistance is, and the better the fuel efficiency is.

<Rolling index>
Using a rolling resistance tester, the rolling resistance when a test tire is run at a rim (15 × 6JJ), internal pressure (230 kPa), load (3.43 kN), speed (80 km / h) is measured and compared. It was displayed as an index when Example 5 was taken as 100. The larger the rolling index, the smaller the rolling resistance and the better the fuel efficiency.

<Wet grip index>
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 index) = (Brake distance of Comparative Example 5) / (Brake distance of each formulation) × 100

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

At the active end of the diene copolymer obtained by copolymerizing a conjugated diene compound, a specific aromatic compound, and a specific silicon compound (silicon-containing vinyl compound) using a polymerization initiator having a specific amino group In an embodiment using a diene copolymer obtained by reacting a specific compound and having a weight average molecular weight Mw within a specific range, the fuel economy, wet grip performance and wear resistance are improved in a well-balanced manner. It was. Note that Comparative Example 6 could not be kneaded because the viscosity was too low.

As a result of comparison between Comparative Examples 1 to 5 and Example 2, the diene copolymer is modified with a specific combination of compounds, so that it has low fuel consumption, wet grip performance and wear resistance (particularly low fuel consumption). ) Can be improved synergistically.

Claims (10)

A monomer comprising a conjugated diene compound, a compound represented by the following general formula (II), and a silicon compound represented by the following general formula (III) using a polymerization initiator represented by the following general formula (I) At the active end of the diene copolymer obtained by copolymerizing the product,
At least one selected from the group consisting of a compound represented by the following general formula (IV), a compound having a group represented by the following general formula (V), and a compound having a group represented by the following general formula (VI) A diene copolymer obtained by reacting the compound with a weight average molecular weight Mw of 1.0 × 10 ^{5 to} 2.5 × 10 ⁶ .

(In the formula, d is 0 or 1, R ¹ represents a hydrocarbylene group having 1 to 100 carbon atoms, and R ² and R ³ are hydrocarbyl groups which may have a substituent, or tri A hydrocarbylsilyl group, or R ² and R ³ may be 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 heteroatom. Represents a good hydrocarbylene group, and M represents an alkali metal atom.)

(Wherein, r represents an integer of 1 to 20, R ¹¹ and R ¹³ each independently represent a hydrocarbyl group having 1 to 10 carbon atoms, and R ¹² represents a hydrocarbylene group having 1 to 10 carbon atoms. And at least one of R ¹¹ , R ¹² and R ¹³ has a group represented by the following general formula (II-1): R ¹¹ and R ¹³ may be bonded to each other.

(In the formula, k is 0 or 1, R ¹⁴ represents a hydrocarbylene group, and R ¹⁵ , R ^16, and R ¹⁷ each independently have a substituted amino group, a hydrocarbyloxy group, or a substituent. Represents an optional hydrocarbyl group.)

(In the formula, R ²¹ represents a hydrogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, or a substituted hydrocarbyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 10, and A ¹ represents , An oxygen atom or a —NR ²² — group (R ²² represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms), and A ² represents a functional group having a nitrogen atom and / or an oxygen atom. Represents.)

(In the formula, p represents an integer of 0 or 1, T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms, and A ³ represents nitrogen. Represents a functional group having an atom.)

(In the formula, m represents an integer of 1 to 11, and A ⁴ represents a functional group having a nitrogen atom.) The diene copolymer according to claim 1, wherein R ¹ in the general formula (I) is a group represented by the following general formula (Ia).

(In the formula, 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 z represents an integer of 1 to 10.) The diene copolymer according to claim 1 or 2, wherein the monomer contains styrene. The diene copolymer according to any one of claims 1 to 3, wherein a content of the compound represented by the general formula (II) in the diene copolymer is 0.05 to 10% by mass. The diene copolymer according to any one of claims 1 to 4, wherein a content of the silicon compound represented by the general formula (III) in the diene copolymer is 0.05 to 10% by mass. A rubber composition comprising 5% by mass or more of the diene copolymer according to claim 1 in 100% by mass of a rubber component. The rubber composition according to claim 6, comprising 5 to 150 parts by mass of silica with respect to 100 parts by mass of the rubber component. The rubber composition according to claim 6 or 7, comprising butadiene rubber and / or styrene butadiene rubber. The rubber composition according to any one of claims 6 to 8, which is used as a rubber composition for tires. A pneumatic tire produced using the rubber composition according to any one of claims 6 to 9 .