JP5882686B2 - Copolymer, rubber composition and pneumatic tire - Google Patents

Description

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

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. Silica has strong self-aggregation property and there is room for improvement in that it is 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 problems and to provide a copolymer that can provide a rubber composition and a pneumatic tire with improved fuel economy and wet grip performance in a well-balanced manner.

As a result of intensive studies and studies to solve the above problems, the present inventors have found 1,3-butadiene and a specific aromatic compound, or 1,3-butadiene, an aromatic vinyl compound and a specific aromatic compound. Pneumatic using a rubber composition containing a copolymer obtained by reacting a compound having a specific functional group with a polymer active terminal obtained by copolymerization and having a weight average molecular weight Mw within a specific range By producing a tire, it has been found that fuel efficiency and wet grip performance are improved in a well-balanced manner, and the present invention has been made.

［式中、Ｒ^１は、炭素原子数が１〜１０の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, the present invention copolymerizes 1,3-butadiene and a compound represented by the following formula (I), or 1,3-butadiene, an aromatic vinyl compound and a compound represented by the following formula (I). A group having a compound represented by the following formula (II), a compound having a group represented by the following formula (III), and a compound having a group represented by the following formula (IV) The present invention relates to a copolymer obtained by reacting at least one kind of selected compound and having a weight average molecular weight Mw of 1.0 × 10 ^{5 to} 2.5 × 10 ⁶ .

[Wherein, R ¹ represents a hydrocarbyl group having 1 to 10 carbon atoms. ]

[Wherein 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, 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. ]

[Wherein, 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. A functional group having an atom is represented. ]

[Wherein, m represents an integer of 1 to 11, and A ⁴ represents a functional group having a nitrogen atom. ]

The content of the compound represented by the above formula (I) is preferably 0.05 to 10% by mass.

It is preferable that content of the said aromatic vinyl compound is 0.1-55 mass%.

The aromatic vinyl compound is preferably styrene.

The present invention also relates to a rubber composition containing the copolymer.

In 100% by mass of the rubber component, the content of the copolymer is preferably 5% by mass or more.

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

According to the present invention, 1,3-butadiene and a specific aromatic compound, or a polymer active terminal obtained by copolymerizing 1,3-butadiene, an aromatic vinyl compound, and a specific aromatic compound are specified. It is a copolymer obtained by reacting a compound having a functional group with a weight average molecular weight Mw within a specific range. Therefore, in a rubber composition and a pneumatic tire using the copolymer, low fuel consumption And wet grip performance can be improved in a well-balanced manner.

［式中、Ｒ^１は、炭素原子数が１〜１０の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。］ <Copolymer>
The copolymer of the present invention comprises 1,3-butadiene and a compound represented by the following formula (I), or 1,3-butadiene, an aromatic vinyl compound and a compound represented by the following formula (I). From a compound represented by the following formula (II), a compound having a group represented by the following formula (III), and a compound having a group represented by the following formula (IV) at the polymer active terminal obtained by polymerization It can be obtained by reacting at least one compound (terminal modifier) selected from the group consisting of: Dispersibility of the filler is improved by the interaction between the compound represented by the following formula (I) contained in the copolymer and silica, and the interaction between the terminal modifier and silica, and the copolymer. The movement of is restrained. As a result, it is possible to obtain a pneumatic tire with reduced hysteresis loss, improved fuel efficiency, and improved wet grip performance. Moreover, by using together the compound represented by a following formula (I), and a terminal modifier, each improvement effect improves synergistically and low-fuel-consumption property and wet grip performance can be improved significantly.

[Wherein, R ¹ represents a hydrocarbyl group having 1 to 10 carbon atoms. ]

[Wherein 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, 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. ]

[Wherein, 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. A functional group having an atom is represented. ]

[Wherein, m represents an integer of 1 to 11, and A ⁴ represents a functional group having a nitrogen atom. ]

(Monomer component)
The copolymer of the present invention uses 1,3-butadiene, a compound represented by the above formula (I), and, if necessary, an aromatic vinyl compound as monomer components.

In the above formula (I), the hydrocarbyl group represented by R ¹ has 1 to 10 carbon atoms. If the number of carbon atoms exceeds 10, the cost tends to increase. Further, there is a tendency that the fuel efficiency and wet grip performance cannot be sufficiently improved. The number of carbon atoms is preferably 1-8, more preferably 1-6, from the viewpoint that the resulting copolymer is highly effective in improving fuel economy and wet grip performance.

Examples of the hydrocarbyl group represented by R ¹ include a monovalent aliphatic hydrocarbon group such as an alkyl group and a monovalent aromatic hydrocarbon group such as an aryl group. R ¹ is preferably an alkyl group, more preferably a methyl group or a tert-butyl group, from the viewpoint that the resulting copolymer is highly effective in improving fuel economy and wet grip performance.

（式中、Ｒ^１は、上記式（Ｉ）中のＲ^１と同様である。） In addition, the compound represented by the following formula (I-1) among the compounds represented by the formula (I) is highly effective in improving fuel economy and wet grip performance due to the obtained copolymer. preferable.

(Wherein, ^{R 1} is the same as ^{R 1} in the formula (I).)

Examples of the compound represented by the formula (I) include p-methoxystyrene, p-ethoxystyrene, p- (n-propoxy) styrene, p- (tert-butoxy) styrene, m-methoxystyrene, and the like. , P-methoxystyrene, and p- (tert-butoxy) styrene are preferable. These may be used alone or in combination of two or more.

The content of the compound represented by the formula (I) in the 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, it is 8 mass% or less. If it is less than 0.05% by mass, it is difficult to obtain an effect of improving fuel economy and wet grip performance, while if it exceeds 10% by mass, the cost tends to be high.

As the aromatic vinyl compound, styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and the like can be used, and styrene can be preferably used. When the copolymer contains an aromatic vinyl compound, the content of the aromatic vinyl compound is preferably 0.1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. Further, it is preferably 55% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and still more preferably 25% by mass or less. If it is less than 0.1% by mass, the wet grip performance tends to deteriorate, whereas if it exceeds 55% by mass, the fuel efficiency tends to deteriorate.

The content of 1,3-butadiene in the copolymer is not particularly limited, and may be appropriately adjusted according to the content of other components, but is preferably 40% by mass or more, more preferably 60% by mass or more. In addition, it is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less. If it is in the said range, the effect of this invention will be acquired favorably.

The content of the compound represented by the formula (I), 1,3-butadiene and the aromatic vinyl compound in the copolymer can be measured by the method of Examples described later.

(Terminal modifier)
The copolymer of the present invention comprises a compound represented by the following formula (II), a compound having a group represented by the following formula (III), and a compound having a group represented by the following formula (IV). The terminal is modified by at least one selected compound (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 formula (II) will be described.

[Wherein 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, 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. ]

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

R ^{21 in} formula (II) represents a hydrogen atom, a hydrocarbyl group having 1 to 6 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. And more preferably a methoxymethyl group.

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

A ^{1 in} Formula (II) 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} formula (II) 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.

［式中、Ｒ^２３及びＲ^２４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^２３及びＲ^２４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^２３及びＲ^２４は窒素に二重結合で結合する同一の基であってもよい。］ A ² is preferably a group or a hydroxyl group represented by the following formula (IIa), and more preferably a group represented by the following formula (IIa).

[Wherein R ²³ and R ²⁴ each independently have 1 to 6 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 ²³ and R ²⁴ may be bonded to form a ring structure together with a nitrogen atom, and R ²³ and R ²⁴ may be the same group bonded to nitrogen by a double bond. ]

Examples of R ²³ and R ^{24 in} formula (IIa) 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 ²³ and R ²⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, and an 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 ²³ and R ^{24 includes} 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 for R ²³ and R ²⁴ 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 ²³ and R ²⁴ are bonded is a divalent group having 2 to 12 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. 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 ²³ and R ²⁴ 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.

The same group bonded to the nitrogen of R ²³ and R ^{24 with} a double bond is 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 ²³ and R ²⁴ 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 ²³ and R ²⁴ is preferably an alkoxyalkyl group, an alkylene oxide group, or an alkylene oxide alkyl group. The substituted silyl group for R ²³ and R ²⁴ 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 ²³ and R ²⁴ are preferably a nitrogen-containing group to which R ²³ and R ²⁴ are bonded, an alkyl group, an alkoxyalkyl group, an alkylene oxide group, an alkylene oxide alkyl group, or a substituted silyl group, and more preferably an alkyl group. A group, an alkylene oxide group, an alkylene oxide alkyl group, and a trialkylsilyl group.

Examples of the group represented by the formula (IIa) 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.
In this specification, the di (alkylene oxide) amino group represents an amino group in which two hydrogen atoms bonded to a nitrogen atom are substituted with two alkylene oxide groups, and the di (alkylene oxide alkyl) amino group Represents an amino group in which two hydrogen atoms bonded to a nitrogen atom are substituted with two alkylene oxide alkyl groups.

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 group represented by the formula (IIa) is preferably an acyclic amino group, more preferably a dialkylamino group, a dialkylamino group, and a dialkylamino group, from the viewpoint of low fuel consumption, wet grip performance, long-term stability and availability of the compound. (Alkylene oxide) amino group, di (alkylene oxide alkyl) amino group, di (trialkylsilyl) amino group.

Examples of the compound represented by the formula (IIa) 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.

Examples of the compound represented by the formula (II) include acrylate compounds and methacrylate compounds as compounds in which A ¹ is an oxygen atom.

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 the 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 formula (II) is preferably a compound in which A ² is a group represented by formula (IIa), more preferably from the viewpoint of improving fuel economy and wet grip performance in a well-balanced manner. , A ¹ is an amino group, and A ² is a group represented by the formula (IIa), more preferably, A ¹ is a secondary amino group (—NH—), and A ² is a formula It is a compound which is a group represented by (IIa).

As a compound in which A ¹ is a secondary amino group and A ² is a group represented by the formula (IIa),
Preferably,
N- (3-dialkylaminopropyl) acrylamide,
N- (3-dialkylaminopropyl) methacrylamide;
More preferably,
N- (3-dimethylaminopropyl) acrylamide,
N- (3-diethylaminopropyl) acrylamide,
N- (3-dimethylaminopropyl) methacrylamide,
N- (3-diethylaminopropyl) 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 formula (III) will be described.

[Wherein, 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. A functional group having an atom is represented. ]

In formula (III), 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.

Examples of the compound having a group represented by the formula (III) include a compound having a group represented by the following formula (IIIa) in which p in the formula (III) is 0 and A ³ is an amino group. it can.

Examples of the compound having a group represented by the formula (IIIa) 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 formula (IIIa) include a carboxylic acid amide compound represented by the following formula (IIIa-1).

[Wherein R ³¹ 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 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 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, Particularly 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} formula (IIIa-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 formula (III) include formamide compounds such as formamide, N, N-dimethylformamide, N, N-diethylformamide; acetamide, N, N-dimethylacetamide, N, N-diethylacetamide , Aminoacetamide, N, N-dimethyl-N ′, N′-dimethylaminoacetamide, N, N-dimethylaminoacetamide, N-ethylaminoacetamide, N, N-dimethyl-N′-ethylaminoacetamide, N, N -Acetamide compounds such as dimethylaminoacetamide, 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。］ Examples of the cyclic compound having a group represented by the formula (IIIa) include a compound represented by the following formula (IIIa-2) or the following formula (IIIa-3).

[Wherein, h represents an integer of 0 to 10, and R ³⁴ and R ³⁵ each independently represents a hydrocarbyl group having 1 to 20 carbon atoms or a substituted hydrocarbyl group having 1 to 20 carbon atoms. ]

[Wherein, 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 formula (IIIa-2) or formula (IIIa-3) are each independently a hydrocarbyl group having 1 to 20 carbon atoms or a substituted hydrocarbyl group having 1 to 20 carbon atoms. Represents. 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} formula (IIIa-2) are preferably hydrocarbyl groups, more preferably alkyl groups, and still more preferably methyl groups.

R ^{36 in} formula (IIIa-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 Formula (IIIa-2) or Formula (IIIa-3) each represents an integer of 0 to 10. From the viewpoint of improving fuel economy and wet grip performance 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 formula (IIIa-2) include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di (n-propyl) -2. -Mentioning 1,3-hydrocarbyl-substituted-2-imidazolidinones such as imidazolidinone, 1,3-di (t-butyl) -2-imidazolidinone, 1,3-diphenyl-2-imidazolidinone Can do. 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 formula (IIIa-3) include β-forms such as N-methyl-β-propiolactam, N- (t-butyl) -β-propiolactam, and N-phenyl-β-propiolactam. A propiolactam compound;
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 formula (IIIa-3) is preferably a 2-pyrrolidone compound or an ε-caprolactam compound, and more preferably 1-hydrocarbyl substituted-2-pyrrolidone, N-hydrocarbyl substituted-ε-caprolactam. More preferred are 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。］ Examples of the compound having a group represented by the formula (III) include compounds having a group represented by the following formula (IIIb) in which p in the formula (III) is 1 and A is an amino group. .

[Wherein, 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 formula (IIIb) include benzaldehyde compounds, acetophenone compounds, and benzophenone compounds.

［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 formula (IIIb) include a compound represented by the following formula (IIIb-1).

[Wherein, 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, and particularly preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. 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} formula (IIIb-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 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 formula (IIIb-1) include dialkylamino-substituted benzaldehyde compounds such as 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 3,5-bis (dihexylamino) -benzaldehyde; 4′-aminoacetophenone, etc. Amino-substituted acetophenone compounds; dialkylamino-substituted acetophenone compounds such as 4′-dimethylaminoacetophenone and 4′-diethylaminoacetophenone; heterocycles such as 4-morpholinoacetophenone, 4′-imidazol-1-yl-acetophenone and 4-pyrazolylacetophenone 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 formula (IIIb-1) is preferably a substituted acetophenone compound or a substituted benzophenone compound, and represented by the following formula (IIIb-1-1) or the following formula (IIIb-1-2). Compounds 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 is more, a plurality of Y ¹ are the same But it can be different. ]

[Wherein, 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, Y ² there are a plurality of, 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 formula (IIIb-1-1) or formula (IIIb-1-2) represent a functional group having a nitrogen atom, and are amino group, isocyano group, cyano group, pyridyl group, 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 formula (IIIb-1) is more preferably a heterocyclic group-substituted acetophenone compound, a dialkylamino-substituted benzophenone compound, or a heterocyclic group-substituted benzophenone compound, and particularly preferably 4′-imidazole-1 -Yl-acetophenone, 4-morpholinoacetophenone, 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4,4'-bis (dimethylamino) -benzophenone, 4,4'-bis (diethylamino) -benzophenone, 4-morpholinobenzophenone It is.

［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 formula (IV) will be described.

[Wherein, 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 and wet grip performance in a well-balanced manner, it is preferably 1 or more, and preferably 4 or less from the viewpoint of improving economy during production. 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、ｋ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 formula (IV) include a compound represented by the following formula (IV-1).

[Wherein, k represents an integer of 0 to 10, R ⁴¹ represents a hydrocarbyl group having 1 to 5 carbon atoms, R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ each independently represent 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. ]

K in the formula (IV-1) represents an integer of 0 to 10. From the viewpoint of improving economy, it is preferably 3 or less, more preferably 0.

R ^{41 in} formula (IV-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} formula (IV-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 to 5 carbon atoms. 5 represents a hydrocarbyloxy group, and when there are a plurality of R ⁴² and R ⁴³ , 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 and wet grip performance with good balance 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} formula (IV-1) each independently have 1 carbon atom which may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. R ⁴⁶ and R ⁴⁷ may be bonded to form a ring structure with a nitrogen atom, and R ⁴⁶ and R ⁴⁷ may be the same group bonded to the nitrogen by a double bond. Good.

Examples of R ⁴⁶ and R ^{47 in} formula (IV-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 a nitrogen atom is preferably an acyclic amino group, more preferably a dialkyl, from the viewpoint of low fuel consumption, wet grip performance, long-term stability and availability of the compound. An amino group, more preferably a dimethylamino group or a diethylamino group.

Examples of the compound represented by the formula (IV-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 fuel economy and wet grip performance 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 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.

<Method for producing copolymer>
The copolymer of the present invention in which the main chain and the terminal are modified includes 1,3-butadiene and a compound represented by the above formula (I), or 1,3-butadiene, an aromatic vinyl compound and the above formula (I). The compound represented by the above formula (II), the compound having the group represented by the above formula (III) and the above formula (IV) at the active terminal of the polymer obtained by copolymerizing the compound represented by It can be produced by reacting at least one compound selected from the group consisting of compounds having a group represented by the following method.

(Polymerization method)
There is no restriction | limiting in particular about the polymerization method of the said copolymer, All can use a solution polymerization method, a gas phase polymerization method, and a bulk polymerization method, and a solution polymerization method is preferable from a viewpoint of the ease of handling. Further, the polymerization mode may be either a batch type or a continuous type.

When the solution polymerization method is used, the monomer concentration in the solution (total of 1,3-butadiene, aromatic vinyl compound, compound represented by formula (I), etc.) is preferably 5% by mass or more. Preferably it is 10 mass% or more. When the monomer concentration in the solution is less than 5% by mass, the amount of the copolymer obtained 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. If the monomer concentration in the solution exceeds 50% by mass, the solution viscosity becomes too high, stirring becomes difficult, and polymerization tends to be difficult.

(Polymerization initiator in anionic polymerization)
When anionic polymerization is performed, the polymerization initiator is not particularly limited, but an organic lithium compound is preferably used. As the organic lithium compound, those having an alkyl group having 2 to 20 carbon atoms are preferable. For example, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, tert -Octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, reaction products of diisopropenylbenzene and butyl lithium, etc. Among these, n-butyllithium or sec-butyllithium is preferable from the viewpoints of availability and safety.

(Method of anionic polymerization)
There is no restriction | limiting in particular as a method of manufacturing a copolymer by anionic polymerization using the said organolithium compound as a polymerization initiator, A conventionally well-known method can be used. Specifically, in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic, or aromatic hydrocarbon compound, butyl lithium or the like is used as a polymerization initiator, and a randomizer is used as necessary. In the presence of 1,3-butadiene and the compound represented by the formula (I), and if necessary, an aromatic vinyl compound or the like may be anionically polymerized. In addition, after anionic polymerization, you may add a well-known anti-aging agent and alcohol etc. for the purpose of stopping a polymerization reaction as needed.

(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 microstructure control of a conjugated diene moiety in a copolymer (for example, an increase in 1,2-bonds in butadiene, etc.) and a control of the composition distribution of monomer units in the copolymer (for example, It is a compound having an action such as a butadiene unit, randomization of a styrene unit, etc. in a butadiene-styrene copolymer. 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 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.

Examples of the modification method using a modifier include a method in which a copolymer whose main chain is modified by anionic polymerization is synthesized, and then the copolymer and the modifier are brought into contact with each other. It reacts with the functional group of the modifier. As a result, a copolymer having a modified main chain and terminal is obtained. The amount of the modifier to be reacted is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the copolymer. In the copolymer of the present invention, at least one terminal is preferably modified, and both terminals are more preferably modified.

In the present invention, after carrying out the modification reaction with the above-mentioned modifier, a known anti-aging agent or alcohol may be added as necessary to stop the polymerization reaction.

<Rubber composition>
(Rubber component)
The above copolymer can be used as a rubber component of a rubber composition. The content of the copolymer in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, and particularly preferably 35% 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 efficiency and wet grip performance. Further, the content of the copolymer is preferably 90% by mass or less, more preferably 70% by mass or less. When it exceeds 90 mass%, it tends to be expensive.

The above 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 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 because they exhibit a good balance between low fuel consumption and wet grip performance. These rubber components may be used alone or in combination of two or more.

When the rubber composition of the present invention contains NR, the content of NR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 15% by mass or more, and preferably 35% by mass. Hereinafter, it is more preferably 25% by mass or less. Within the above range, low fuel consumption and wet grip performance can be obtained in a well-balanced manner.

When the rubber composition of the present invention contains BR, the content of BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 15% by mass or more, and preferably 35% by mass. Hereinafter, it is more preferably 25% by mass or less. Within the above range, low fuel consumption and wet grip performance can be obtained in a well-balanced manner.

When the rubber composition of the present invention contains SBR, the content of SBR in 100% by mass of the rubber component is preferably 35% by mass or more, more preferably 45% by mass or more, and preferably 85% by mass. Hereinafter, it is more preferably 75% by mass or less, and still more preferably 65% by mass or less. Within the above range, low fuel consumption and wet grip performance can be obtained in a well-balanced manner.

(silica)
The rubber composition of the present invention preferably contains silica as a reinforcing agent. Dispersion of silica is promoted by the copolymer, and the effect of improving fuel economy and wet grip performance can be enhanced. 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, and preferably 300 m ² / g or less, more preferably 250 m ² / g. It is as follows. 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.
In addition, the nitrogen adsorption specific surface area by the BET method of a silica can be measured by the method based on ASTM D3037-81.

The content of silica is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 30 parts by mass or more, particularly preferably 50 parts by mass or more, relative to 100 parts by mass of the rubber component. Preferably it is 150 mass parts or less, More 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 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 150 m ² / g or less. is there. 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 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. 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 30 parts by mass or less, more preferably 10 parts by mass or less. If it exceeds 30 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. Is mentioned. 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 and wet grip performance 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.

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.
n-hexane: manufactured by Kanto Chemical Co., Ltd .: styrene manufactured by Kanto Chemical Co., Ltd. 1,3-butadiene: manufactured by Tokyo Chemical Industry Co., Ltd. p-methoxystyrene: manufactured by Kanto Chemical Co., Ltd. (expressed by the formula (I) Compound)
p- (tert-Butoxy) styrene: Wako Pure Chemical Industries, Ltd. (compound represented by formula (I))
Tetramethylethylenediamine: n-butyllithium manufactured by Kanto Chemical Co., Ltd .: 1.6M n-butyllithium hexane solution modifier manufactured by Kanto Chemical Co., Ltd. A-1: N- (3- manufactured by Tokyo Chemical Industry Co., Ltd. Dimethylaminopropyl) acrylamide modifier A-2: 4,4′-bis (diethylamino) benzophenone modifier A-3 manufactured by Tokyo Chemical Industry Co., Ltd. 1,3-dimethyl-2 manufactured by Tokyo Chemical Industry Co., Ltd. -Imidazolidinone modifier A-4: 1-phenyl-2-pyrrolidone modifier A-5 manufactured by Tokyo Chemical Industry Co., Ltd .: N-methyl-ε-caprolactam modifier A- manufactured by Tokyo Chemical Industry Co., Ltd. 6: N, N-dimethylformamide dimethyl acetal modifier manufactured by Tokyo Chemical Industry Co., Ltd. A-7: 4- (dimethylamino) butyraldehyde dimethyl acetal modified by Tokyo Chemical Industry Co., Ltd. A-8: N, N-dimethylbenzamide modifier A-9: 4′-aminoacetophenone 2,6-tert-butyl-p-cresol manufactured by Tokyo Chemical Industry Co., Ltd. : Nocrack 200 manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

<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 contents of the compound represented by formula (I) (p-methoxystyrene, p- (tert-butoxy) styrene), styrene, and 1,3-butadiene in the copolymer were calculated.

<Synthesis of copolymer>
(Copolymer (1))
Add 1500 ml of n-hexane, 100 mmol of styrene, 800 mmol of 1,3-butadiene, 5 mmol of p-methoxystyrene, 0.2 mmol of tetramethylethylenediamine, and 0.12 mmol of n-butyllithium to a heat-resistant container sufficiently purged with nitrogen at 0 ° C. Stir for 48 hours. Thereafter, 0.15 mmol of modifier A-1 was added and stirred at 0 ° C. for 15 minutes. Thereafter, alcohol was added to stop the reaction, 1 g of 2,6-tert-butyl-p-cresol was added to the reaction solution, and then copolymer (1) was obtained by reprecipitation purification. The weight average molecular weight of the obtained copolymer (1) is 500,000, the content of the compound represented by the above formula (I) (alkoxystyrene component content) is 1.2% by mass, and the styrene content (styrene). The component content was 19% by mass.

(Copolymer (2) to (15))
Synthesis was performed in the same manner as for the copolymer (1) using the recipe in Table 1. Table 1 shows the properties of the obtained copolymers (2) to (15).

Below, various chemical | medical agents used by the Example and the comparative example are demonstrated.
NR: RSS # 3
BR: Ubepol BR150B manufactured by Ube Industries, Ltd.
SBR: SL574 manufactured by JSR Corporation
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 (N ₂ SA: 96 m ² / manufactured by Mitsubishi Chemical Corporation)
g, DBP absorption: 124 ml / 100 g)
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Anti-aging agent: NOCRACK 6C (N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine) manufactured by Ouchi Shinsei Chemical Co., Ltd.
Stearic acid: Zinc stearate manufactured by NOF Corporation: Zinc Hua No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd. 1: Noxeller CZ manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Vulcanization accelerator 2: Noxeller D from Ouchi Shinsei Chemical Co., Ltd.

(Examples and Comparative Examples)
According to the blending content shown in Table 2, materials other than sulfur and vulcanization accelerator were kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer manufactured by Kobe Steel Co., Ltd. Obtained. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes under the condition of 80 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized at 170 ° C. for 15 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 10 minutes, and tested. Tires (size: 195 / 65R15) were manufactured.
The obtained vulcanized rubber composition and the test tire were evaluated by the following test methods.

(Low fuel consumption)
Using a spectrometer manufactured by Ueshima Seisakusho, tan δ was measured at a dynamic strain amplitude of 1%, a frequency of 10 Hz, and a temperature of 50 ° C. And the measurement result was displayed as an index according to the following formula. The larger the index, the lower the rolling resistance and the better the fuel efficiency.
(Low fuel consumption index) = (tan δ of Comparative Example 3) / (tan δ of each formulation) × 100

(Wet grip performance (1))
Wet grip performance was evaluated using a flat belt friction tester (FR5010 type) manufactured by Ueshima Seisakusho. A cylindrical rubber test piece having a width of 20 mm and a diameter of 100 mm made of the above vulcanized rubber composition was used as a sample, and the slip ratio of the sample with respect to the road surface was 0 to 0 at a speed of 20 km / hour, a load of 4 kgf, and a road surface temperature of 20 ° C. The maximum value of the friction coefficient detected at that time was read up to 70%. And the measurement result was displayed as an index according to the following formula. A larger index indicates better wet grip performance.
(Wet grip performance (1) index) = (maximum friction coefficient of each formulation) / (maximum friction coefficient of Comparative Example 3) × 100

(Wet grip performance (2))
On a test course with wet water and wet road surface, the test tire is mounted on a 2000 cc domestic FR vehicle, braked at a speed of 70 km / h, and the distance traveled between braking the tire and stopping (Brake distance) was measured. And the measurement result was displayed as an index according to the following formula. A larger index indicates better wet grip performance.
(Wet grip performance (2) index) = (Brake distance of Comparative Example 3) / (Brake distance of each formulation) × 100

As shown in Table 2, 1,3-butadiene and a specific aromatic compound, or a polymer active terminal obtained by copolymerizing 1,3-butadiene, an aromatic vinyl compound and a specific aromatic compound, The rubber composition of an example including a copolymer obtained by reacting a compound having a specific functional group and having a weight average molecular weight Mw within a specific range is lower in fuel consumption than the rubber composition of a comparative example. Improved wet grip performance in a well-balanced manner.

Claims (7)

A monomer unit based on a compound represented by the monomer units and the following formula based on 1,3-butadiene (I), or, monomer unit based on 1,3-butadiene, monomer units derived from styrene And having a monomer unit based on a compound represented by the following formula (I):
The compound represented by the following formula (II), at least one compound selected from the group consisting of a compound having a group represented by a compound having a group represented by the following formula (III) and formula (IV) The end is denatured ,
A copolymer having a weight average molecular weight Mw of 1.0 × 10 ^{5 to} 2.5 × 10 ⁶ .

[Wherein, R ¹ represents a hydrocarbyl group having 1 to 10 carbon atoms. ]

[Wherein 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, 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 group or a hydroxyl group represented by the following formula (IIa). ]

[Wherein, 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 amino Represents a group. ]

[Wherein, m represents an integer of 1 to 11, and A ⁴ represents an amino group. ]

[Wherein R ²³ and R ²⁴ each independently have 1 to 6 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 ²³ and R ²⁴ may be bonded to form a ring structure together with a nitrogen atom, and R ²³ and R ²⁴ may be the same group bonded to nitrogen by a double bond. ] The copolymer according to claim 1, wherein the content of the monomer unit based on the compound represented by the formula (I) is 0.05 to 10% by mass. The copolymer according to claim 1 or 2, wherein the content of the monomer unit based on styrene is 0.1 to 55% by mass. The rubber composition containing the copolymer in any one of Claims 1-3 . The rubber composition according to claim 4 , wherein the content of the copolymer is 5% by mass or more in 100% by mass of the rubber component. The rubber composition according to claim 4 or 5, comprising 5 to 150 parts by mass of silica with respect to 100 parts by mass of the rubber component. A pneumatic tire produced using the rubber composition according to any of claims 4-6.