JP5902447B2 - Rubber composition and pneumatic tire - Google Patents

Description

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

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

As a method for improving fuel economy, for example, Patent Document 1 proposes a method using a diene rubber (modified rubber) modified with an organosilicon compound containing an amino group and an alkoxy group. However, when the modified rubber is used, the fuel efficiency is improved, while the Mooney viscosity is increased and the processability tends to be deteriorated. In addition, the strength required for the rubber composition for automobile tires also includes breaking strength, but the breaking strength is generally in contradiction to low fuel consumption, and each performance can be obtained in a high level with a good balance. It was difficult.

JP 2000-344955 A

An object of the present invention is to solve the above-mentioned problems and to provide a rubber composition that can improve fuel economy, breaking strength, and processability in a well-balanced manner, and a pneumatic tire using the rubber composition.

（式（Ｉ）中、ｉは０又は１であり、Ｒ^１１は炭素原子数１〜１００のヒドロカルビレン基を表し、Ｒ^１２及びＲ^１３は、置換基を有してもよいヒドロカルビル基、又は、トリヒドロカルビルシリル基を表すか、あるいは、Ｒ^１２とＲ^１３とが結合して、ケイ素原子、窒素原子及び酸素原子からなる原子群から選択される少なくとも１種の原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｍはアルカリ金属原子を表す。） The present invention provides a nitrogen atom and an active terminal of a copolymer obtained by polymerizing a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound using a polymerization initiator represented by the following formula (I). And / or a conjugated diene polymer obtained by reacting a compound containing a silicon atom, silica, and a silane coupling agent having a mercapto group, the rubber component containing 100% by mass of the conjugated diene polymer. Content is 25-50 mass%, Content of the said silica with respect to 100 mass parts of said rubber components is 40-80 mass parts, Content of the said silane coupling agent with respect to 100 mass parts of said silica is 1-20. It is related with the rubber composition which is a mass part.

(In Formula (I), i is 0 or 1, R ¹¹ represents a hydrocarbylene group having 1 to 100 carbon atoms, R ¹² and R ¹³ are hydrocarbyl groups which may have a substituent, Alternatively, it represents a trihydrocarbylsilyl group, or R ¹² and R ¹³ are bonded to each other and have at least one atom selected from the atomic group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a hetero atom. Represents an optionally hydrocarbylene group, and M represents an alkali metal atom.)

（式（Ｉａ）中、Ｒ^１４は共役ジエン化合物由来の構造単位及び／又は芳香族ビニル化合物由来の構造単位からなるヒドロカルビレン基を表し、ｎは１〜１０の整数を表す。） R ^{11 in the} above formula (I) is preferably a group represented by the following formula (Ia).

(In formula (Ia), R ¹⁴ represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, and n represents an integer of 1 to 10.)

R ^{14 in the} above formula (Ia) is preferably a hydrocarbylene group composed of 1 to 10 structural units derived from isoprene.

（式（ＩＩ）中、ｍは０又は１であり、Ｒ^２１はヒドロカルビレン基を表し、Ｘ^１、Ｘ^２及びＸ^３は置換アミノ基、ヒドロカルビルオキシ基、又は置換基を有していてもよいヒドロカルビル基を表す。） The silicon-containing vinyl compound is preferably a compound represented by the following formula (II).

(In formula (II), m is 0 or 1, R ²¹ represents a hydrocarbylene group, and X ¹ , X ² and X ³ have a substituted amino group, a hydrocarbyloxy group, or a substituent. Represents a good hydrocarbyl group.)

The conjugated diene polymer preferably has a structural unit derived from an aromatic vinyl compound.

The nitrogen adsorption specific surface area of the silica is preferably 40 to 400 m ² / g.

The silica preferably contains silica (1) having a nitrogen adsorption specific surface area of 40 m ² / g or more and less than 120 m ² / g and silica (2) having a nitrogen adsorption specific surface area of 120 m ² / g or more.

The rubber composition preferably contains 1 to 20 parts by mass of a liquid resin having a softening point of -20 to 20 ° C with respect to 100 parts by mass of the rubber component.

The rubber composition comprises a silica (1) having a nitrogen adsorption specific surface area of 40 m ² / g or more and less than 120 m ² / g and a silica (2) having a nitrogen adsorption specific surface area of 120 m ² / g or more, Preferably contains 1 to 20 parts by mass of a liquid resin having a softening point of -20 to 20 ° C with respect to 100 parts by mass of the rubber component.

（式（１）中、Ｒ^１０１〜Ｒ^１０３は、分岐若しくは非分岐の炭素数１〜１２のアルキル基、分岐若しくは非分岐の炭素数１〜１２のアルコキシ基、又は−Ｏ−（Ｒ^１１１−Ｏ）_ｚ−Ｒ^１１２（ｚ個のＲ^１１１は、分岐若しくは非分岐の炭素数１〜３０の２価の炭化水素基を表す。ｚ個のＲ^１１１はそれぞれ同一でも異なっていてもよい。Ｒ^１１２は、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、炭素数６〜３０のアリール基、又は炭素数７〜３０のアラルキル基を表す。ｚは１〜３０の整数を表す。）で表される基を表す。Ｒ^１０１〜Ｒ^１０３はそれぞれ同一でも異なっていてもよい。Ｒ^１０４は、分岐若しくは非分岐の炭素数１〜６のアルキレン基を表す。）

（式（２）及び（３）中、Ｒ^２０１は水素、ハロゲン、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、分岐若しくは非分岐の炭素数２〜３０のアルキニル基、又は該アルキル基の末端の水素が水酸基若しくはカルボキシル基で置換されたものを表す。Ｒ^２０２は分岐若しくは非分岐の炭素数１〜３０のアルキレン基、分岐若しくは非分岐の炭素数２〜３０のアルケニレン基、又は分岐若しくは非分岐の炭素数２〜３０のアルキニレン基を表す。Ｒ^２０１とＲ^２０２とで環構造を形成してもよい。） The silane coupling agent includes a compound represented by the following formula (1) and / or a binding unit A represented by the following formula (2) and a binding unit B represented by the following formula (3). It is preferable.

(In the formula (1), R ^{101 to} R ¹⁰³ are each a branched or unbranched C 1-12 alkyl group, a branched or unbranched C 1-12 alkoxy group, or —O— (R ¹¹¹ — O) _z- R ¹¹² (z R ¹¹¹ represents a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms. The z R ^{111 s} may be the same as or different from each other. ¹¹² represents a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. Z represents an integer of 1 to 30.) R ^{101 to} R ¹⁰³ may be the same as or different from each other, and R ¹⁰⁴ has 1 to 6 carbon atoms which are branched or unbranched. Represents an alkylene group of

(In the formulas (2) and (3), R ²⁰¹ is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, branched or unbranched alkenyl group having 2 to 30 carbon atoms, branched or unbranched. Or an alkyl group substituted with a hydroxyl group or a carboxyl group, and R ²⁰² represents a branched or unbranched C 1-30 alkylene group, branched or It represents an unbranched C2-C30 alkenylene group or a branched or unbranched C2-C30 alkynylene group, and R ²⁰¹ and R ²⁰² may form a ring structure.)

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

According to the present invention, since it is a rubber composition containing a specific amount of a specific conjugated diene polymer, silica, and a silane coupling agent having a mercapto group, low fuel consumption, breaking strength and processability are obtained. A pneumatic tire improved in a well-balanced manner can be provided.

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

（式（Ｉ）中、ｉは０又は１であり、Ｒ^１１は炭素原子数１〜１００のヒドロカルビレン基を表し、Ｒ^１２及びＲ^１３は、置換基を有してもよいヒドロカルビル基、又は、トリヒドロカルビルシリル基を表すか、あるいは、Ｒ^１２とＲ^１３とが結合して、ケイ素原子、窒素原子及び酸素原子からなる原子群から選択される少なくとも１種の原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｍはアルカリ金属原子を表す。） The conjugated diene polymer according to the present invention is a copolymer obtained by polymerizing a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound using a polymerization initiator represented by the following formula (I). It is obtained by reacting a compound containing a nitrogen atom and / or a silicon atom with the active terminal.

(In Formula (I), i is 0 or 1, R ¹¹ represents a hydrocarbylene group having 1 to 100 carbon atoms, R ¹² and R ¹³ are hydrocarbyl groups which may have a substituent, Alternatively, it represents a trihydrocarbylsilyl group, or R ¹² and R ¹³ are bonded to each other and have at least one atom selected from the atomic group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a hetero atom. Represents an optionally hydrocarbylene group, and M represents an alkali metal atom.)

In this specification, “modify” means that a compound other than these is bonded to a diene compound or a copolymer having a diene compound and an aromatic vinyl compound. In the case of the conjugated diene polymer, the polymer initiation terminal is modified by the polymerization initiator represented by the above formula (I), the main chain is modified by copolymerizing the silicon-containing vinyl compound, the nitrogen atom and / or Alternatively, it has a structure in which the terminating end is modified with a silicon-containing vinyl compound. By blending the conjugated diene polymer as a rubber component, silica can be dispersed well, and fuel economy, breaking strength and processability can be improved in a well-balanced manner. In general, when a modified rubber in which all of the start terminal, main chain, and stop terminal are modified is used, the processability tends to be greatly deteriorated. Since each of the chain and the terminal end is modified with a combination of specific compounds, good processability can be ensured, and the effect of improving fuel economy and breaking strength can be enhanced synergistically. And each improvement effect can be further synergistically improved by mix | blending the silane coupling agent which has a mercapto group with the said conjugated diene type polymer. As a result, low fuel consumption, breaking strength, and workability can be improved in a high-dimensional and well-balanced manner.

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

R ¹¹ in the formula (I) is a hydrocarbylene group having 1 to 100 carbon atoms, preferably a hydrocarbylene group having 6 to 100 carbon atoms, more preferably 7 to 80 carbon atoms. It is a hydrocarbylene group. When the number of carbon atoms in R ¹¹ exceeds 100, the molecular weight of the polymerization initiator increases, and the economy and operability during polymerization may be reduced.
As the polymerization initiator represented by formula (I), the number of carbon atoms of R ¹¹ may be used in combination plural kinds of different compounds.

（式（Ｉａ）中、Ｒ^１４は共役ジエン化合物由来の構造単位及び／又は芳香族ビニル化合物由来の構造単位からなるヒドロカルビレン基を表し、ｎは１〜１０の整数を表す。） R ¹¹ in the formula (I) is preferably a group represented by the following formula (Ia).

(In formula (Ia), R ¹⁴ represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, and n represents an integer of 1 to 10.)

In the formula (Ia), R ¹⁴ represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, preferably a hydrocarbylene group composed of a structural unit derived from isoprene. And more preferably a hydrocarbylene group consisting of 1 to 10 structural units derived from isoprene.

The number of structural units derived from a conjugated diene compound and / or an aromatic vinyl compound in R ¹⁴ is preferably 1 to 10 units, and more preferably 1 to 5 units.

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

R ¹¹ includes a group in which 1 to 10 structural units derived from isoprene and a methylene group are bonded, a group in which 1 to 10 structural units derived from isoprene and an ethylene group are bonded, and a structural unit 1 to 1 derived from isoprene. Examples thereof include a group in which 10 units and a trimethylene group are bonded, and a group in which 1 to 10 structural units derived from isoprene and a trimethylene group are bonded is preferable.

R ¹² and R ^{13 in} formula (I) represent a hydrocarbyl group or trihydrocarbylsilyl group which may have a substituent, or R ¹² and R ¹³ are bonded to each other to form a silicon atom, The hydrocarbylene group which may have as a hetero atom the atom selected from the group which consists of a nitrogen atom and an oxygen atom is represented.

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

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

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

R ¹² and R ¹³ are preferably hydrocarbyl groups, or R ¹² and R ¹³ are preferably bonded to form a hydrocarbylene group, which is a chain alkyl group having 1 to 4 carbon atoms, or a bond It is more preferably an alkylene group having 4 to 7 carbon atoms, and further preferably a methyl group or an ethyl group.

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

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

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

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

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

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

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

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, and myrcene. Two or more kinds may be used. From the viewpoint of availability, 1,3-butadiene and isoprene are preferable.

（式（ＩＩ）中、ｍは０又は１であり、Ｒ^２１はヒドロカルビレン基を表し、Ｘ^１、Ｘ^２及びＸ^３は置換アミノ基、ヒドロカルビルオキシ基、又は置換基を有していてもよいヒドロカルビル基を表す。） The silicon-containing vinyl compound is preferably a compound represented by the following formula (II).

(In formula (II), m is 0 or 1, R ²¹ represents a hydrocarbylene group, and X ¹ , X ² and X ³ have a substituted amino group, a hydrocarbyloxy group, or a substituent. Represents a good hydrocarbyl group.)

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

Examples of the hydrocarbylene group in the formula (II) include an alkylene group, an alkenediyl group, an arylene group, and a group in which an arylene group and an alkylene group are bonded. Examples of the alkylene group include a methylene group, an ethylene group, and a trimethylene group. Examples of the alkenediyl group include a vinylene group and an ethylene-1,1-diyl group. Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the group in which an arylene group and an alkylene group are bonded include a group in which a phenylene group and a methylene group are bonded, and a group in which a phenylene group and an ethylene group are bonded.

R ²¹ is preferably an arylene group, more preferably a phenylene group.

In the formula (II), X ¹ , X ² and X ³ represent a substituted amino group, a hydrocarbyloxy group, or a hydrocarbyl group which may have a substituent. Preferably, at least one of X ¹ , X ² and X ³ is a substituted amino group, more preferably ^{two of} X ¹ , X ² and X ³ are substituted amino groups.

（式（ＩＩａ）中、Ｒ^２２及びＲ^２３は、置換基を有してもよいヒドロカルビル基、又は、トリヒドロカルビルシリル基を表すか、あるいは、Ｒ^２２とＲ^２３とが結合して、窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表す。） The substituted amino group in the formula (II) is preferably a group represented by the following formula (IIa).

(In Formula (IIa), R ²² and R ²³ represent a hydrocarbyl group or a trihydrocarbylsilyl group which may have a substituent, or R ²² and R ²³ are bonded to form a nitrogen atom. And / or a hydrocarbylene group which may have an oxygen atom as a hetero atom.)

The hydrocarbyl group which may have a substituent in formula (IIa) is a hydrocarbyl group or a substituted hydrocarbyl group. Examples of the substituted hydrocarbyl group include a substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group. Hydrocarbyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and n-octyl. A chain alkyl group such as a group; a cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group; and an aryl group such as a phenyl group, a benzyl group, and a naphthyl group. A chain alkyl group is preferred, and a methyl group or an ethyl group is preferred. More preferred. Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, ethoxymethyl group, and methoxyethyl group; aryloxyalkyl groups such as a phenoxymethyl group.

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

The hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom in formula (IIa) as a heteroatom is a heteroatom-containing hydrocarbyl group in which the hydrocarbylene group or heteroatom is a nitrogen atom and / or an oxygen atom. Is a ren group. The heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom and / or an oxygen atom includes a heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom, and a heteroatom-containing hydrocarbylene in which the heteroatom is an oxygen atom You can raise a group. Examples of the hydrocarbylene group include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, decamethylene group, dodecamethylene group, 2,2,4-trimethylhexane-1,6. An alkylene group such as a diyl group; and an alkenediyl group such as a pentane-2-ene-1,5-diyl group. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom include a group represented by —CH═N—CH═CH— and a group represented by —CH═N—CH ₂ —CH ₂ —. be able to. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom include a group represented by —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —.

R ²² and R ²³ are alkyl groups, or R ²² and R ²³ are preferably bonded to form an alkylene group, more preferably an alkyl group, and a methyl group or an ethyl group. Is more preferable.

Among the substituted amino groups represented by the formula (IIa), R ²² and R ²³ are hydrocarbyl groups, and dimethylamino group, diethylamino group, ethylmethylamino group, di-n-propylamino group, diisopropylamino group A dialkylamino group such as di-n-butylamino group, diisobutylamino group, di-sec-butylamino group, di-tert-butylamino group; Group is preferable, and a dimethylamino group, a diethylamino group, and a di-n-butylamino group are more preferable. Examples of the substituted hydrocarbyl group in which R ²² and R ²³ have a hydrocarbyloxy group as a substituent include di (alkoxyalkyl) amino groups such as di (methoxymethyl) amino group and di (ethoxymethyl) amino group. Can do. Examples of R ²² and R ^{23 that} are trihydrocarbylsilyl groups include trialkylsilyl groups such as bis (trimethylsilyl) amino group, bis (tert-butyldimethylsilyl) amino group, and N-trimethylsilyl-N-methylamino group. An amino group can be mentioned.

Among the substituted amino groups represented by the formula (IIa), those in which R ²² and R ²³ are bonded to form a hydrocarbylene group include 1-trimethyleneimino group, 1-pyrrolidino group, 1- Examples include 1-alkyleneimino groups such as piperidino group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-decamethyleneimino group, 1-dodecamethyleneimino group. Examples of the hetero atom-containing hydrocarbylene group in which the hetero atom is a nitrogen atom include a 1-imidazolyl group and a 4,5-dihydro-1-imidazolyl group. Examples of the hetero atom-containing hydrocarbylene group in which the hetero atom is an oxygen atom include a morpholino group.

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

Examples of the hydrocarbyloxy group in the formula (II) include alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, and tert-butoxy group; phenoxy group, benzyloxy And aryloxy groups such as a group.

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

Of the silicon-containing vinyl compounds represented by the formula (II), one of X ¹ , X ² and X ³ is a substituted amino group, and m is 0.
(Dimethylamino) dimethylvinylsilane, (ethylmethylamino) dimethylvinylsilane, (di-n-propylamino) dimethylvinylsilane, (diisopropylamino) dimethylvinylsilane, (dimethylamino) diethylvinylsilane, (ethylmethylamino) diethylvinylsilane, (di (Dialkylamino) dialkylvinylsilanes such as -n-propylamino) diethylvinylsilane, (diisopropylamino) diethylvinylsilane; [bis (trimethylsilyl) amino] dimethylvinylsilane, [bis (t-butyldimethylsilyl) amino] dimethylvinylsilane, [bis [Bis (trialkyl) amino] diethylvinylsilane, [bis (t-butyldimethylsilyl) amino] diethylvinylsilane, etc. (Silyl) amino] dialkylvinylsilane; (dimethylamino) di (methoxymethyl) vinylsilane, (dimethylamino) di (methoxyethyl) vinylsilane, (dimethylamino) di (ethoxymethyl) vinylsilane, (dimethylamino) di (ethoxyethyl) vinylsilane (Dialkylamino) di (alkoxyalkyl) such as (diethylamino) di (methoxymethyl) vinylsilane, (diethylamino) di (methoxyethyl) vinylsilane, (diethylamino) di (ethoxymethyl) vinylsilane, (diethylamino) di (ethoxyethyl) vinylsilane ) Vinylsilane; pyrrolidinodimethylvinylsilane, piperidinodimethylvinylsilane, hexamethyleneiminodimethylvinylsilane, 4,5-dihydroimidazolyldimethylvinyl Silane, can be mentioned morpholino cyclic amino dialkylvinylsilane compounds such as dimethyl vinyl silane.

Among the silicon-containing vinyl compounds represented by the formula (II), one of X ¹ , X ² and X ³ is a substituted amino group and m is 1,
(Dimethylamino) dimethyl-4-vinylphenylsilane, (dimethylamino) dimethyl-3-vinylphenylsilane, (diethylamino) dimethyl-4-vinylphenylsilane, (diethylamino) dimethyl-3-vinylphenylsilane, (di-n -Propylamino) dimethyl-4-vinylphenylsilane, (di-n-propylamino) dimethyl-3-vinylphenylsilane, (di-n-butylamino) dimethyl-4-vinylphenylsilane, (di-n-butyl) Amino) dimethyl-3-vinylphenylsilane, (dimethylamino) diethyl-4-vinylphenylsilane, (dimethylamino) diethyl-3-vinylphenylsilane, (diethylamino) diethyl-4-vinylphenylsilane, (diethylamino) diethyl- 3-vinyl pheny Silane, (di-n-propylamino) diethyl-4-vinylphenylsilane, (di-n-propylamino) diethyl-3-vinylphenylsilane, (di-n-butylamino) diethyl-4-vinylphenylsilane, Mention may be made of (dialkylamino) dialkylvinylphenylsilanes such as (di-n-butylamino) diethyl-3-vinylphenylsilane.

Of the silicon-containing vinyl compounds represented by the formula (II), ^{two of} X ¹ , X ² and X ³ are substituted amino groups, and m is 0.
Bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (di-n-propylamino) methylvinylsilane, bis (di-n-butylamino) methylvinylsilane, bis (dimethylamino) ethylvinylsilane, bis (diethylamino) ) Bis (dialkylamino) alkylvinylsilanes such as ethylvinylsilane, bis (di-n-propylamino) ethylvinylsilane, bis (di-n-butylamino) ethylvinylsilane; bis [bis (trimethylsilyl) amino] methylvinylsilane, bis [ Bis (tert-butyldimethylsilyl) amino] methylvinylsilane, bis [bis (trimethylsilyl) amino] ethylvinylsilane, bis [bis (tert-butyldimethylsilyl) amino] ethylvinyl Bis [bis (trialkylsilyl) amino] alkyl vinyl silanes such as orchid; bis (dimethylamino) methoxymethyl vinyl silane, bis (dimethylamino) methoxyethyl vinyl silane, bis (dimethylamino) ethoxymethyl vinyl silane, bis (dimethylamino) ethoxyethyl Bis (dialkylamino) alkoxyalkylsilanes such as vinylsilane, bis (diethylamino) methoxymethylvinylsilane, bis (diethylamino) methoxyethylvinylsilane, bis (diethylamino) ethoxymethylvinylsilane, bis (dimethylamino) ethoxyethylvinylsilane; bis (pyrrolidino) methyl Vinylsilane, bis (piperidino) methylvinylsilane, bis (hexamethyleneimino) methylvinylsilane, bis (4,5- It can be mentioned hydro imidazolylmethyl) methyl vinyl silane, bis (morpholino) bis (cyclic amino such as methyl vinyl silane) alkyl vinyl silane compounds.

Among the silicon-containing vinyl compounds represented by the formula (II), ^{two of} X ¹ , X ² and X ³ are substituted amino groups, and m is 1,
Bis (dimethylamino) methyl-4-vinylphenylsilane, bis (dimethylamino) methyl-3-vinylphenylsilane, bis (diethylamino) methyl-4-vinylphenylsilane, bis (diethylamino) methyl-3-vinylphenylsilane, Bis (di-n-propylamino) methyl-4-vinylphenylsilane, bis (di-n-propylamino) methyl-3-vinylphenylsilane, bis (di-n-butylamino) methyl-4-vinylphenylsilane Bis (di-n-butylamino) methyl-3-vinylphenylsilane, bis (dimethylamino) ethyl-4-vinylphenylsilane, bis (dimethylamino) ethyl-3-vinylphenylsilane, bis (diethylamino) ethyl- 4-vinylphenylsilane, bis (diethylamino) Til-3-vinylphenylsilane, bis (di-n-propylamino) ethyl-4-vinylphenylsilane, bis (di-n-propylamino) ethyl-3-vinylphenylsilane, bis (di-n-butylamino) And bis (dialkylamino) alkylvinylphenylsilane such as ethyl-4-vinylphenylsilane and bis (di-n-butylamino) ethyl-3-vinylphenylsilane.

Of the silicon-containing vinyl compounds represented by the formula (II), three of X ¹ , X ² and X ³ are substituted amino groups, and m is 0.
Examples include tris (dialkylamino) vinylsilane such as tris (dimethylamino) vinylsilane, tris (diethylamino) vinylsilane, tris (di-n-propylamino) vinylsilane, tris (di-n-butylamino) vinylsilane.

Of the silicon-containing vinyl compounds represented by the formula (II), three of X ¹ , X ² and X ³ are substituted amino groups, and m is 1,
Tris (dimethylamino) -4-vinylphenylsilane, tris (dimethylamino) -3-vinylphenylsilane, tris (diethylamino) -4-vinylphenylsilane, tris (diethylamino) -3-vinylphenylsilane, tris (di- n-propylamino) -4-vinylphenylsilane, tris (di-n-propylamino) -3-vinylphenylsilane, tris (di-n-butylamino) -4-vinylphenylsilane, tris (di-n- And tris (dialkylamino) vinylphenylsilane such as butylamino) -3-vinylphenylsilane.

Among the silicon-containing vinyl compounds represented by the formula (II), as compounds in which X ¹ , X ² and X ³ are not substituted amino groups and m is 0,
Trialkoxyvinylsilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxyvinylsilane; dialkoxyalkylvinylsilanes such as methyldimethoxyvinylsilane and methyldiethoxyvinylsilane; di (tert-pentoxy) phenylvinylsilane, di (tert-butoxy) phenylvinylsilane Dialkoxyarylvinylsilanes; monoalkoxydialkylvinylsilanes such as dimethylmethoxyvinylsilane; monoalkoxydiarylvinylsilanes such as tert-butoxydiphenylvinylsilane, tert-pentoxydiphenylvinylsilane; tert-butoxymethylphenylvinylsilane, tert-butoxyethylphenylvinylsilane, etc. Monoalkoxyalkylary Vinylsilane; tris (beta-methoxyethoxy) substitution such as vinyl silane alkoxy vinyl silane compounds can be mentioned.

Further, examples of the silicon-containing vinyl compound include 4-N, N-bis (trimethylsilyl) aminostyrene, bis (trialkylsilyl) aminostyrene such as 3-N, N-bis (trimethylsilyl) aminostyrene; 4-bis (trimethylsilyl). ) Bis (trialkylsilyl) aminoalkylstyrene such as aminomethylstyrene, 3-bis (trimethylsilyl) aminomethylstyrene, 4-bis (trimethylsilyl) aminoethylstyrene, 3-bis (trimethylsilyl) aminoethylstyrene .

The silicon-containing vinyl compound is preferably a compound represented by formula (II), more preferably a compound in which m in formula (II) is 0, and among X ¹ , X ² and X ³ in formula (II) More preferred are compounds in which two are dialkylamino groups.

Particularly preferred compounds as the silicon-containing vinyl compound are bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, and bis (di-n-butylamino) methylvinylsilane.

In the production of the conjugated diene polymer, the amount of the silicon-containing vinyl compound used is 100% by mass based on the total amount of monomer components used in the polymerization, and the fuel economy, breaking strength and processability are improved in a well-balanced manner. Therefore, Preferably it is 0.01 mass% or more, More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to increase economic efficiency and to increase the tensile strength at break, the content is preferably 20% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less.

In the production of the conjugated diene polymer, a polymerizable monomer may be used as the monomer component in addition to the conjugated diene compound and the silicon-containing vinyl compound. Examples of the monomer include aromatic vinyl compounds, vinyl nitriles and unsaturated carboxylic acid esters. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene. Examples of the vinyl nitrile include acrylonitrile, and examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. In these, an aromatic vinyl compound is preferable and styrene is more preferable.

When an aromatic vinyl compound is used in the production of the conjugated diene polymer, the amount of the aromatic vinyl compound used is preferably 10% by mass, with the total amount of the conjugated diene compound and the aromatic vinyl compound being 100% by mass. It is at least mass% (the amount of conjugated diene compound used is 90% by mass or less), more preferably at least 15% by mass (the amount of conjugated diene compound used is 85% by mass or less). From the viewpoint of low fuel consumption, the amount of aromatic vinyl compound used is preferably 50% by mass or less (the amount of conjugated diene compound used is 50% by mass or more), more preferably 45% by mass or less (conjugated diene). The amount of the compound used is 55% by mass or more).

In the production of the conjugated diene polymer, the polymerization is preferably performed in a hydrocarbon solvent. The hydrocarbon solvent is a solvent that does not deactivate the polymerization initiator of formula (I), and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Examples of the aliphatic hydrocarbon include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, n-heptane, and n-octane. Examples of the aromatic hydrocarbon include benzene, toluene, xylene, and ethylbenzene. Examples of the alicyclic hydrocarbon include cyclopentane and cyclohexane. The hydrocarbon solvent may be a mixture of various components such as industrial hexane. Preferably, it is a hydrocarbon having 2 to 12 carbon atoms.

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

In the production of the conjugated diene polymer, a polymerization initiator may be supplied to the polymerization reactor before supplying the monomer component to the polymerization reactor. The polymerization initiator may be supplied to the polymerization reactor after being supplied to the reactor, or a part of the monomer components used for the polymerization may be supplied to the polymerization reactor and then supplied to the polymerization reactor. Good. Moreover, a polymerization initiator may be supplied to a polymerization reactor at a time, and may be supplied continuously.

In the production of the conjugated diene polymer, the monomer component may be supplied to the polymerization reactor at a time, may be supplied continuously, or may be supplied intermittently. Moreover, each monomer may be supplied separately to the polymerization reactor or may be supplied simultaneously.

The polymerization temperature in the production of the conjugated diene polymer is usually 25 to 100 ° C, preferably 35 to 90 ° C. More preferably, it is 50-80 degreeC. The polymerization time is usually 10 minutes to 5 hours.

The conjugated diene polymer is prepared by polymerizing a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound using a polymerization initiator represented by the formula (I) (active terminal (copolymer)). It can be obtained by reacting a compound containing a nitrogen atom and / or a silicon atom with the active terminal of the polymer (which is considered to have an alkali metal derived from the polymerization initiator) (terminal modification reaction). Specifically, a compound containing a nitrogen atom and / or a silicon atom is added to the polymerization solution and mixed. The amount of the compound containing nitrogen atoms and / or silicon atoms added to the polymerization solution is usually 0.1 to 3 mol per 1 mol of the alkali metal derived from the polymerization initiator represented by the formula (I) used. , Preferably, it is 0.5-2 mol, More preferably, it is 0.7-1.5 mol.

The reaction temperature of the terminal modification reaction is usually 25 to 100 ° C, preferably 35 to 90 ° C, more preferably 50 to 80 ° C. The reaction time for the terminal reaction is usually 60 seconds to 5 hours, preferably 5 minutes to 1 hour, more preferably 15 minutes to 1 hour.

Among the compounds containing a nitrogen atom and / or a silicon atom, preferred are compounds containing a nitrogen atom and a carbonyl group.

（式（ＩＩＩ）中、Ｒ^３１は置換基を有してもよいヒドロカルビル基、Ｒ^３２と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基、あるいは、Ｒ^３４と結合して２価基を表し、Ｒ^３２は置換基を有してもよいヒドロカルビル基、あるいは、Ｒ^３１と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ^３４は置換基を有してもよいヒドロカルビル基、水素原子、あるいは、Ｒ^３１と結合して２価基を表す。また、Ｒ^３３は２価基を表し、ｋは０又は１を表す。） As the compound containing a nitrogen atom and a carbonyl group, a compound represented by the following formula (III) is preferable.

(In the formula (III), R ³¹ is a hydrocarbyl group which may have a substituent, a hydrocarbylene group which may be bonded to R ³² and have a nitrogen atom and / or an oxygen atom as a hetero atom, or represents divalent group bonded to R ^34, R ³² are have an optionally substituted hydrocarbyl group, or a nitrogen atom and / or oxygen atom bonded to R ³¹ as a hetero atom R ³⁴ may be a hydrocarbyl group which may have a substituent, a hydrogen atom, or a divalent group bonded to R ^31. R ³³ represents a divalent group. , K represents 0 or 1.)

In the formula (III), the hydrocarbyl group which may have a substituent of R ³¹ , R ³² and R ³⁴ is a hydrocarbyl group or a substituted hydrocarbyl group. Examples of the substituted hydrocarbyl group include a substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group, and a substituted hydrocarbyl group in which the substituent is a substituted amino group. Examples of the hydrocarbyl group include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group; alkenyl groups such as vinyl group, allyl group and isopropenyl group; and aryl groups such as phenyl group. be able to. Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, and an ethoxyethyl group. Examples of the substituted hydrocarbyl group in which the substituent is a substituted amino group include 2- (N, N-dimethylamino) ethyl group, 2- (N, N-diethylamino) ethyl group, and 3- (N, N-dimethylamino) propyl. Group, (N, N-dialkylamino) alkyl group such as 3- (N, N-diethylamino) propyl group; 4- (N, N-dimethylamino) phenyl group, 3- (N, N-dimethylamino) phenyl Groups, (N, N-dialkylamino) aryl groups such as 4- (N, N-diethylamino) phenyl group, 3- (N, N-diethylamino) phenyl group; 4- (N, N-dimethylamino) methylphenyl Groups, (N, N-dialkylamino) alkylaryl groups such as 4- (N, N-dimethylamino) ethylphenyl group; 3-pyrrolidinopropyl group, 3-piperidinop group Cyclic amino group-containing alkyl groups such as a pill group and 3-imidazolylpropyl group; Cyclic amino group-containing aryl groups such as a 4-pyrrolidinophenyl group, 4-piperidinophenyl group and 4-imidazolylphenyl group; 4-pyrrolidino Examples thereof include cyclic amino group-containing alkylaryl groups such as ethylphenyl group, 4-piperidinoethylphenyl group, and 4-imidazolylethylphenyl group.

In the formula (III), the hydrocarbylene group optionally having a nitrogen atom and / or an oxygen atom to which R ³¹ and R ³² are bonded as a hetero atom is a hydrocarbylene group, or a hetero atom is a nitrogen atom and And / or a heteroatom-containing hydrocarbylene group which is an oxygen atom. The heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom and / or an oxygen atom includes a heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom, and a heteroatom-containing hydrocarbylene in which the heteroatom is an oxygen atom You can raise a group. As hydrocarbylene groups, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, pentan-2-ene-1,5-diyl group, 2,2,4-trimethylhexane-1,6-diyl An alkylene group such as a group; and an arylene group such as a 1,4-phenylene group. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom include a group represented by —CH═N—CH═CH— and a group represented by —CH═N—CH ₂ —CH ₂ —. be able to. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom include groups represented by — (CH ₂ ) _s —O— (CH ₂ ) _t — (s and t are integers of 1 or more). Can do.

In the formula (III), the divalent group in which R ³¹ and R ³⁴ are bonded and the divalent group of R ³³ include a hydrocarbylene group, a heteroatom-containing hydrocarbylene group in which the hetero atom is a nitrogen atom, hetero A heteroatom-containing hydrocarbylene group in which the atom is an oxygen atom, a group in which a hydrocarbylene group and an oxygen atom are bonded, a hydrocarbylene group and a group represented by —NR ³⁵ — (R ³⁵ is a hydrocarbyl group or a hydrogen atom And a group bonded to each other. As hydrocarbylene groups, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, pentan-2-ene-1,5-diyl group, 2,2,4-trimethylhexane-1,6-diyl An alkylene group such as a group; and an arylene group such as a 1,4-phenylene group. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom include a group represented by —CH═N—CH═CH— and a group represented by —CH═N—CH ₂ —CH ₂ —. be able to. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom include groups represented by — (CH ₂ ) _s —O— (CH ₂ ) _t — (s and t are integers of 1 or more). Can do. Examples of the group in which the hydrocarbylene group and the oxygen atom are bonded to each other include a group represented by — (CH ₂ ) _r —O— (r represents an integer of 1 or more). As a group in which a hydrocarbylene group and a group represented by —NR ³⁵ — (R ³⁵ represents a hydrocarbyl group or a hydrogen atom) are bonded, a group represented by — (CH ₂ ) _p —NR ³⁵ — ( R ³⁵ represents a hydrocarbyl group (preferably a hydrocarbyl group having 1 to 6 carbon atoms) or a hydrogen atom, and p represents an integer of 1 or more.

（式（ＩＩＩａ）中、Ｒ^３１は置換基を有してもよいヒドロカルビル基を表すか、Ｒ^３２と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ^３２は置換基を有してもよいヒドロカルビル基を表すか、Ｒ^３１と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ^３４は置換基を有してもよいヒドロカルビル基又は水素原子を表す。） Preferred examples of the compound represented by the formula (III) include a compound represented by the following formula (IIIa) in which k is 0 and R ³⁴ is a hydrocarbyl group or a hydrogen atom which may have a substituent. it can.

(In formula (IIIa), R ³¹ represents a hydrocarbyl group which may have a substituent, or a hydrocarbylene which may be bonded to R ³² and have a nitrogen atom and / or an oxygen atom as a hetero atom. R ³² represents a hydrocarbyl group which may have a substituent or a hydrocarbylene group which may combine with R ³¹ and have a nitrogen atom and / or an oxygen atom as a hetero atom. , R ³⁴ represents a hydrocarbyl group or a hydrogen atom which may have a substituent.

In the formula (IIIa), a hydrocarbyl group which may have a substituent of R ³¹ , R ³² and R ³⁴ , a nitrogen atom and / or an oxygen atom to which R ³¹ and R ³² are bonded have a hetero atom. The description and examples of the preferred hydrocarbylene group are the same as those described in the description of formula (III).

In the formula (IIIa), R ³¹ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R ³² or a hetero atom is a nitrogen atom. It is a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or an alkylene group having 3 to 10 carbon atoms bonded to R ³² , —CH═N—CH═ It is a group represented by CH— or a group represented by —CH═N—CH ₂ —CH ₂ —. More preferably, it is a C1-C6 alkyl group. Particularly preferred is a methyl group or an ethyl group.

In the formula (IIIa), R ³² is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms or a hetero atom bonded to R ³¹ is a nitrogen atom. It is a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or an alkylene group having 3 to 10 carbon atoms bonded to R ³¹ , —CH═N—CH═ It is a group represented by CH— or a group represented by —CH═N—CH ₂ —CH ₂ —. More preferably, it is a C1-C6 alkyl group. Particularly preferred is a methyl group or an ethyl group.

In the formula (IIIa), R ³⁴ is preferably a hydrocarbyl group or a hydrogen atom, more preferably a hydrocarbyl group or a hydrogen atom having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms or A hydrogen atom, particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

Among the compounds represented by the formula (IIIa), those in which R ³⁴ is a hydrocarbyl group include N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-N-ethylacetamide and the like. -Dihydrocarbylacetamide; N, N-dihydrocarbylacrylamide such as N-dimethylacrylamide, N, N-diethylacrylamide, N-methyl-N-ethylacrylamide; N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide N, N-dihydrocarbylmethacrylamide such as N-methyl-N-ethylmethacrylamide.

Among the compounds represented by the formula (IIIa), those in which R ³⁴ is a hydrogen atom include N, N-dimethylformamide, N, N-dimethylformamide, N-methyl-N-ethylformamide and the like. -Dihydrocarbylformamide can be mentioned.

（式（ＩＩＩｂ）中、Ｒ^３２は置換基を有してもよいヒドロカルビル基を表し、Ｒ^３６はヒドロカルビレン基又はヒドロカルビレン基と−ＮＲ^３５−で表される基とが結合した基を表し、Ｒ^３５はヒドロカルビル基又は水素原子を表す。） Preferred examples of the compound represented by the formula (III) include a compound represented by the following formula (IIIb) in which k is 0 and R ³⁴ is bonded to R ³¹ to form a divalent group.

(In the formula (IIIb), R ³² represents a hydrocarbyl group which may have a substituent, and R ³⁶ is a group in which a hydrocarbylene group or a hydrocarbylene group is bonded to a group represented by —NR ³⁵ —. And R ³⁵ represents a hydrocarbyl group or a hydrogen atom.)

In the formula (IIIb), the description and illustration of the hydrocarbyl group which may have a substituent of R ³² are the same as those described in the description of the formula (III).

In the formula (IIIb), the hydrocarbylene group of R ³⁶ includes trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, pentan-2-ene-1,5-diyl group, 2,2,4- Examples thereof include alkylene groups such as trimethylhexane-1,6-diyl group; and arylene groups such as 1,4-phenylene group. The group of R ³⁶ to which a hydrocarbylene group and a group represented by —NR ³⁵ — (R ³⁵ represents a hydrocarbyl group or a hydrogen atom) is bonded to — (CH ₂ ) _p —NR ³⁵ —. And a group represented by the formula (R ³⁵ represents a hydrocarbyl group or a hydrogen atom, and p represents an integer of 1 or more).

In the formula (IIIb), R ³² is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and further preferably Is an alkyl group having 1 to 6 carbon atoms or a phenyl group, particularly preferably a methyl group, an ethyl group or a phenyl group.

In the formula (IIIb), R ³⁶ is preferably a hydrocarbylene group having 1 to 10 carbon atoms, or a group represented by —NR ³⁵ — and a hydrocarbylene group having 1 to 10 carbon atoms (R ³⁵ is A hydrocarbyl group (preferably a hydrocarbyl group having 1 to 10 carbon atoms) or a hydrogen atom), and more preferably an alkylene group having 3 to 6 carbon atoms or — (CH ₂ ) _p —. A group represented by NR ³⁵ — (R ³⁵ represents a hydrocarbyl group (preferably a hydrocarbyl group having 1 to 10 carbon atoms), and p represents an integer of 1 or more (preferably an integer of 2 to 5)). And more preferably a trimethylene group, a tetramethylene group, a pentamethylene group, or a group represented by — (CH ₂ ) ₂ —N (CH ₃ ) —.

Among the compounds represented by formula (IIIb), those in which R ³⁶ is a hydrocarbylene group include N-hydrocarbyl- such as N-methyl-β-propiolactam, N-phenyl-β-propiolactam, and the like. β-propiolactam; N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-methyl-5-methyl-2- N-hydrocarbyl-2-pyrrolidone such as pyrrolidone; N-hydrocarbyl-2-piperidone such as N-methyl-2-piperidone, N-vinyl-2-piperidone, N-phenyl-2-piperidone; N-methyl-ε- N-hydrocarbyl-ε-caprolactam such as caprolactam, N-phenyl-ε-caprolactam; N-methyl-ω-laurylacta , N- vinyl -ω- can be mentioned N- hydrocarbyl -ω- Lau Lilo lactams such Lau Lilo lactams, among them N- phenyl-2-pyrrolidone, N- methyl -ε- caprolactam are preferred.

Of the compounds represented by formula (IIIb), R ³⁶ is a group in which a hydrocarbylene group and a group represented by —NR ³⁵ — are bonded (R ³⁵ represents a hydrocarbyl group or a hydrogen atom). 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-divinyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone Examples include 1,3-dihydrocarbyl-2-imidazolidinone such as non-one, among which 1,3-dimethyl-2-imidazolidinone is preferable.

（式（ＩＩＩｃ）中、Ｒ^３１は置換基を有してもよいヒドロカルビル基を表すか、あるいはＲ^３２と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ^３２は置換基を有してもよいヒドロカルビル基を表すか、あるいはＲ^３１と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ^３３はヒドロカルビレン基を表し、Ｒ^３４は置換基を有してもよいヒドロカルビル基又は水素原子を表す。） Preferable compounds represented by the formula (III) include compounds represented by the following formula (IIIc) in which k is 1 and R ³³ is a hydrocarbylene group.

(In the formula (IIIc), R ³¹ represents a hydrocarbyl group which may have a substituent, or a hydrocarbyl which may be bonded to R ³² and have a nitrogen atom and / or an oxygen atom as a hetero atom. R ³² represents a hydrocarbyl group which may have a substituent, or R ³² may be bonded to R ³¹ and may have a nitrogen atom and / or an oxygen atom as a hetero atom R ³³ represents a hydrocarbylene group, and R ³⁴ represents a hydrocarbyl group or a hydrogen atom which may have a substituent.

In the formula (IIIc), a hydrocarbyl group which may have a substituent of R ³¹ , R ³² and R ³⁴ , and a nitrogen atom and / or an oxygen atom to which R ³¹ and R ³² are bonded have a hetero atom. The description and illustration of the preferred hydrocarbylene group, the hydrocarbylene group of R ³³ are the same as those described in the description of formula (III).

In the formula (IIIc), R ³³ is preferably a hydrocarbylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms, More preferred are an alkylene group having 1 to 6 carbon atoms or a phenylene group, and particularly preferred are an ethylene group, a trimethylene group and a 1,4-phenylene group.

In the formula (IIIc), R ³⁴ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a substituted hydrocarbyl group having 1 to 10 carbon atoms in which the substituent is a dialkylamino group, more preferably 1 carbon atom. An alkyl group having 6 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, or a dialkylaminoalkyl group having 1 to 6 carbon atoms or a dialkylaminoaryl group having 6 to 10 carbon atoms, more preferably a methyl group or an ethyl group. Group, phenyl group, 3-dimethylaminoethyl group, 4-diethylaminophenyl group.

In the formula (IIIc), R ³¹ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R ³² , or a hetero atom is a nitrogen atom or an oxygen atom It is a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or a bond to R ³² An alkylene group having 3 to 10 carbon atoms, a group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, — (CH ₂ ) ₂ A group represented by —O— (CH ₂ ) ₂ —, more preferably an alkyl group having 1 to 6 carbon atoms, or an alkylene group having 3 to 6 carbon atoms bonded to R ³² , — CH = N—CH═CH— A group represented by —CH═N—CH ₂ —CH ₂ —, particularly preferably a methyl group, an ethyl group, or a bond with R ³² to form a tetramethylene group, a hexamethylene group, —CH. = N-CH = CH-.

In the formula (IIIc), R ³² is preferably a hydrocarbyl group having 1 to 10 carbon atoms, a hydrocarbylene group having 3 to 10 carbon atoms bonded to R ³¹ , or a hetero atom having a nitrogen atom or oxygen It is a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or a bond with R ³¹ An alkylene group having 3 to 10 carbon atoms, a group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, — (CH ₂ ) ₂ A group represented by —O— (CH ₂ ) ₂ —, more preferably an alkyl group having 1 to 6 carbon atoms, or an alkylene group having 3 to 6 carbon atoms bonded to R ³¹ ; CH = N—CH═CH— A group represented by —CH═N—CH ₂ —CH ₂ —, particularly preferably a methyl group, an ethyl group, or a bond with R ³¹ to form a tetramethylene group, a hexamethylene group, —CH. = N-CH = CH-.

Among the compounds represented by the formula (IIIc), as the compound in which R ³⁴ is a hydrocarbyl group,
4-N, N-dihydrocarbylaminoacetophenone such as 4- (N, N-dimethylamino) acetophenone, 4-N-methyl-N-ethylaminoacetophenone, 4-N, N-diethylaminoacetophenone; 4 ′-(imidazole Examples include 4-cyclic aminoacetophenone compounds such as -1-yl) acetophenone and 4-pyrazolylacetophenone, among which 4-cyclic aminoacetophenone compounds are preferable, and 4 ′-(imidazol-1-yl) acetophenone is more preferable. .

Among the compounds represented by the formula (IIIc), as the compound in which R ³⁴ is a substituted hydrocarbyl group,
Bis (dihydrocarbylaminoalkyl) ketones such as 1,7-bis (methylethylamino) -4-heptanone, 1,3-bis (diphenylamino) -2-propanone; 4-N, N-dimethylaminobenzophenone, 4 4- (dihydrocarbylamino) benzophenone such as -N, N-di-t-butylaminobenzophenone, 4-N, N-diphenylaminobenzophenone; 4,4'-bis (dimethylamino) benzophenone, 4,4'- 4,4'-bis (dihydrocarbylamino) benzophenone such as bis (diethylamino) benzophenone and 4,4'-bis (diphenylamino) benzophenone can be mentioned, among which 4,4'-bis (dihydrocarbylamino) benzophenone 4,4′-bis (diethylamino) benzofe Emissions is more preferable.

（式（ＩＩＩｄ）中、Ｒ^３１は置換基を有してもよいヒドロカルビル基を表すか、あるいはＲ^３２と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ^３２は置換基を有してもよいヒドロカルビル基を表すか、あるいはＲ^３１と結合して窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基を表し、Ｒ^３７はヒドロカルビレン基を表し、Ａは酸素原子又は−ＮＲ^３５−を表し、Ｒ^３５はヒドロカルビル基又は水素原子を表し、Ｒ^３４は置換基を有してもよいヒドロカルビル基又は水素原子を表す。） As a preferable compound represented by the formula (III), k is 1, and R ³³ is a group in which a hydrocarbylene group and an oxygen atom are bonded, or a group represented by a hydrocarbylene group and —NR ³⁵ — ( R ³⁵ may be a compound represented by the following formula (IIId), which is a group bonded to a hydrocarbyl group or a hydrogen atom.

(In the formula (IIId), R ³¹ represents a hydrocarbyl group which may have a substituent, or a hydrocarbyl which may be bonded to R ³² and have a nitrogen atom and / or an oxygen atom as a hetero atom. R ³² represents a hydrocarbyl group which may have a substituent, or R ³² may be bonded to R ³¹ and may have a nitrogen atom and / or an oxygen atom as a hetero atom R ³⁷ represents a hydrocarbylene group, A represents an oxygen atom or —NR ³⁵ —, R ³⁵ represents a hydrocarbyl group or a hydrogen atom, and R ³⁴ represents an optionally substituted hydrocarbyl group or Represents a hydrogen atom.)

In the formula (IIId), a hydrocarbyl group which may have a substituent of R ³¹ , R ³² and R ³⁴ , a nitrogen atom and / or an oxygen atom to which R ³¹ and R ³² are bonded have a hetero atom. The description and examples of the preferred hydrocarbylene group are the same as those described in the description of formula (III). The hydrocarbyl group of R ³⁵ is the same as that described for the hydrocarbyl group of R ³¹ , R ³² , and R ³⁴ .

In formula (IIId), A is preferably an oxygen atom or a group represented by —NR ³⁵ — (R ³⁵ is a hydrocarbyl group (preferably a hydrocarbyl group having 1 to 5 carbon atoms) or a hydrogen atom). , More preferably an oxygen atom or a group represented by —NH—, and still more preferably a group represented by —NH—.

In formula (IIId), the hydrocarbylene group of R ³⁷ is trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, pentan-2-ene-1,5-diyl group, 2,2,4- Examples thereof include alkylene groups such as trimethylhexane-1,6-diyl group; and arylene groups such as 1,4-phenylene group.

In the formula (IIId), R ³⁴ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, and further preferably a vinyl group.

In the formula (IIId), R ³⁷ is preferably a hydrocarbylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an ethylene group or a trimethylene group. Particularly preferred is a trimethylene group.

In the formula (IIId), R ³¹ is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R ³² , or a hetero atom is a nitrogen atom or oxygen It is a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or a bond to R ³² An alkylene group having 3 to 10 carbon atoms, a group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, — (CH ₂ ) ₂ A group represented by —O— (CH ₂ ) ₂ —, more preferably an alkyl group having 1 to 6 carbon atoms, or an alkylene group having 3 to 6 carbon atoms bonded to R ³² , — CH = N—CH═CH— A group represented by —CH═N—CH ₂ —CH ₂ —, particularly preferably a methyl group, an ethyl group, or a bond with R ³² to form a tetramethylene group, a hexamethylene group, —CH. = N-CH = CH-.

In the formula (IIId), R ³² is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R ³¹ , or a hetero atom is a nitrogen atom or an oxygen atom. It is a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or a bond with R ³¹ An alkylene group having 3 to 10 carbon atoms, a group represented by —CH═N—CH═CH—, a group represented by —CH═N—CH ₂ —CH ₂ —, — (CH ₂ ) ₂ A group represented by —O— (CH ₂ ) ₂ —, more preferably an alkyl group having 1 to 6 carbon atoms, or an alkylene group having 3 to 6 carbon atoms bonded to R ³¹ ; CH = N—CH═CH— A group represented by —CH═N—CH ₂ —CH ₂ —, particularly preferably a methyl group, an ethyl group, or a bond with R ³¹ to form a tetramethylene group, a hexamethylene group, —CH. = N-CH = CH-.

Among the compounds represented by the formula (IIId), as the compound in which A is an oxygen atom,
2-N, N-dimethylaminoethyl acrylate, 2-N, N-dihydrocarbylaminoethyl acrylate such as 2-N, N-diethylaminoethyl acrylate; 3-N, such as 3-N, N-dimethylaminopropyl acrylate N-dihydrocarbylaminopropyl acrylate; 2-N, N-dihydrocarbylaminoethyl methacrylate such as 2-N, N-dimethylaminoethyl methacrylate and 2-N, N-diethylaminoethyl methacrylate; 3-N, N-dimethylamino 3-N, N-dihydrocarbylaminopropyl methacrylate such as propyl methacrylate can be mentioned, 3-N, N-dihydrocarbylaminopropyl acrylate is preferred, and 3-N, N-dimethylaminopropyl acrylate is more preferred There.

Among the compounds represented by the formula (IIId), as the compound wherein A is a group represented by —NR ³⁵ — (R ³⁵ represents a hydrocarbyl group or a hydrogen atom),
N, N-dihydrocarbylaminoethylacrylamide such as N, N-dimethylaminoethylacrylamide, N, N-diethylaminoethylacrylamide; N, N- such as N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide Dihydrocarbylaminopropylacrylamide; N, N-dihydrocarbylaminobutylacrylamide such as N, N-dimethylaminobutylacrylamide, N, N-diethylaminobutylacrylamide; N, N-dimethylaminoethylmethacrylamide, N, N-diethylaminoethyl N, N-dihydrocarbylaminoethyl methacrylamide such as methacrylamide; N, N-dimethylaminopropyl methacrylamide, N, N-diethylaminopropyl N, N-dihydrocarbylaminopropyl methacrylamide such as tacrylamide; N, N-dihydrocarbylaminobutyl methacrylamide such as N, N-dimethylaminobutyl methacrylamide and N, N-diethylaminobutyl methacrylamide; N, N-dihydrocarbylaminopropylacrylamide is preferred, and N, N-dimethylaminopropylacrylamide is more preferred.

A preferred compound represented by the formula (III) is a compound represented by the formula (IIId), among which N, N-dihydrocarbylaminopropylacrylamide is particularly preferred, and N, N-dimethylaminopropylacrylamide is most preferred. .

In addition to the above, a compound containing an alkoxysilyl group can also be mentioned as a preferable compound containing a nitrogen atom and / or a silicon atom.

（式（ＩＶ）中、Ｒ^４１はヒドロカルビル基を表し、Ｒ^４２、Ｒ^４３はヒドロカルビル基又はヒドロカルビルオキシ基を表し、Ｒ^４４は置換基を有してもよいヒドロカルビル基又はトリヒドロカルビルシリル基を表すか、あるいはＲ^４５と結合して、ケイ素原子、窒素原子及び酸素原子からなる原子群より選択される少なくとも一種の原子をヘテロ原子として有してもよいヒドロカルビレン基を表し、Ｒ^４５は置換基を有してもよいヒドロカルビル基又はトリヒドロカルビルシリル基を表すか、あるいはＲ^４４と結合して、ケイ素原子、窒素原子及び酸素原子からなる原子群より選択される少なくとも一種の原子をヘテロ原子として有してもよいヒドロカルビレン基を表し、ｊは１〜５の整数を表す。） As the compound containing an alkoxysilyl group, a compound containing a nitrogen atom and an alkoxysilyl group is preferable, and a compound represented by the following formula (IV) is more preferable.

(In formula (IV), R ⁴¹ represents a hydrocarbyl group, R ⁴² and R ⁴³ represent a hydrocarbyl group or a hydrocarbyloxy group, and R ⁴⁴ represents a hydrocarbyl group or a trihydrocarbylsilyl group which may have a substituent. carded or combined with R ^45,, represents a silicon atom, a nitrogen atom and hydrocarbylene group optionally having at least one atom as a hetero atom selected from the group of atoms consisting of oxygen atoms, R ⁴⁵ is substituted represent a hydrocarbyl group or a trihydrocarbylsilyl group which may have a group, or combined with R ^44, at least one atom selected from the group of atoms of silicon atoms, nitrogen atoms and oxygen atoms as a hetero atom (It represents a hydrocarbylene group that may be present, and j represents an integer of 1 to 5.)

In the above formula (IV), the hydrocarbyl group which may have a substituent is a hydrocarbyl group or a substituted hydrocarbyl group. Examples of hydrocarbyl groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, and n-butyl groups; alkenyl groups such as vinyl, allyl, and isopropenyl groups; and aryl groups such as phenyl groups. It is preferably an alkyl group, more preferably a methyl group or an ethyl group. Examples of the substituted hydrocarbyl group include oxacycloalkyl groups such as an oxiranyl group and a tetrahydrofuranyl group, and a tetrahydrofuranyl group is preferable.

In this specification, the oxacycloalkyl group represents a group in which CH ₂ on the alicyclic ring of the cycloalkyl group is replaced with an oxygen atom.

Hydrocarbyloxy groups include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy; aryloxy such as phenoxy and benzyloxy Group, and preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.

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

The hydrocarbylene group which may have at least one atom selected from the atomic group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a hetero atom is a hydrocarbylene group, or the hetero atom is a silicon atom or a nitrogen atom And a heteroatom-containing hydrocarbylene group that is at least one atom selected from the group consisting of oxygen atoms. As the heteroatom-containing hydrocarbylene group in which the heteroatom is at least one atom selected from the group consisting of a silicon atom, a nitrogen atom and an oxygen atom, the heteroatom-containing hydrocarbylene group in which the heteroatom is a silicon atom, Examples thereof include a heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom and a heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom. Examples of the hydrocarbylene group include a tetramethylene group, a pentamethylene group, a hexamethylene group, a pentan-2-ene-1,5-diyl group, and a 2,2,4-trimethylhexane-1,6-diyl group. An alkylene group can be mentioned, Among these, an alkylene group having 4 to 7 carbon atoms is preferable, and a pentamethylene group or a hexamethylene group is particularly preferable. Examples of the heteroatom-containing hydrocarbylene group in which the heteroatom is a silicon atom include a group represented by —Si (CH ₃ ) ₂ —CH ₂ —CH ₂ —Si (CH ₃ ) ₂ —. The heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom includes a group represented by —CH═N—CH═CH— or a group represented by —CH═N—CH ₂ —CH ₂ —. I can give you. Examples include a heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom, and a group represented by —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —.

In the above formula (IV), R ⁴¹ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. R ⁴² and R ⁴³ are preferably a hydrocarbyloxy group, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group. R ⁴⁴ and R ⁴⁵ are preferably hydrocarbyl groups, more preferably alkyl groups having 1 to 4 carbon atoms, and still more preferably methyl groups or ethyl groups. J is preferably an integer of 2 to 4.

Examples of the compound represented by the formula (IV) include 3-dimethylaminopropyltriethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 3-diethylaminopropyltriethoxysilane, 3-diethylaminopropyltrimethoxysilane, and 3-dimethyl. [(Dialkylamino) alkyl] alkoxysilane compounds such as aminopropylmethyldiethoxysilane, 2-dimethylaminoethyltriethoxysilane, 2-dimethylaminoethyltrimethoxysilane; hexamethyleneiminomethyltrimethoxysilane, 3-hexamethyleneimino Cyclic amino such as propyltriethoxysilane, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) -4,5-imidazole [Di (tetrahydrofuranyl) amino] alkylalkoxysilane compounds such as 3- [di (tetrahydrofuranyl) amino] propyltrimethoxysilane and 3- [di (tetrahydrofuranyl) amino] propyltriethoxysilane; N N, N-bis (trialkylsilyl) aminoalkylalkoxysilane compounds such as N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, Of these, [(dialkylamino) alkyl] alkoxysilane compounds are preferred, and 3-dimethylaminopropyltriethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 3-diethylaminopropylto Silane, 3-diethylaminopropyl trimethoxysilane is more preferred.

As a compound containing an alkoxysilyl group, in addition to the compound containing a nitrogen atom and an alkoxysilyl group,
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane; trialkoxyhydrocarbylsilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane; trimethoxychlorosilane, Trialkoxyhalosilanes such as triethoxychlorosilane and tri-n-propoxychlorosilane; dialkoxydihydrocarbylsilanes such as dimethoxydimethylsilane, diethoxydimethylsilane and dimethoxydiethylsilane; dimethoxydichlorosilane, diethoxydichlorosilane and di-n- Dialkoxydihalosilanes such as propoxydichlorosilane; monoalkoxytrihydrocarbylsilanes such as methoxytrimethylsilane Monoalkoxytrihalosilanes such as methoxytrichlorosilane and ethoxytrichlorosilane; 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl) methyldimethoxysilane, 3-glycid (Glycidoxyalkyl) alkoxysilane compounds such as xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane; 2- (3,4-epoxycyclohexyl) ethyl (3,4-epoxycyclohexyl) alkyl alcohols such as trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane Sisilane compounds; alkoxysilylalkyl succinic anhydrides such as 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride; 3-methacryloyloxypropyl trimethoxysilane, 3-methacryloyloxypropyl And (methacryloyloxyalkyl) alkoxysilane compounds such as triethoxysilane.

Moreover, the compound containing an alkoxysilyl group may contain a nitrogen atom and a carbonyl group. Examples of the compound containing an alkoxysilyl group and containing a nitrogen atom and a carbonyl group include tris [3- (trimethoxysilyl) propyl] isocyanurate, tris [3- (triethoxysilyl) propyl] isocyanurate, tris [3 Examples include tris [(alkoxysilyl) alkyl] isocyanurate compounds such as-(tripropoxysilyl) propyl] isocyanurate and tris [3- (tributoxysilyl) propyl] isocyanurate, among which tris [3- (tri Methoxysilyl) propyl] isocyanurate is preferred.

In the method for producing the conjugated diene polymer, a coupling agent may be added to the hydrocarbon solution of the conjugated diene polymer from the start of polymerization of the monomer to the recovery of the polymer described later. Examples of the coupling agent include compounds represented by the following formula (V).
R ⁵¹ _a ML _4-a (V)
(In the formula (V), R ⁵¹ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aryl group, M represents a silicon atom or a tin atom, L represents a halogen atom or a hydrocarbyloxy group, and a represents 0 to 0. Represents an integer of 2.)

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

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

In the method for producing the conjugated diene polymer, an unreacted active terminal may be treated with an alcohol such as methanol or isopropyl alcohol before recovering the polymer described later.

As a method for recovering the conjugated diene polymer from the conjugated diene polymer hydrocarbon solution, a known method can be used. For example, (A) a method of adding a coagulant to the conjugated diene polymer hydrocarbon solution. (B) A method of adding steam to the hydrocarbon solution of the conjugated diene polymer (steam stripping treatment) can be mentioned. The recovered conjugated diene polymer may be dried by a known dryer such as a band dryer or an extrusion dryer.

In the conjugated diene polymer, the content of the structural unit derived from the polymerization initiator represented by the formula (I) is from the viewpoint of improving the fuel efficiency, breaking strength and processability in a balanced manner, Preferably, it is 0.0001 mmol / g polymer or more, more preferably 0.001 mmol / g polymer or more, preferably 0.15 mmol / g polymer or less, more preferably 0.1 mmol / g polymer or less. is there.

In the conjugated diene polymer, the content of the structural unit derived from the silicon-containing vinyl compound is preferably 0.01 mmol / per polymer unit mass from the viewpoint of improving the fuel efficiency, breaking strength and processability in a balanced manner. g polymer or more, more preferably 0.02 mmol / g polymer or more, preferably 0.4 mmol / g polymer or less, more preferably 0.2 mmol / g polymer or less.

（式（ＩＩｂ）中、ｍ、Ｒ^２１、Ｘ^１、Ｘ^２及びＸ^３は、式（ＩＩ）におけるものと同一である。） From the viewpoint of improving the fuel efficiency, breaking strength and processability in a balanced manner, the conjugated diene polymer preferably has a structural unit derived from the compound represented by the formula (II). In addition, the structural unit derived from the compound represented by the formula (II) in the conjugated diene polymer means a structural unit represented by the following formula (IIb).

(In the formula (IIb), m, R ²¹ , X ¹ , X ² and X ³ are the same as those in the formula (II).)

In the conjugated diene polymer according to the present invention, in the structural unit derived from the compound represented by formula (II) in the conjugated diene polymer, at least one of X ¹ , X ² and X ³ is substituted with a hydroxyl group. More preferably, two or more of them are substituted with hydroxyl groups, and more preferably, two are substituted with hydroxyl groups. Thereby, the improvement effect of low-fuel-consumption property, breaking strength, and workability can be heightened. The method for substituting X ¹ , X ² and X ³ with a hydroxyl group is not particularly limited, and an example is a method by steam stripping treatment.

The conjugated diene polymer preferably has a structural unit (aromatic vinyl unit) derived from an aromatic vinyl compound from the viewpoint of improving fuel economy, breaking strength and processability in a balanced manner. When the conjugated diene polymer has an aromatic vinyl unit, the content of the aromatic vinyl unit in the conjugated diene polymer is such that the structural unit derived from the conjugated diene compound (conjugated diene unit) and the aromatic vinyl unit. And the total amount is preferably 10% by mass or more (content of the conjugated diene unit content compound is 90% by mass or less), more preferably 15% by mass or more (content of the conjugated diene unit is 85% by mass or less). Further, from the viewpoint of low fuel consumption, the content of the aromatic vinyl unit is preferably 50% by mass or less (the content of the conjugated diene unit is 50% by mass or more), more preferably 45% by mass or less (conjugated diene). The unit content is 55% by mass or more).

When the conjugated diene polymer has a structural unit based on an aromatic vinyl compound, the vinyl bond content (vinyl content) of the conjugated diene polymer is low fuel consumption, with the conjugated diene unit content being 100 mol%. From this viewpoint, it is preferably 80 mol% or less, more preferably 70 mol% or less.

In particular, from the viewpoint of improving the breaking strength, the conjugated diene polymer preferably does not have an aromatic vinyl compound structural unit. In this case, the vinyl bond content (vinyl content) of the conjugated diene polymer. The conjugated diene unit content is 100 mol%, preferably 20 mol% or less, more preferably 15 mol% or less.

In addition, the vinyl bond amount of the said conjugated diene type polymer can be measured by the method as described in the Example mentioned later.

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

The conjugated diene polymer can be used in the rubber composition of the present invention as a rubber component.

The content of the conjugated diene polymer in 100% by mass of the rubber component is 25% by mass or more, preferably 30% by mass or more. If the amount is less than 25% by mass, the effect of improving fuel economy tends to be difficult to obtain. The content of the conjugated diene polymer is 50% by mass or less, preferably 45% by mass or less. If it exceeds 50 mass%, the fracture strength tends to decrease and the cost tends to increase.

The conjugated diene polymer is preferably used in combination with other rubber components. As another rubber component, a polyisoprene rubber can be preferably used. By blending the polyisoprene-based rubber, the breaking strength is improved, and the rubber is better packed at the time of kneading, so that productivity can be improved.

Examples of the polyisoprene rubber include natural rubber (NR) and polyisoprene rubber (IR). NR is not particularly limited. For example, SIR20, RSS # 3, TSR20, deproteinized natural rubber (DPNR), high purity natural rubber (HPNR), epoxidized natural rubber (ENR), etc., which are common in the tire industry Can be used. Similarly, IR that is common in the tire industry can be used.

When the rubber composition of the present invention contains a polyisoprene rubber, the content of the polyisoprene rubber in 100% by mass of the rubber component is preferably 20% by mass or more, more preferably 50% by mass or more. If it is less than 20% by mass, the effect of improving the breaking strength may not be sufficiently obtained. Further, the content of the polyisoprene rubber is preferably 75% by mass or less, more preferably 70% by mass or less. When the content of the polyisoprene rubber exceeds 75% by mass, processability tends to deteriorate.

Examples of the rubber component that can be used in addition to the polyisoprene rubber include conventional styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), butadiene-isoprene copolymer rubber, and butyl rubber. Moreover, an ethylene-propylene copolymer, an ethylene-octene copolymer, etc. can be mentioned. Two or more of these rubber components may be used in combination. Among them, from the viewpoint that fuel economy, rubber strength, adhesiveness and processability can be improved in a balanced manner, those containing 50% by mass or more of a structural unit derived from a conjugated diene compound can be preferably used. , BR and SBR are preferable.

The BR is not particularly limited. For example, BR1220 manufactured by Nippon Zeon Co., Ltd., BR130B manufactured by Ube Industries, Ltd. Commonly used in the tire industry such as BR containing syndiotactic polybutadiene crystals can be used. Similarly, the SBR is not particularly limited, and, for example, those commonly used in the tire industry such as Nipol NS116R manufactured by Nippon Zeon Co., Ltd. can be used.

The rubber composition of the present invention contains silica. The silica is not particularly limited, and examples thereof include dry process silica (anhydrous silica), wet process silica (hydrous silica), and wet process silica is preferable because of its large number of silanol groups.

The nitrogen adsorption specific surface area (N ₂ SA) of silica is preferably 40 m ² / g or more, more preferably 50 m ² / g or more. If it is less than 40 m ² / g, the reinforcing effect is small, and the fracture strength tends to decrease. The _N 2 SA of the silica is preferably 400 meters ² / g or less, more preferably 360 m ² / g, more preferably not more than 300m ² / g. When it exceeds 400 m < ² > / g, it will become difficult to disperse | distribute a silica and there exists a tendency for low-fuel-consumption property and workability to deteriorate.
The _N 2 SA of silica is a value determined by the BET method in accordance with ASTM D3037-93.

The content of silica (when two or more types of silica are used, the total amount) is 40 parts by mass or more, preferably 45 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 40 parts by mass, the effect of blending silica cannot be sufficiently obtained, and the fracture strength tends to be lowered. The silica content is 80 parts by mass or less, preferably 75 parts by mass or less. When it exceeds 80 mass parts, there exists a tendency for workability to deteriorate.

Silica one kind may be used alone, it is preferable to use a combination of two or _{more, N} 2 SA is ^{40 m} 2 / g or more, 120 m and ² / g less than the silica _{(1), N} 2 SA is More preferably, 120 m ² / g or more of silica (2) is used in combination. By blending silica (1) and (2) together with the conjugated diene polymer, silica (1) and (2) can be dispersed well, and the improvement effect of each performance can be enhanced synergistically. It can greatly improve fuel efficiency and breaking strength. Moreover, the improvement effect of each performance can further be heightened by using silica (1) and (2) and the silane coupling agent which has a mercapto group together.

Silica (1) is not particularly limited, and for example, Ultrazil 360 manufactured by Degussa, Z40 manufactured by Rhodia, RP80 manufactured by Rhodia, and the like can be obtained. Similarly, the silica (2) is not particularly limited, and can be obtained as, for example, Zeosyl 1205MP manufactured by Rhodia. These may be used alone or in combination of two or more.

In silica (1) and (2), N ₂ SA preferably satisfies the following formula.
It is preferable to satisfy the relation of ≧ 1.4 _(N 2 SA of the silica (1)) (silica _(N 2 SA of 2)) /, of (Silica _(N 2 SA of 2)) / (silica (1) More preferably, the relationship of N ₂ SA) ≧ 2.0 is satisfied. If it is less than 1.4, the difference in particle diameter between silica (1) and (2) is small, and the dispersion improving effect by blending two types of silica tends to be insufficient.

N ₂ SA of silica (1) is 40 m ² / g or more, preferably 50 m ² / g or more. If it is less than 40 m ² / g, sufficient reinforcing properties cannot be obtained, and the fracture strength may be reduced. Also, _N 2 SA of the silica (1) is less than 120 m ² / g, preferably 100 m ² / g, more preferably at most ^{80 m} 2 / g. If it is 120 m ² / g or more, there is a possibility that the effect of the combined use of silica (1) and (2) cannot be obtained sufficiently.

N ₂ SA of silica (2) is 120 m ² / g or more, preferably 150 m ² / g or more. If it is less than 120 m ² / g, the effect of the combined use of silica (1) and (2) may not be sufficiently obtained. Also, _N 2 SA of the silica (2) is preferably 250 meters ² / g, more preferably at most 220 m ² / g. When it exceeds 250 m ² / g, fuel economy and processability tend to deteriorate.

The contents of silica (1) and (2) preferably satisfy the following formula.
(Content of silica (1)) × 0.06 ≦ (content of silica (2)) ≦ (content of silica (1)) × 15
If the content of silica (2) is less than 0.06 times the content of silica (1), sufficient rubber strength tends not to be obtained. Moreover, when content of a silica (2) exceeds 15 times of content of a silica (1), there exists a tendency for rolling resistance to increase. The content of silica (2) is more preferably 0.3 times or more and more preferably 0.5 times or more of the content of silica (1). Further, the content of silica (2) is more preferably 7 times or less, and further preferably 4 times or less, of the content of silica (1).

The content of silica (1) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 5 parts by mass, the fuel economy may not be sufficiently improved. Further, the content of silica (1) is preferably 70 parts by mass or less, more preferably 65 parts by mass or less. If it exceeds 70 parts by mass, the fuel efficiency is good, but the breaking strength tends to decrease.

The content of silica (2) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 5 parts by mass, sufficient fracture strength may not be obtained. Further, the content of silica (2) is preferably 70 parts by mass or less, more preferably 65 parts by mass or less. When it exceeds 70 mass parts, although fracture strength is favorable, there exists a tendency for workability to deteriorate.

The total content of silica (1) and (2) is preferably 40 parts by mass or more, more preferably 45 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 40 parts by mass, a sufficient reinforcing effect due to the blend of silica (1) and (2) may not be obtained. The total content of silica (1) and (2) is preferably 80 parts by mass or less, more preferably 75 parts by mass or less. When the amount exceeds 80 parts by mass, it is difficult to uniformly disperse silica in the rubber composition, and not only the processability of the rubber composition is deteriorated but also rolling resistance may be increased.

The rubber composition of the present invention contains a silane coupling agent having a mercapto group. By blending a silane coupling agent having a mercapto group with the conjugated diene polymer, silica can be dispersed well and each performance can be improved synergistically. Moreover, the improvement effect of each performance can further be heightened by using together the above-mentioned silica (1) and (2) and the specific liquid resin mentioned later with the silane coupling agent which has a mercapto group.

（式（１）中、Ｒ^１０１〜Ｒ^１０３は、分岐若しくは非分岐の炭素数１〜１２のアルキル基、分岐若しくは非分岐の炭素数１〜１２のアルコキシ基、又は−Ｏ−（Ｒ^１１１−Ｏ）_ｚ−Ｒ^１１２（ｚ個のＲ^１１１は、分岐若しくは非分岐の炭素数１〜３０の２価の炭化水素基を表す。ｚ個のＲ^１１１はそれぞれ同一でも異なっていてもよい。Ｒ^１１２は、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、炭素数６〜３０のアリール基、又は炭素数７〜３０のアラルキル基を表す。ｚは１〜３０の整数を表す。）で表される基を表す。Ｒ^１０１〜Ｒ^１０３はそれぞれ同一でも異なっていてもよい。Ｒ^１０４は、分岐若しくは非分岐の炭素数１〜６のアルキレン基を表す。）

（式（２）及び（３）中、Ｒ^２０１は水素、ハロゲン、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、分岐若しくは非分岐の炭素数２〜３０のアルキニル基、又は該アルキル基の末端の水素が水酸基若しくはカルボキシル基で置換されたものを表す。Ｒ^２０２は分岐若しくは非分岐の炭素数１〜３０のアルキレン基、分岐若しくは非分岐の炭素数２〜３０のアルケニレン基、又は分岐若しくは非分岐の炭素数２〜３０のアルキニレン基を表す。Ｒ^２０１とＲ^２０２とで環構造を形成してもよい。） Examples of the silane coupling agent having a mercapto group include a compound represented by the following formula (1) and / or a binding unit A represented by the following formula (2) and a binding unit B represented by the following formula (3). The compound containing can be used conveniently.

(In the formula (1), R ^{101 to} R ¹⁰³ are each a branched or unbranched C 1-12 alkyl group, a branched or unbranched C 1-12 alkoxy group, or —O— (R ¹¹¹ — O) _z- R ¹¹² (z R ¹¹¹ represents a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms. The z R ^{111 s} may be the same as or different from each other. ¹¹² represents a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. Z represents an integer of 1 to 30.) R ^{101 to} R ¹⁰³ may be the same as or different from each other, and R ¹⁰⁴ has 1 to 6 carbon atoms which are branched or unbranched. Represents an alkylene group of

(In the formulas (2) and (3), R ²⁰¹ is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, branched or unbranched alkenyl group having 2 to 30 carbon atoms, branched or unbranched. Or an alkyl group substituted with a hydroxyl group or a carboxyl group, and R ²⁰² represents a branched or unbranched C 1-30 alkylene group, branched or It represents an unbranched C2-C30 alkenylene group or a branched or unbranched C2-C30 alkynylene group, and R ²⁰¹ and R ²⁰² may form a ring structure.)

Hereinafter, the compound represented by Formula (1) is demonstrated.

By using the compound represented by Formula (1), silica is dispersed well, and the effects of the present invention are obtained well. In particular, the fuel efficiency can be greatly improved.

R ^{101 to} R ¹⁰³ are each a branched or unbranched alkyl group having 1 to 12 carbon atoms, a branched or unbranched alkoxy group having 1 to 12 carbon atoms, or —O— (R ¹¹¹ —O) _z —R ¹¹² . Represents the group represented. From the viewpoint that the effect of the present invention can be obtained satisfactorily, at least one of R ^{101 to} R ¹⁰³ is preferably a group represented by —O— (R ¹¹¹ —O) _z —R ¹¹² , and two of them are — More preferably, it is a group represented by O— (R ¹¹¹ —O) _z —R ¹¹² , and one is a branched or unbranched C 1-12 alkoxy group.

Examples of the branched or unbranched alkyl group having 1 to 12 carbon atoms (preferably 1 to 5 carbon atoms) represented by R ^{101 to} R ¹⁰³ include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group and the like.

Examples of the branched or unbranched alkoxy group having 1 to 12 carbon atoms (preferably 1 to 5 carbon atoms) of R ^{101 to} R ¹⁰³ include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, n- Examples include butoxy, iso-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy and the like.

In —O— (R ¹¹¹ —O) _z —R ¹¹² of R ^{101 to} R ¹⁰³ , R ¹¹¹ represents a branched or unbranched carbon number of 1 to 30 (preferably having 1 to 15 carbon atoms, more preferably 1 carbon number). To 3) a divalent hydrocarbon group.
Examples of the hydrocarbon group include a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenylene group having 2 to 30 carbon atoms, and a branched or unbranched alkynylene group having 2 to 30 carbon atoms. And an arylene group having 6 to 30 carbon atoms. Of these, a branched or unbranched alkylene group having 1 to 30 carbon atoms is preferable.

Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms (preferably 1 to 15 carbon atoms, more preferably 1 to 3 carbon atoms) of R ¹¹¹ include, for example, a methylene group, an ethylene group, a propylene group, and a butylene group. Pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like.

Examples of the branched or unbranched carbon atoms 2-30 alkenylene group (preferably 2 to 15 carbon atoms, more preferably 2 to 3 carbon atoms) of R ^111, for example, vinylene group, propenylene group, 2-propenylene Group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group, 1-hexenylene group, 2-hexenylene group, 1-octenylene group and the like.

Examples of the branched or unbranched carbon atoms 2-30 alkynylene group (preferably 2 to 15 carbon atoms, more preferably 2 to 3 carbon atoms) of R ^111, for example, ethynylene group, propynylene group, butynylene group, pentynylene group Hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecynylene group, dodecynylene group and the like.

Examples of the arylene group having 6 to 30 carbon atoms (preferably 6 to 15 carbon atoms) of R ¹¹¹ include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.

z represents an integer of 1 to 30 (preferably 2 to 20, more preferably 3 to 7, further preferably 5 to 6).

R ¹¹² represents a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. Represent. Of these, a branched or unbranched alkyl group having 1 to 30 carbon atoms is preferable.

Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms (preferably 3 to 25 carbon atoms, more preferably 10 to 15 carbon atoms) of R ¹¹² include, for example, a methyl group, an ethyl group, an n-propyl group, Isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group and the like.

Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms (preferably 3 to 25 carbon atoms, more preferably 10 to 15 carbon atoms) for R ¹¹² include, for example, a vinyl group, a 1-propenyl group, and 2-propenyl. Group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group Group, pentadecenyl group, octadecenyl group and the like.

Examples of the aryl group having 6 to 30 carbon atoms (preferably 10 to 20 carbon atoms) of R ¹¹² include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms (preferably 10 to 20 carbon atoms) of R ¹¹² include a benzyl group and a phenethyl group.

Specific examples of the group represented by —O— (R ¹¹¹ —O) _z —R ¹¹² include, for example, —O— (C ₂ H ₄ —O) ₅ —C ₁₁ H ₂₃ , —O— (C _{2 H 4 -O) 5 -C 12 H} 25, -O- (C 2 H 4 -O) 5 -C 13 H 27, -O- (C 2 H 4 -O) 5 -C 14 H 29, -O _{- (C 2 H 4 -O)} 5 -C 15 H 31, -O- (C 2 H 4 -O) 3 -C 13 H 27, -O- (C 2 H 4 -O) 4 -C 13 H _{27, -O- (C 2 H 4} -O) 6 -C 13 H 27, such as _{-O- (C 2 H 4 -O)} 7 -C 13 H 27 and the like. Among _{these, -O- (C 2 H 4 -O} ) 5 -C 11 H 23, -O- (C 2 H 4 -O) 5 -C 13 H 27, -O- (C 2 H 4 -O) 5 _{-C 15 H 31, -O- (C} 2 H 4 -O) 6 -C 13 H 27 are preferable.

Examples of the branched or unbranched alkylene group having 1 to 6 carbon atoms (preferably 1 to 5 carbon atoms) of R ¹⁰⁴ include the same groups as the branched or unbranched alkylene group having 1 to 30 carbon atoms of R ^111. Can give.

Examples of the compound represented by the formula (1) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and the following formula: The compound represented by the following formula (Si363 manufactured by EVONIK-DEGUSSA) and the like can be used, and a compound represented by the following formula can be preferably used. These may be used alone or in combination of two or more.

Next, the compound containing the bond unit A represented by the formula (2) and the bond unit B represented by the formula (3) will be described.

The compound containing the bond unit A represented by the formula (2) and the bond unit B represented by the formula (3) is more viscous during processing than a polysulfide silane such as bis- (3-triethoxysilylpropyl) tetrasulfide. The rise is suppressed. This is presumably because the increase in Mooney viscosity is small because the sulfide portion of the bond unit A is a C—S—C bond and is thermally stable compared to tetrasulfide and disulfide.

Moreover, the shortening of the scorch time is suppressed as compared with mercaptosilane such as 3-mercaptopropyltrimethoxysilane. This is because the bonding unit B has a structure of mercaptosilane, but the —C ₇ H ₁₅ part of the bonding unit A covers the —SH group of the bonding unit B, so that it does not easily react with the polymer and scorch is not easily generated. This is probably because of this.

In the silane coupling agent having the above structure, the content of the bond unit A is preferably 30 from the viewpoint that the effect of suppressing the increase in viscosity during processing and the effect of suppressing the shortening of the scorch time can be enhanced. It is at least mol%, more preferably at least 50 mol%, preferably at most 99 mol%, more preferably at most 90 mol%. Further, the content of the bond unit B is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, preferably 70 mol% or less, more preferably 65 mol% or less, More preferably, it is 55 mol% or less. Further, the total content of the binding units A and B is preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.
The content of the bond units A and B is an amount including the case where the bond units A and B are located at the terminal of the silane coupling agent. The form in which the bonding units A and B are located at the end of the silane coupling agent is not particularly limited, as long as the units corresponding to the formulas (2) and (3) indicating the bonding units A and B are formed. .

Examples of the halogen for R ²⁰¹ include chlorine, bromine, and fluorine.

^Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms of R ²⁰¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert- Examples thereof include a butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, and a decyl group. The number of carbon atoms of the alkyl group is preferably 1-12.

^Examples of the branched or unbranched C 2-30 alkenyl group of R ²⁰¹ include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, and 2-pentenyl. Group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group and the like. The alkenyl group preferably has 2 to 12 carbon atoms.

^Examples of the branched or unbranched alkynyl group having 2 to 30 carbon atoms of R ²⁰¹ include ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, And dodecynyl group. The alkynyl group preferably has 2 to 12 carbon atoms.

Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms of R ²⁰² include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, Examples include dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like. The alkylene group preferably has 1 to 12 carbon atoms.

^Examples of the branched or unbranched C2-C30 alkenylene group of R202 include vinylene group, 1-propenylene group, 2-propenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group and 2-pentenylene. Group, 1-hexenylene group, 2-hexenylene group, 1-octenylene group and the like. The alkenylene group preferably has 2 to 12 carbon atoms.

Examples of branched or unbranched alkynylene group having 2 to 30 carbon atoms R ^202, ethynylene group, propynylene group, butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, nonynylene group, decynylene group, undecynylene group, And dodecynylene group. The alkynylene group preferably has 2 to 12 carbon atoms.

In the compound containing the bond unit A represented by the formula (2) and the bond unit B represented by the formula (3), the repetition of the total of the repeating number (x) of the bonding unit A and the repeating number (y) of the bonding unit B The number (x + y) is preferably in the range of 3 to 300. Within this range, since the mercaptosilane of the bond unit B is covered by —C ₇ H ₁₅ of the bond unit A, it is possible to suppress the scorch time from being shortened and to have good reactivity with silica and rubber components. Can be secured.

For example, NXT-Z30, NXT-Z45, NXT-Z60, etc. manufactured by Momentive are used as the compound containing the binding unit A represented by the formula (2) and the coupling unit B represented by the formula (3). Can do. These may be used alone or in combination of two or more.

Content of the silane coupling agent which has a mercapto group is 1 mass part or more with respect to 100 mass parts of silica, Preferably it is 3 mass parts or more. If it is less than 1 part by mass, the viscosity of the unvulcanized rubber composition is high, and good processability may not be ensured. Moreover, content of the silane coupling agent which has a mercapto group is 20 mass parts or less, Preferably it is 10 mass parts or less. If it exceeds 20 parts by mass, the rubber strength tends to decrease.

In the rubber composition of the present invention, other silane coupling agents may be used in combination with the silane coupling agent having a mercapto group. Examples of other silane coupling agents include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (2-triethoxysilylpropyl) tetrasulfide. These can be used alone or in any combination. Of these, bis (3-triethoxysilylpropyl) tetrasulfide is preferably used from the viewpoint that the effect of improving the reinforcing property and workability is great.

The content of the other silane coupling agent is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, preferably 100 parts by mass or more with respect to 100 parts by mass of silica, from the viewpoint of ensuring good processability. Is 10 parts by mass or less. From the same viewpoint, the content of other silane coupling agents is preferably less than the content of silane coupling agents having a mercapto group.

The rubber composition of the present invention preferably contains a liquid resin having a softening point of -20 to 20 ° C. By blending the liquid resin together with the conjugated diene polymer, the effect of improving each performance can be increased synergistically, and particularly, the fuel efficiency and processability can be greatly improved. Moreover, the improvement effect of each performance can further be heightened by using together the said liquid resin and the above-mentioned silane coupling agent which has a mercapto group.

The liquid resin has a softening point lower than that of the solid resin, and is liquid at 70 ° C., which is considered to have a correlation in rolling resistance characteristics. Therefore, it is considered that when a liquid resin is blended, the polymer can move easily, energy loss is reduced, and fuel efficiency is improved.

Examples of the liquid resin include liquid petroleum-based or coal-based resins such as liquid coumarone indene resin, liquid indene resin, liquid α-methylstyrene resin, liquid vinyltoluene resin, and liquid polyisopentane resin. Among these, liquid coumarone indene resin is preferable because it has a large effect of improving fuel economy.

The softening point of the liquid resin is −20 ° C. or higher, preferably −5 ° C. or higher, more preferably 0 ° C. or higher. When the temperature is lower than -20 ° C, the viscosity of the liquid resin becomes too low, and the kneadability with the rubber component tends to deteriorate. The softening point of the liquid resin is 20 ° C. or lower, preferably 19 ° C. or lower, more preferably 17 ° C. or lower. When it exceeds 20 ° C., energy loss increases and fuel efficiency tends to deteriorate.
In this specification, the softening point is a temperature at which a sphere descends when a softening point defined in JIS K 6220-1: 2001 is measured with a ring and ball softening point measuring apparatus.

The content of the liquid resin is preferably 1 part by mass or more, more preferably 6 parts by mass or more, and still more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 1 part by mass, fuel economy may not be sufficiently improved. The content of the liquid resin is preferably 20 parts by mass or less, more preferably 16 parts by mass or less. If it exceeds 20 parts by mass, good processability can be obtained, while low fuel consumption tends to deteriorate.

Known additives can be used, such as sulfur vulcanizing agents; thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, guanidine vulcanization accelerators. Vulcanization accelerators such as stearic acid and zinc oxide; organic peroxides; fillers such as carbon black, calcium carbonate, talc, alumina, clay, aluminum hydroxide and mica; Examples include processing aids such as lubricants; anti-aging agents.

Examples of the carbon black include furnace black (furness carbon black) such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF; acetylene black (acetylene carbon black); FT and Examples thereof include thermal black (thermal carbon black) such as MT; channel black (channel carbon black) such as EPC, MPC and CC; graphite and the like. These can be used alone or in combination of two or more.

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 60 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 10 parts by mass or less. If it exceeds 60 parts by mass, the fuel efficiency tends to deteriorate.

Nitrogen adsorption specific surface area _(N 2 SA) of carbon black is usually 5 to 200 m ² / g, the lower limit is preferably ^{50 m} 2 / g, the upper limit is 150 meters ² / g. Carbon black has a dibutyl phthalate (DBP) absorption amount of usually 5 to 300 ml / 100 g, preferably a lower limit of 80 ml / 100 g and an upper limit of 180 ml / 100 g. 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 fracture strength 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. As a commercial item, Tokai Carbon Co., Ltd. trade name SHIEST 6, SEAST 7HM, SEAST KH, Degussa trade name CK3, Special Black 4A, etc. can be used.

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

Examples of the vulcanization accelerator include 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and thiazole vulcanization accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethylthiuram. Thiuram vulcanization accelerators such as disulfides; N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N -Sulfenamide vulcanization accelerators such as oxyethylene-2-benzothiazole sulfenamide and N, N'-diisopropyl-2-benzothiazole sulfenamide; diphenylguanidine, diortolylguanidine, orthotolylbiguanidine What guanidine-based vulcanization accelerator can be mentioned, its amount is preferably from 0.1 to 5 parts by mass with respect to 100 parts by mass of the rubber component, more preferably from 0.2 to 3 parts by weight.

As a method for producing a rubber composition by blending the conjugated diene polymer with other rubber components or additives, a known method, for example, using a known mixer such as a roll or a banbury for each component. A kneading method can be used.

As kneading conditions, when additives other than the vulcanizing agent and the vulcanization accelerator are blended, the kneading temperature is usually 50 to 200 ° C., preferably 80 to 190 ° C., and the kneading time is usually 30 seconds. -30 minutes, preferably 1-30 minutes.

When blending a vulcanizing agent and a vulcanization accelerator, the kneading temperature is usually 100 ° C. or lower, preferably room temperature to 80 ° C. A composition containing a vulcanizing agent and a vulcanization accelerator is usually used after vulcanization treatment such as press vulcanization. The vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.

The rubber composition of the present invention has an excellent balance of low fuel consumption, breaking strength and processability, and can achieve a remarkable improvement effect of these performances.

The rubber composition of the present invention can be used for each member of a tire and can be suitably used for a bead apex. The bead apex is a member disposed on the inner side of the tire clinch so as to extend radially outward from the bead core. Specifically, FIGS. 1 to 3 of Japanese Patent Application Laid-Open No. 2008-38140, and Japanese Patent Application Laid-Open No. 2004-339287. This is a member shown in FIG.

The pneumatic tire of the present invention is manufactured by a usual method. That is, the rubber composition is kneaded using a normal tire tread processing method, for example, a roll, a Banbury mixer, a kneader, etc., and the resulting unvulcanized rubber composition is composed of a base tread and a cap tread. An unvulcanized tire is formed by extruding into the shape of a tread of the layer and bonding together with other members by a normal method on a tire molding machine. The unvulcanized tire can be heated and pressurized in a vulcanizer to obtain the pneumatic tire of the present invention.

The pneumatic tire of the present invention can be suitably used as a tire for passenger cars.

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

ピペリジン：東京化成工業（株）製
ジアミルアミン：東京化成工業（株）製
２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール：大内新興化学工業（株）製のノクラック２００
ビス（ジメチルアミノ）メチルビニルシラン：信越化学工業（株）製
Ｎ−（３−ジメチルアミノプロピル）アクリルアミド：東京化成工業（株）製
３−ジエチルアミノプロピルトリエトキシシラン：アヅマックス（株）製
ｓｅｃ−ブチルリチウム溶液：関東化学（株）製（１．０ｍｏｌ／Ｌ）
シクロヘキサン：関東化学（株）製 Hereinafter, various chemicals used at the time of synthesis and polymerization will be described together. In addition, the chemical | medical agent refine | purified according to the usual method as needed.
THF: anhydrous tetrahydrofuran hydride manufactured by Kanto Chemical Co., Ltd .: diethylamine manufactured by Kanto Chemical Co., Ltd .: methyl vinyl dichlorosilane manufactured by Kanto Chemical Co., Ltd .: anhydrous hexane manufactured by Shin-Etsu Chemical Co., Ltd .: styrene manufactured by Kanto Chemical Co., Ltd. : Kanto Chemical Co., Ltd. Butadiene: Tokyo Chemical Industry Co., Ltd. 1,3-Butadiene TMEDA: Kanto Chemical Co., Ltd. tetramethylethylenediamine n-butyllithium solution: Kanto Chemical Co., Ltd. 1.6M n- Butyllithium hexane solution initiator (1): Compound obtained by binding two units of structural units derived from isoprene to AI-200CE2 (3- (N, N-dimethylamino) -1-propyllithium manufactured by FMC Compound)) (0.9M)

Piperidine: Tokyo Chemical Industry Co., Ltd. Diamylamine: Tokyo Chemical Industry Co., Ltd. 2,6-di-tert-butyl-p-cresol: Nouchi 200 manufactured by Ouchi Shinsei Chemical Co., Ltd.
Bis (dimethylamino) methylvinylsilane: N- (3-dimethylaminopropyl) acrylamide manufactured by Shin-Etsu Chemical Co., Ltd .: 3-diethylaminopropyltriethoxysilane manufactured by Tokyo Chemical Industry Co., Ltd .: sec-butyllithium manufactured by AMAX Co., Ltd. Solution: manufactured by Kanto Chemical Co., Inc. (1.0 mol / L)
Cyclohexane: manufactured by Kanto Chemical Co., Inc.

<Preparation of modifier (1) (terminal modifier)>
Under a nitrogen atmosphere, 15.6 g of N- (3-dimethylaminopropyl) acrylamide was placed in a 100 ml volumetric flask, and anhydrous hexane was added to make a total volume of 100 ml.

<Preparation of modifier (2) (main chain modifier)>
1000 mL of THF and 13 g of sodium hydride were added to a 2 L three-necked flask sufficiently purged with nitrogen, and 36.5 g of diethylamine was slowly added dropwise with stirring on an ice-water bath. After stirring for 30 minutes, 36 g of methylvinyldichlorosilane was added dropwise over 30 minutes and stirred for 2 hours. The resulting solution was concentrated, filtered, and purified by distillation under reduced pressure to synthesize bis (diethylamino) methylvinylsilane. 21.4 g of the obtained bis (diethylamino) methylvinylsilane was placed in a 100 ml volumetric flask under a nitrogen atmosphere, and anhydrous hexane was further added to make a total volume of 100 ml.

<Preparation of modifier (3) (terminal modifier)>
Under a nitrogen atmosphere, 27.7 g of 3-diethylaminopropyltriethoxysilane was placed in a 100 ml volumetric flask, and anhydrous hexane was added to make a total volume of 100 ml.

<Analysis of copolymer>
The copolymer (conjugated diene polymer) obtained by the following was analyzed by the following method.

<Measurement of weight average molecular weight Mw and number average molecular weight Mn>
The weight average molecular weight Mw and number average molecular weight Mn of the copolymer are gel permeation chromatograph (GPC) (GPC-8000 series, manufactured by Tosoh Corporation, detector: differential refractometer, column: TSKGEL manufactured by Tosoh Corporation). Based on the measured value by SUPERMALTPORE HZ-M), it was determined as a standard polystyrene equivalent value. From the measurement results, the molecular weight distribution Mw / Mn was calculated.

<Structural identification of copolymer>
The structure identification (styrene content, vinyl content) of the copolymer was performed using a JNM-ECA series apparatus manufactured by JEOL Ltd. The measurement was conducted after drying under reduced pressure, 0.1 g of the polymer dissolved in 15 ml of toluene, slowly poured into 30 ml of methanol and reprecipitated.

<Synthesis of copolymer (1)>
In a 30 L pressure vessel sufficiently purged with nitrogen, 18 L of n-hexane, 600 g of styrene, 1400 g of butadiene, 40 mL of modifier (2) and 10 mmol of TMEDA were added, and the temperature was raised to 40 ° C. Next, after adding 19 mL of initiator (1), it heated up at 50 degreeC and stirred for 3 hours. Next, 20 mL of the modifier (1) was added and stirred for 30 minutes. After adding 15 mL of methanol and 0.1 g of 2,6-tert-butyl-p-cresol to the reaction solution, the aggregate is recovered from the polymer solution by a steam stripping treatment, and the obtained aggregate is dried under reduced pressure for 24 hours. Copolymer (1) was obtained. The silicon-containing vinyl compound (modifier (2)) added was 0.43 g per 100 g of the monomer component. The charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component. The amount of the nitrogen atom and / or silicon atom-containing compound (modifier (1)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.

<Synthesis of copolymer (2)>
A copolymer (2) was obtained by the same formulation as the synthesis of the copolymer (1) except that 19 mL of the initiator (1) was changed to 10.6 mL of the n-butyllithium solution. The silicon-containing vinyl compound (modifier (2)) added was 0.43 g per 100 g of the monomer component. The amount of the nitrogen atom and / or silicon atom-containing compound (modifier (1)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.

<Synthesis of copolymer (3)>
In a 30 L pressure vessel sufficiently substituted with nitrogen, 18 L of n-hexane, 600 g of styrene, 1400 g of butadiene and 10 mmol of TMEDA were added, and the temperature was raised to 40 ° C. Next, after adding 11 mL of n-butyllithium solutions, it heated up at 50 degreeC and stirred for 3 hours. Next, 1 mL of methanol and 0.1 g of 2,6-tert-butyl-p-cresol are added to the reaction solution, and then aggregates are collected from the polymer solution by steam stripping, and the obtained aggregates are recovered for 24 hours. It was dried under reduced pressure to obtain a copolymer (3).

<Synthesis of copolymer (4)>
When recovering the aggregate from the polymer solution, instead of the steam stripping treatment, the polymer solution (1) was recovered except that the polymer solution was evaporated at room temperature for 24 hours and then dried under reduced pressure. The copolymer (4) was obtained by the same formulation as in the synthesis of). The silicon-containing vinyl compound (modifier (2)) added was 0.43 g per 100 g of the monomer component. The charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component. The amount of the nitrogen atom and / or silicon atom-containing compound (modifier (1)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.

<Synthesis of copolymer (5)>
A copolymer (5) was obtained by the same formulation as the synthesis of the copolymer (1) except that 40 mL of the modifier (2) was changed to 0 mL and 20 mL of the modifier (1) was changed to 0 mL. The charged polymerization initiator (initiator (1)) was 8.5 mmol per 100 g of the monomer component.

<Synthesis of copolymer (6)>
The copolymer (6) was prepared in the same formulation as the synthesis of the copolymer (1) except that 19 mL of the initiator (1) was changed to 6.8 mL of n-butyllithium solution and 20 mL of the modifier (1) was changed to 0 mL. Got. The silicon-containing vinyl compound (modifier (2)) added was 0.43 g per 100 g of the monomer component.

<Synthesis of copolymer (7)>
A copolymer (7) was obtained by the same formulation as the synthesis of the copolymer (1) except that 20 mL of the modifier (1) was changed to 20 mL of the modifier (3). The silicon-containing vinyl compound (modifier (2)) added was 0.32 g per 100 g of the monomer component. The charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component. The amount of the nitrogen atom and / or silicon atom-containing compound (modifier (3)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.

<Synthesis of copolymer (8)>
When recovering the aggregate from the polymer solution, instead of the steam stripping treatment, the copolymer solution (7) was used except that the polymer solution was evaporated at room temperature for 24 hours and then dried under reduced pressure. The copolymer (8) was obtained by the same formulation as the synthesis of). The silicon-containing vinyl compound (modifier (2)) added was 0.32 g per 100 g of the monomer component. The charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component. The amount of the nitrogen atom and / or silicon atom-containing compound (modifier (3)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.

<Synthesis of copolymer (9)>
The copolymer (9) was prepared by the same formulation as the synthesis of the copolymer (7) except that 19 mL of the initiator (1) was changed to 10.6 mL of n-butyllithium solution and 40 mL of the modifier (2) was changed to 0 mL. Got. In addition, the compound (modifier (3)) containing the introduced nitrogen atom and / or silicon atom was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.

<Synthesis of copolymer (10)>
Except for changing the amount of styrene to 0 g, the amount of butadiene to 2000 g, TMEDA 10 mmoL to THF 5 mmoL, and initiator (1) 19 mL to initiator (1) 23 mL, the same formulation as the synthesis of copolymer (1) Copolymer (10) was obtained. The silicon-containing vinyl compound (modifier (2)) added was 0.43 g per 100 g of the monomer component. The charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component. The amount of the nitrogen atom and / or silicon atom-containing compound (modifier (1)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.

<Synthesis of copolymer (11)>
When collecting the aggregate from the polymer solution, instead of the steam stripping treatment, the polymer solution (10) was collected except that the polymer solution was evaporated at room temperature for 24 hours and then dried under reduced pressure. The copolymer (11) was obtained by the same formulation as in the synthesis of). The silicon-containing vinyl compound (modifier (2)) added was 0.43 g per 100 g of the monomer component. The charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component. The amount of the nitrogen atom and / or silicon atom-containing compound (modifier (1)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.

The monomer components of the copolymers (1) to (11) are summarized in Table 1.

Below, various chemical | medical agents used by the Example and the comparative example are demonstrated.
Copolymers (1) to (11): Synthetic natural rubber by the above method: TSR20
Butadiene rubber: Ubepol BR150B manufactured by Ube Industries, Ltd.
Silica 1: Ultrasil 360 manufactured by EVONIK-DEGUSSA (N ₂ SA: 50 m ² / g)
Silica 2: Zeosyl 1205MP (N ₂ SA: 200 m ² / g) manufactured by Rhodia
Silane coupling agent 1: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by EVONIK-DEGUSSA
Silane coupling agent 2: NXT-Z45 manufactured by Momentive (compound containing bonding unit A and bonding unit B (bonding unit A: 55 mol%, bonding unit B: 45 mol%))
Silane coupling agent 3: Si363 manufactured by EVONIK-DEGUSSA
Carbon black: Dia Black N339 manufactured by Mitsubishi Chemical Corporation (N ₂ SA: 96 m ² / g, DBP absorption: 124 ml / 100 g)
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Solid resin: Escorez 1102 manufactured by ExxonMobil
Liquid resin: NOVARES C10 (liquid coumarone indene resin, softening point: 5 to 15 ° C.) manufactured by Rutkers Chemical Co.
Anti-aging agent: Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.
Stearic acid: Beads manufactured by NOF Corporation Zinc stearate zinc oxide: Zinc flower No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powdered sulfur vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd .: Sumitomo Chemical Co., Ltd. Soxinol CZ

(Examples and Comparative Examples)
In accordance with the formulation shown in Tables 2 to 4, materials other than sulfur and a vulcanization accelerator were kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer manufactured by Kobe Steel, Ltd., and mixed. A kneaded paste was obtained. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes under the condition of 80 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized with a 0.5 mm thick mold at 170 ° C. for 20 minutes to obtain a vulcanized rubber composition.
Further, the obtained unvulcanized rubber composition is molded into a bead apex shape and bonded together with other tire members on a tire molding machine to form an unvulcanized tire, and vulcanized at 170 ° C. for 12 minutes. A test tire (size: 195 / 65R15) was produced.

<Evaluation items and test methods>
In the following evaluation items, the reference comparative example in Tables 2 and 3 was set as Comparative Example 1, and the reference comparative example in Table 4 was set as Comparative Example 22.

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

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

<Destruction energy>
Using a No. 3 dumbbell made of the above vulcanized rubber composition, a tensile test was conducted in accordance with JIS K 6251: 2010 “Vulcanized rubber and thermoplastic rubber-Determination of tensile properties” to determine the breaking strength (TB) The time elongation (EB) was measured, and the fracture energy (TB × EB / 2) was calculated. Then, the breaking energy of the reference comparative example was set to 100, and the breaking energy of each formulation was displayed as an index according to the following formula. It shows that fracture strength is so high that a numerical value is large.
(Fracture energy index) = (Fracture energy of each formulation) / (Fracture energy of reference comparative example) × 100

<Mooney viscosity>
In accordance with JIS K 6300-1: 2001 "Unvulcanized rubber-Physical properties-Part 1: Determination of viscosity and scorch time by Mooney viscometer", heat by preheating for 1 minute using a Mooney viscosity tester. Under the temperature condition of 130 ° C., the small rotor was rotated, and the Mooney viscosity (ML _{1 +} 4/130 ° C.) of the unvulcanized rubber composition after 4 minutes was measured. The result is expressed as an index. The larger the value, the lower the Mooney viscosity and the better the workability (kneading workability). The index was calculated by the following formula.
(Mooney viscosity index) = (Mooney viscosity of reference comparative example) / (Mooney viscosity of each formulation) × 100

<Processability of unvulcanized rubber sheet>
The unvulcanized rubber composition was extruded and formed into a rubber sheet having a thickness of 1.0 mm with a roll, and the state of the resulting rubber sheet was confirmed. The case where the ears were not cut off and there was no problem in the skin of the fabric was indicated by ○, and the case where it was not indicated by ×.

As shown in Tables 2 to 4, the examples have a specific amine structure at the initiation terminal, a structural unit derived from a silicon-containing compound in the main chain portion, and a nitrogen atom and / or a silicon atom at the termination terminal. Containing a specific amount of a conjugated diene copolymer having a structural unit derived from the compound to be contained, silica, and a silane coupling agent having a mercapto group, so that it has low fuel consumption compared to the rubber composition of the comparative example The fracture strength and workability were improved in a well-balanced manner.

Examples 9 to 20 in which two types of silica having a specific nitrogen adsorption specific surface area and / or a liquid resin having a specific softening point were blended with the conjugated diene polymer and a silane coupling agent having a mercapto group The performance was greatly improved, and in particular, Examples 17 to 20 using all of these showed the highest performance.

Claims (10)

At the active terminal of the copolymer obtained by polymerizing a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound using a polymerization initiator represented by the following formula (I), a nitrogen atom and / or a silicon atom A conjugated diene polymer obtained by reacting a compound containing
Polyisoprene rubber,
Silica,
A silane coupling agent having a mercapto group,
The conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, and myrcene. ,
The silicon-containing vinyl compound is a compound represented by the following formula (II):
The compound containing the nitrogen atom and / or silicon atom is a compound represented by the following formula (III) or a compound represented by the following formula (IV),
In 100% by mass of the rubber component, the content of the conjugated diene polymer is 25 to 50% by mass , the content of the polyisoprene rubber is 20 to 75% by mass ,
Content of the said silica with respect to 100 mass parts of said rubber components is 40-80 mass parts,
The rubber composition for bead apex whose content of the said silane coupling agent with respect to 100 mass parts of said silicas is 1-20 mass parts.

(In Formula (I), i is 0 or 1, R ¹¹ represents a hydrocarbylene group having 1 to 100 carbon atoms, R ¹² and R ¹³ are hydrocarbyl groups which may have a substituent, Alternatively, it represents a trihydrocarbylsilyl group, or R ¹² and R ¹³ are bonded to each other and have at least one atom selected from the atomic group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a hetero atom. Represents an optionally hydrocarbylene group, and M represents an alkali metal atom.)

(In formula (II), m is 0 or 1, R ²¹ represents a hydrocarbylene group, and X ¹ , X ² and X ³ have a substituted amino group, a hydrocarbyloxy group, or a substituent. Represents a good hydrocarbyl group.)

(In the formula (III), R ³¹ is a hydrocarbyl group which may have a substituent, a hydrocarbylene group which may be bonded to R ³² and have a nitrogen atom and / or an oxygen atom as a hetero atom, or represents divalent group bonded to R ^34, R ³² are have an optionally substituted hydrocarbyl group, or a nitrogen atom and / or oxygen atom bonded to R ³¹ as a hetero atom R ³⁴ may be a hydrocarbyl group which may have a substituent, a hydrogen atom, or a divalent group bonded to R ^31. R ³³ represents a divalent group. , K represents 0 or 1.)

(In the formula (IV), R ⁴¹ represents a hydrocarbyl group, R ⁴² and R ⁴³ represent a hydrocarbyl group or a hydrocarbyloxy group, and R ⁴⁴ represents a hydrocarbyl group or a trihydrocarbylsilyl group which may have a substituent. carded or combined with R ^45,, represents a silicon atom, a nitrogen atom and hydrocarbylene group optionally having at least one atom as a hetero atom selected from the group of atoms consisting of oxygen atoms, R ⁴⁵ is substituted represent a hydrocarbyl group or a trihydrocarbylsilyl group which may have a group, or combined with R ^44, at least one atom selected from the group of atoms of silicon atoms, nitrogen atoms and oxygen atoms as a hetero atom (It represents a hydrocarbylene group that may be present, and j represents an integer of 1 to 5.) The rubber composition for bead apex according to claim 1, wherein R ^{11 in the} formula (I) is a group represented by the following formula (Ia).

(In formula (Ia), R ¹⁴ represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, and n represents an integer of 1 to 10.) The rubber composition for bead apex according to claim 2, wherein R ^{14 in the} formula (Ia) is a hydrocarbylene group composed of 1 to 10 structural units derived from isoprene. The rubber composition for bead apex according to any one of claims 1 to 3 , wherein the conjugated diene polymer has a structural unit derived from an aromatic vinyl compound. Rubber composition for a bead apex according to any of claims 1-4 nitrogen adsorption specific surface area of the silica is 40 to 400 ² / g. The silica, the nitrogen adsorption specific surface area of ^{40 m} 2 / g or more, 120 m ² / g less than the silica (1), according to claim 1 to 5 nitrogen adsorption specific surface area comprising a 120 m ² / g or more silica (2) The rubber composition for bead apex according to any one of the above. The rubber composition for bead apex according to any one of claims 1 to 6 , comprising 1 to 20 parts by mass of a liquid resin having a softening point of -20 to 20 ° C with respect to 100 parts by mass of the rubber component. The silica includes a silica (1) having a nitrogen adsorption specific surface area of 40 m ² / g or more and less than 120 m ² / g, and a silica (2) having a nitrogen adsorption specific surface area of 120 m ² / g or more,
The rubber composition for bead apex according to any one of claims 1 to 7 , comprising 1 to 20 parts by mass of a liquid resin having a softening point of -20 to 20 ° C with respect to 100 parts by mass of the rubber component. The silane coupling agent is a compound containing a compound represented by the following formula (1) and / or a binding unit A represented by the following formula (2) and a binding unit B represented by the following formula (3). The bead apex rubber composition according to any one of claims 1 to 8 .

(In the formula (1), R ^{101 to} R ¹⁰³ are each a branched or unbranched C 1-12 alkyl group, a branched or unbranched C 1-12 alkoxy group, or —O— (R ¹¹¹ — O) _z- R ¹¹² (z R ¹¹¹ represents a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms. The z R ^{111 s} may be the same as or different from each other. ¹¹² represents a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. Z represents an integer of 1 to 30.) R ^{101 to} R ¹⁰³ may be the same as or different from each other, and R ¹⁰⁴ has 1 to 6 carbon atoms which are branched or unbranched. Represents an alkylene group of

(In the formulas (2) and (3), R ²⁰¹ is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, branched or unbranched alkenyl group having 2 to 30 carbon atoms, branched or unbranched. Or an alkyl group substituted with a hydroxyl group or a carboxyl group, and R ²⁰² represents a branched or unbranched C 1-30 alkylene group, branched or It represents an unbranched C2-C30 alkenylene group or a branched or unbranched C2-C30 alkynylene group, and R ²⁰¹ and R ²⁰² may form a ring structure.) A pneumatic tire produced using the rubber composition for a bead apex according to any of claims 1-9.