JP5933310B2 - Rubber composition for truck / bus tire and truck / bus tire - Google Patents

Description

TECHNICAL FIELD The present invention relates to a rubber composition for truck and bus tires and a truck and bus tire produced using the rubber composition.

In recent years, in the transportation industry, tires with excellent fuel efficiency have been desired for the reasons of increased costs associated with soaring fuel costs and increased costs due to the introduction of environmental regulations. As a rubber composition for an automobile tire, a rubber composition containing a conjugated diene polymer such as natural rubber or polybutadiene and a filler such as carbon black or silica is used.

As a method for improving fuel efficiency, for example, Patent Documents 1 to 3 propose a method of giving affinity to silica by adding a specific polar group to rubber in a compound containing silica. However, in recent years, further improvement in fuel efficiency has been demanded. Among automobile tires, truck and bus tires are particularly required to have excellent wear resistance and rubber strength, but these performances are incompatible with low fuel consumption, so each performance is balanced at a high level. It was difficult to get well.

JP 2001-114939 A JP 2005-126604 A JP 2005-325206 A

The present invention solves the above problems and provides a rubber composition for truck and bus tires that can improve fuel economy, wear resistance, and rubber strength in a well-balanced manner, and a truck and bus tire produced using the same. Objective.

［式中、Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立に、下式（Ｉａ）で表される基、水酸基、ヒドロカルビル基又は置換ヒドロカルビル基を表し、Ｘ^１、Ｘ^２及びＸ^３の少なくとも１つが、下式（Ｉａ）で表される基又は水酸基である。］

［式中、Ｒ^１及びＲ^２は、それぞれ独立に、炭素原子数が１〜６のヒドロカルビル基、炭素原子数が１〜６の置換ヒドロカルビル基、シリル基又は置換シリル基を表し、Ｒ^１及びＲ^２は結合して窒素原子と共に環構造を形成していてもよい。］

［式中、ｎは１〜１０の整数を表し、Ｒ^１１、Ｒ^１２及びＲ^１３は、それぞれ独立に、炭素原子数が１〜４のヒドロカルビル基又は炭素原子数が１〜４のヒドロカルビルオキシ基を表し、Ｒ^１１、Ｒ^１２及びＲ^１３の少なくとも１つがヒドロカルビルオキシ基であり、Ａ^１は窒素原子を有する官能基を表す。］

［式中、ｐは０又は１の整数を表し、Ｔは、炭素原子数が１〜２０のヒドロカルビレン基又は炭素原子数が１〜２０の置換ヒドロカルビレン基を表し、Ａ^２は窒素原子を有する官能基を表す。］

［式中、ｇは、１〜１０の整数を表し、Ｒ^２１は、水素原子、炭素原子数が１〜６のヒドロカルビル基又は炭素原子数が１〜６の置換ヒドロカルビル基を表し、Ａ^３は、酸素原子又は−ＮＲ^２２−基（Ｒ^２２は、水素原子又は炭素原子数が１〜１０のヒドロカルビル基を表す。）を表し、Ａ^４は、窒素原子及び／又は酸素原子を有する官能基を表す。］

［式中、ｗは１〜１１の整数を表し、Ａ^５は窒素原子を有する官能基を表す。］ The present invention contains a rubber component and silica, and has a structural unit based on a conjugated diene and a structural unit represented by the following formula (I) in 100% by mass of the rubber component, A compound represented by the following formula (III), a compound represented by the following formula (IV), a group represented by the following formula (V) and / or a formula represented by the following formula (VI): A conjugated diene polymer in which at least one end of the polymer is modified with at least one compound selected from the group consisting of a silicon compound having a group represented by formula (VII) and a compound having a group represented by the following formula (VII): This is related to a rubber composition for truck and bus tires in which the content of silica is 5% by mass or more and the content of silica is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

[Wherein, X ¹ , X ² and X ³ each independently represent a group represented by the following formula (Ia), a hydroxyl group, a hydrocarbyl group or a substituted hydrocarbyl group, and at least ^one of X ¹ , X ² and X ³ One is a group or a hydroxyl group represented by the following formula (Ia). ]

[Wherein, R ¹ and R ² independently denote a hydrocarbyl group having 1 to 6 carbon atoms, a substituted hydrocarbyl group having 1-6 carbon atoms, or a substituted silyl group, R ¹ and R ² may be bonded to form a ring structure with the nitrogen atom. ]

[Wherein, n represents an integer of 1 to 10, and R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbyl group having 1 to 4 carbon atoms or a hydrocarbyloxy group having 1 to 4 carbon atoms. Wherein at least one of R ¹¹ , R ¹² and R ¹³ is a hydrocarbyloxy group, and A ¹ represents a functional group having a nitrogen atom. ]

[Wherein, p represents an integer of 0 or 1, T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms, and A ² represents nitrogen. A functional group having an atom is represented. ]

[Wherein, g represents an integer of 1 to 10, R ²¹ represents a hydrogen atom, a hydrocarbyl group having 1 to 6 carbon atoms, or a substituted hydrocarbyl group having 1 to 6 carbon atoms, and A ³ represents , An oxygen atom or a —NR ²² — group (R ²² represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms), and A ⁴ represents a functional group having a nitrogen atom and / or an oxygen atom. Represent. ]

[Wherein, w represents an integer of 1 to 11, and A ⁵ represents a functional group having a nitrogen atom. ]

R ¹ and R ^{2 in} formula (Ia) are preferably hydrocarbyl groups having 1 to 6 carbon atoms.

^Two of X ¹ , X ² and X ^{3 in} the formula (I) are preferably a group or a hydroxyl group represented by the formula (Ia).

The vinyl bond content of the conjugated diene polymer is preferably 10 mol% or more and 80 mol% or less, with the content of structural units based on the conjugated diene being 100 mol%.

The rubber composition preferably contains natural rubber and / or butadiene rubber.

It is preferable that the nitrogen adsorption specific surface area of a silica is 40-400 m < ² > / g.

The present invention also relates to a truck / bus tire produced using the rubber composition.

According to the present invention, since it is a rubber composition in which a specific amount of a specific conjugated diene polymer and silica are blended in predetermined amounts, a truck / bus tire with improved fuel efficiency, wear resistance and rubber strength in a well-balanced manner. Can provide.

［式中、Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立に、下式（Ｉａ）で表される基、水酸基、ヒドロカルビル基又は置換ヒドロカルビル基を表し、Ｘ^１、Ｘ^２及びＸ^３の少なくとも１つが、下式（Ｉａ）で表される基又は水酸基である。］

［式中、Ｒ^１及びＲ^２は、それぞれ独立に、炭素原子数が１〜６のヒドロカルビル基、炭素原子数が１〜６の置換ヒドロカルビル基、シリル基又は置換シリル基を表し、Ｒ^１及びＲ^２は結合して窒素原子と共に環構造を形成していてもよい。］

［式中、ｎは１〜１０の整数を表し、Ｒ^１１、Ｒ^１２及びＲ^１３は、それぞれ独立に、炭素原子数が１〜４のヒドロカルビル基又は炭素原子数が１〜４のヒドロカルビルオキシ基を表し、Ｒ^１１、Ｒ^１２及びＲ^１３の少なくとも１つがヒドロカルビルオキシ基であり、Ａ^１は窒素原子を有する官能基を表す。］

［式中、ｐは０又は１の整数を表し、Ｔは、炭素原子数が１〜２０のヒドロカルビレン基又は炭素原子数が１〜２０の置換ヒドロカルビレン基を表し、Ａ^２は窒素原子を有する官能基を表す。］

［式中、ｇは、１〜１０の整数を表し、Ｒ^２１は、水素原子、炭素原子数が１〜６のヒドロカルビル基又は炭素原子数が１〜６の置換ヒドロカルビル基を表し、Ａ^３は、酸素原子又は−ＮＲ^２２−基（Ｒ^２２は、水素原子又は炭素原子数が１〜１０のヒドロカルビル基を表す。）を表し、Ａ^４は、窒素原子及び／又は酸素原子を有する官能基を表す。］

［式中、ｗは１〜１１の整数を表し、Ａ^５は窒素原子を有する官能基を表す。］ The rubber composition of the present invention has a structural unit based on a conjugated diene and a structural unit represented by the following formula (I), a compound represented by the following formula (II), and represented by the following formula (III): A compound having a group, a compound represented by the following formula (IV), a silicon compound having a group represented by the following formula (V) and / or a group represented by the following formula (VI), and the following formula (VII): A conjugated diene polymer in which at least one end of the polymer is modified with at least one compound selected from the group consisting of compounds having a group represented by formula (I) and silica.

[Wherein, X ¹ , X ² and X ³ each independently represent a group represented by the following formula (Ia), a hydroxyl group, a hydrocarbyl group or a substituted hydrocarbyl group, and at least ^one of X ¹ , X ² and X ³ One is a group or a hydroxyl group represented by the following formula (Ia). ]

[Wherein, R ¹ and R ² independently denote a hydrocarbyl group having 1 to 6 carbon atoms, a substituted hydrocarbyl group having 1-6 carbon atoms, or a substituted silyl group, R ¹ and R ² may be bonded to form a ring structure with the nitrogen atom. ]

[Wherein, n represents an integer of 1 to 10, and R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbyl group having 1 to 4 carbon atoms or a hydrocarbyloxy group having 1 to 4 carbon atoms. Wherein at least one of R ¹¹ , R ¹² and R ¹³ is a hydrocarbyloxy group, and A ¹ represents a functional group having a nitrogen atom. ]

[Wherein, p represents an integer of 0 or 1, T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms, and A ² represents nitrogen. A functional group having an atom is represented. ]

[Wherein, g represents an integer of 1 to 10, R ²¹ represents a hydrogen atom, a hydrocarbyl group having 1 to 6 carbon atoms, or a substituted hydrocarbyl group having 1 to 6 carbon atoms, and A ³ represents , An oxygen atom or a —NR ²² — group (R ²² represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms), and A ⁴ represents a functional group having a nitrogen atom and / or an oxygen atom. Represent. ]

[Wherein, w represents an integer of 1 to 11, and A ⁵ represents a functional group having a nitrogen atom. ]

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

X ¹ , X ² and X ³ in formula (I) of the structural unit represented by formula (I) each independently represent a group represented by formula (Ia), a hydroxyl group, a hydrocarbyl group or a substituted hydrocarbyl group. , X ¹ , X ² and X ³ are a group represented by the formula (Ia) or a hydroxyl group.

R ¹ and R ^{2 in} formula (Ia) each independently represent a hydrocarbyl group having 1 to 6 carbon atoms, a substituted hydrocarbyl group having 1 to 6 carbon atoms, a silyl group, or a substituted silyl group, and R ¹ And R ² may be bonded together to form a ring structure together with the nitrogen atom.

As used herein, a hydrocarbyl group represents a monovalent hydrocarbon residue. Here, the hydrocarbon residue represents a group obtained by removing hydrogen from a hydrocarbon. A substituted hydrocarbyl group represents a group in which one or more hydrogen atoms of a monovalent hydrocarbon residue are substituted with a substituent. The hydrocarbyloxy group represents a group in which a hydrogen atom of a hydroxyl group is substituted with a hydrocarbyl group, and the substituted hydrocarbyloxy group represents a group in which one or more hydrogen atoms of the hydrocarbyloxy group are substituted with a substituent. The hydrocarbylene group represents a divalent hydrocarbon residue. The substituted hydrocarbylene group represents a group in which one or more hydrogen atoms of a divalent hydrocarbon residue are substituted with a substituent. The substituted silyl group represents a group in which one or more hydrogen atoms of the silyl group are substituted with a substituent.

Examples of the hydrocarbyl group having 1 to 6 carbon atoms of R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- Examples thereof include alkyl groups such as pentyl group, neopentyl group, isopentyl group and n-hexyl group; cycloalkyl groups such as cyclohexyl group; phenyl groups and the like.

The substituted hydrocarbyl group having 1 to 6 carbon atoms in R ¹ and R ² includes at least one group selected from the group consisting of a group having a nitrogen atom, a group having an oxygen atom, and a group having a silicon atom. The substituted hydrocarbyl group which has as a substituent can be mention | raise | lifted. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl Group, alkoxyalkyl group such as methoxyethyl group, ethoxymethyl group, ethoxyethyl group and the like, and groups having a silicon atom as a substituent include trialkylsilylalkyl groups such as trimethylsilylmethyl group, etc. I can give you.

Examples of the substituted silyl group for R ¹ and R ² include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group.

The group to which R ¹ and R ² are bonded is a divalent group having 1 to 12 carbon atoms that may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. Group. For example, an alkylene group such as a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; an oxydialkylene group such as an oxydiethylene group and an oxydipropylene group; and —CH ₂ CH ₂ —NH—CH ₂ — And a nitrogen-containing group such as a group represented by —CH ₂ CH ₂ —N═CH—.

The group to which R ¹ and R ² are bonded is preferably a nitrogen-containing group, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—. Is more preferable.

The hydrocarbyl group of R ¹ and R ² is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, further preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, Group, n-butyl group is particularly preferred. The substituted hydrocarbyl group for R ¹ and R ² is preferably an alkoxyalkyl group, and more preferably an alkoxyalkyl group having 1 to 4 carbon atoms. The substituted silyl group for R ¹ and R ² is preferably a trialkylsilyl group, and more preferably a trimethylsilyl group.

R ¹ and R ² are preferably an alkyl group, an alkoxyalkyl group, a substituted silyl group, or a nitrogen-containing group to which R ¹ and R ² are bonded, more preferably an alkyl group, still more preferably carbon. It is an alkyl group having 1 to 4 atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.

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

Examples of the acyclic amino group include dimethylamino group, diethylamino group, di (n-propyl) amino group, di (isopropyl) amino group, di (n-butyl) amino group, di (sec-butyl) amino group, di ( dialkylamino groups such as tert-butyl) amino group, di (neopentyl) amino group, ethylmethylamino group; di (methoxymethyl) amino group, di (methoxyethyl) amino group, di (ethoxymethyl) amino group, di ( And di (alkoxyalkyl) amino groups such as ethoxyethyl) amino group; and di (trialkylsilyl) amino groups such as di (trimethylsilyl) amino group and di (t-butyldimethylsilyl) amino group.

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

The group represented by the formula (Ia) is preferably an acyclic amino group, more preferably a dialkylamino group, and still more preferably 1 to 1 carbon atoms from the viewpoint of economy and availability. A dialkylamino group substituted with 4 alkyl groups, and more preferably a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, and a di (n-butyl) amino group.

Examples of the hydrocarbyl group of X ^{1 to} X ^{3 in} the formula (I) include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. be able to. Examples of the substituted hydrocarbyl group include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and an ethoxyethyl group.

The hydrocarbyl group of X ^{1 to} X ³ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group. Furthermore, the substituted hydrocarbyl group X ¹ to X ^3, preferably an alkoxyalkyl group, more preferably an alkoxyalkyl group having 1 to 4 carbon atoms.

The hydrocarbyl group and substituted hydrocarbyl group of X ^{1 to} X ³ are preferably an alkyl group or an alkoxyalkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. It is an alkoxyalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.

At least one of X ¹ , X ² and X ^{3 in} the formula (I) is a group or a hydroxyl group represented by the formula (Ia). Preferably, two or more of X ¹ , X ² and X ³ are a group or a hydroxyl group represented by the formula (Ia), more preferably ^{two of} X ¹ , X ² and X ³ are represented by the formula (Ia ) Or a hydroxyl group. Further, fuel economy, abrasion resistance and rubber strength in terms of good balance is obtained at a high level, preferably at least one of hydroxyl group of X ^1, X ² and X ^3, X ^1, X ² and X More preferably, two or more of ³ are hydroxyl groups, and ^{two of} X ¹ , X ² and X ³ are more preferably hydroxyl groups.

From the viewpoint of improving fuel economy, wear resistance, and rubber strength in a well-balanced manner, the constitutional unit represented by the formula (I) is a constitution in which ^{two of} X ¹ , X ² and X ³ are acyclic amino groups or hydroxyl groups. Units are preferred. As the structural unit in which ^{two of} X ¹ , X ² and X ³ are acyclic amino groups, bis (dialkylamino) alkylvinylsilane units are preferred, bis (dimethylamino) methylvinylsilane units, bis (diethylamino) methylvinylsilane units, Bis (di (n-propyl) amino) methylvinylsilane units and bis (di (n-butyl) amino) methylvinylsilane units are more preferred. As the structural unit in which two of X ¹ , X ² and X ³ are hydroxyl groups, a dihydroxyalkylvinylsilane unit is preferable, and a dihydroxymethylvinylsilane unit is more preferable.

The content of the structural unit represented by the formula (I) in the conjugated diene polymer is preferably about 0.000 per unit mass of the polymer from the viewpoint of improving fuel economy, wear resistance, and rubber strength in a balanced manner. It is 001 mmol / g polymer or more and 0.1 mmol / g polymer or less. More preferably, it is 0.002 mmol / g polymer or more and 0.07 mmol / g polymer or less. More preferably, it is 0.003 mmol / g polymer or more and 0.05 mmol / g polymer or less.

In the conjugated diene polymer, at least one end of the polymer is modified with a specific compound (modifiers 1 to 5). Thereby, interaction with silica arises and low fuel consumption, abrasion resistance, and rubber strength can be improved with good balance.

［式中、ｎは１〜１０の整数を表し、Ｒ^１１、Ｒ^１２及びＲ^１３は、それぞれ独立に、炭素原子数が１〜４のヒドロカルビル基又は炭素原子数が１〜４のヒドロカルビルオキシ基を表し、Ｒ^１１、Ｒ^１２及びＲ^１３の少なくとも１つがヒドロカルビルオキシ基であり、Ａ^１は窒素原子を有する官能基を表す。］ Hereinafter, the compound (Modifier 1) represented by the following formula (II) will be described.

[Wherein, n represents an integer of 1 to 10, and R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbyl group having 1 to 4 carbon atoms or a hydrocarbyloxy group having 1 to 4 carbon atoms. Wherein at least one of R ¹¹ , R ¹² and R ¹³ is a hydrocarbyloxy group, and A ¹ represents a functional group having a nitrogen atom. ]

R ¹¹ , R ¹² and R ^{13 in} formula (II) each independently represent a hydrocarbyl group having 1 to 4 carbon atoms or a hydrocarbyloxy group having 1 to 4 carbon atoms, and R ¹¹ , R ¹² and At least one of R ¹³ is a hydrocarbyloxy group.

Examples of the hydrocarbyl group of R ¹¹ , R ¹² and R ¹³ include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, alkyl groups such as tert-butyl groups, and the like. Can do. Moreover, as hydrocarbyloxy group of R < ¹¹ >, R < ¹² > and R < ¹³ >, alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and t-butoxy group Can give.

The hydrocarbyl group of R ¹¹ , R ¹² and R ¹³ is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group. . Further, the hydrocarbyloxy group of R ¹¹ , R ¹² and R ¹³ is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms, and still more preferably a methoxy group or ethoxy group. It is a group.

As R ¹¹ , R ¹² and R ¹³ , preferably, at least two of R ¹¹ , R ¹² and R ¹³ are hydrocarbyloxy groups, from the viewpoint of improving fuel economy, wear resistance and rubber strength in a balanced manner. Preferably, three of R ¹¹ , R ¹² and R ¹³ are hydrocarbyloxy groups.

N in the formula (II) represents an integer of 1 to 10. From the viewpoint of improving fuel economy, wear resistance and rubber strength in a well-balanced manner, it is preferably 3 or more, and from the viewpoint of improving economy, it is preferably 4 or less. Particularly preferred is 3.

A ^{1 in the} formula (II) is a functional group having a nitrogen atom, and examples thereof include an amino group, an isocyano group, a cyano group, a pyridyl group, a piperidyl group, a pyrazinyl group, and a morpholino group.

［式中、Ｒ^１４及びＲ^１５は、それぞれ独立に、窒素原子、酸素原子及びケイ素原子からなる原子群から選ばれる少なくとも１種の原子を有していてもよい炭素原子数が１〜６の基を表し、Ｒ^１４及びＲ^１５は結合して窒素原子と共に環構造を形成していてもよく、Ｒ^１４及びＲ^１５は窒素に二重結合で結合する同一の基であってもよい。］ A ¹ is preferably a group represented by the following formula (IIa).

[Wherein R ¹⁴ and R ¹⁵ each independently have 1 to 6 carbon atoms which may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. R ¹⁴ and R ¹⁵ may be bonded to form a ring structure with the nitrogen atom, and R ¹⁴ and R ¹⁵ may be the same group bonded to the nitrogen by a double bond. ]

Examples of R ¹⁴ and R ^{15 in} the formula (IIa) include a hydrocarbyl group having 1 to 6 carbon atoms, a substituted hydrocarbyl group having 1 to 6 carbon atoms, and a substituted silyl group.

Examples of the hydrocarbyl group of R ¹⁴ and R ¹⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, and isopentyl group. And alkyl groups such as n-hexyl group; cycloalkyl groups such as cyclohexyl group; phenyl groups and the like.

The substituted hydrocarbyl group of R ¹⁴ and R ^{15 is} a substituted hydrocarbyl group having at least one group selected from the group consisting of a group having a nitrogen atom, a group having an oxygen atom and a group having a silicon atom as a substituent. I can give you. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl Group, alkoxyalkyl group such as methoxyethyl group, ethoxymethyl group, ethoxyethyl group; alkylene oxide group such as epoxy group, tetrahydrofuranyl group; alkylene oxide alkyl group such as glycidyl group, tetrahydrofurfuryl group, etc. Examples of the group having a group having a silicon atom as a substituent include a trialkylsilylalkyl group such as a trimethylsilylmethyl group.
In the present specification, the alkylene oxide group represents a monovalent group obtained by removing a hydrogen atom from a ring of a cyclic ether compound. The alkylene oxide alkyl group represents a group in which one or more hydrogen atoms of the alkyl group are substituted with an alkylene oxide group.

Examples of the substituted silyl group for R ¹⁴ and R ¹⁵ include a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group; a trialkoxysilyl group such as a trimethoxysilyl group.

The group to which R ¹⁴ and R ¹⁵ are bonded is a divalent divalent having 2 to 12 carbon atoms that may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. Group. For example, an alkylene group such as a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; an oxydialkylene group such as an oxydiethylene group and an oxydipropylene group; and —CH ₂ CH ₂ —NH—CH ₂ — And a nitrogen-containing group such as a group represented by —CH ₂ CH ₂ —N═CH—.

The group to which R ¹⁴ and R ¹⁵ are bonded is preferably a nitrogen-containing group, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—. Is more preferable.

As the same group bonded to the nitrogen of R ¹⁴ and R ^{15 with} a double bond, the number of carbon atoms optionally having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom 2 to 12 divalent groups. Examples thereof include an ethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene group, 1-methylethylidene group, 4-N, N-dimethylaminobenzylidene group.

The hydrocarbyl group of R ¹⁴ and R ¹⁵ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group, an ethyl group, or an n-propyl group. , An n-butyl group, and more preferably a methyl group or an ethyl group. The substituted hydrocarbyl group for R ¹⁴ and R ¹⁵ is preferably an alkoxyalkyl group, an alkylene oxide group, or an alkylene oxide alkyl group. The substituted silyl group for R ¹⁴ and R ¹⁵ is preferably a trialkylsilyl group or a trialkoxysilyl group, more preferably a trialkylsilyl group, still more preferably a trimethylsilyl group or a triethylsilyl group. .

R ¹⁴ and R ¹⁵ are preferably a nitrogen-containing group, an alkyl group, an alkoxyalkyl group, an alkylene oxide group, an alkylene oxide alkyl group or a substituted silyl group to which R ¹⁴ and R ¹⁵ are bonded, and more preferably an alkyl group. A group, an alkylene oxide group, an alkylene oxide alkyl group, and a trialkylsilyl group.

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

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

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

The group represented by the formula (IIa) is preferably an acyclic amino group, more preferably a dialkylamino group, from the viewpoints of fuel economy, abrasion resistance, rubber strength, long-term stability and availability of the compound. A group, a di (alkylene oxide) amino group, a di (alkylene oxide alkyl) amino group, and a di (trialkylsilyl) amino group.

As the compound represented by the formula (II), the formula (IIa) is a dialkylamino group, a di (alkoxyalkyl) amino group, a di (alkyleneoxide) amino group, a di (alkyleneoxidealkyl) amino group, a trialkylsilyl group. Examples thereof include compounds that are non-cyclic amino groups such as a group.

As the compound in which the formula (IIa) is a dialkylamino group,
[3- (dimethylamino) propyl] trimethoxysilane,
[3- (diethylamino) propyl] trimethoxysilane,
[3- (ethylmethylamino) propyl] trimethoxysilane,
[3- (dimethylamino) propyl] triethoxysilane,
[3- (diethylamino) propyl] triethoxysilane,
[3- (dialkylamino) propyl] trialkoxysilanes such as [3- (ethylmethylamino) propyl] triethoxysilane;

[3- (dimethylamino) propyl] methyldimethoxysilane,
[3- (diethylamino) propyl] methyldimethoxysilane,
[3- (ethylmethylamino) propyl] methyldimethoxysilane,
[3- (dimethylamino) propyl] ethyldimethoxysilane,
[3- (diethylamino) propyl] ethyldimethoxysilane,
[3- (ethylmethylamino) propyl] ethyldimethoxysilane,
[3- (dimethylamino) propyl] methyldiethoxysilane,
[3- (diethylamino) propyl] methyldiethoxysilane,
[3- (ethylmethylamino) propyl] methyldiethoxysilane,
[3- (dimethylamino) propyl] ethyldiethoxysilane,
[3- (diethylamino) propyl] ethyldiethoxysilane,
[3- (dialkylamino) propyl] alkyl dialkoxysilanes such as [3- (ethylmethylamino) propyl] ethyldiethoxysilane;

[3- (dimethylamino) propyl] dimethylmethoxysilane,
[3- (diethylamino) propyl] dimethylmethoxysilane,
[3- (dimethylamino) propyl] diethylmethoxysilane,
[3- (diethylamino) propyl] diethylmethoxysilane,
[3- (dimethylamino) propyl] dimethylethoxysilane,
[3- (diethylamino) propyl] dimethylethoxysilane,
[3- (dimethylamino) propyl] diethylethoxysilane,
[3- (Dialkylamino) propyl] dialkylalkoxysilanes such as [3- (diethylamino) propyl] diethylethoxysilane can be mentioned.

As the compound in which the formula (IIa) is a di (alkoxyalkyl) amino group,
{3- [di (methoxymethyl) amino] propyl} trimethoxysilane,
{3- [di (ethoxymethyl) amino] propyl} trimethoxysilane,
{3- [di (methoxyethyl) amino] propyl} trimethoxysilane,
{3- [di (ethoxyethyl) amino] propyl} trimethoxysilane,
{3- [di (methoxymethyl) amino] propyl} triethoxysilane,
{3- [di (ethoxymethyl) amino] propyl} triethoxysilane,
{3- [di (methoxyethyl) amino] propyl} triethoxysilane,
{3- [di (alkoxyalkyl) amino] propyl} trialkoxysilanes such as {3- [di (ethoxyethyl) amino] propyl} triethoxysilane;

{3- [di (methoxymethyl) amino] propyl} methyldimethoxysilane,
{3- [di (ethoxymethyl) amino] propyl} methyldimethoxysilane,
{3- [di (methoxyethyl) amino] propyl} methyldimethoxysilane,
{3- [di (ethoxyethyl) amino] propyl} methyldimethoxysilane,
{3- [di (methoxymethyl) amino] propyl} ethyldimethoxysilane,
{3- [di (ethoxymethyl) amino] propyl} ethyldimethoxysilane,
{3- [di (methoxyethyl) amino] propyl} ethyldimethoxysilane,
{3- [di (ethoxyethyl) amino] propyl} ethyldimethoxysilane,
{3- [di (methoxymethyl) amino] propyl} methyldiethoxysilane,
{3- [di (ethoxymethyl) amino] propyl} methyldiethoxysilane,
{3- [di (methoxyethyl) amino] propyl} methyldiethoxysilane,
{3- [di (ethoxyethyl) amino] propyl} methyldiethoxysilane,
{3- [di (methoxymethyl) amino] propyl} ethyldiethoxysilane,
{3- [di (ethoxymethyl) amino] propyl} ethyldiethoxysilane,
{3- [di (methoxyethyl) amino] propyl} ethyldiethoxysilane,
{3- [di (alkoxyalkyl) amino] propyl} alkyldialkoxysilanes such as {3- [di (ethoxyethyl) amino] propyl} ethyldiethoxysilane;

{3- [di (methoxymethyl) amino] propyl} dimethylmethoxysilane,
{3- [di (ethoxymethyl) amino] propyl} dimethylmethoxysilane,
{3- [di (methoxyethyl) amino] propyl} dimethylmethoxysilane,
{3- [di (ethoxyethyl) amino] propyl} dimethylmethoxysilane,
{3- [di (methoxymethyl) amino] propyl} diethylmethoxysilane,
{3- [di (ethoxymethyl) amino] propyl} diethylmethoxysilane,
{3- [di (methoxyethyl) amino] propyl} diethylmethoxysilane,
{3- [di (ethoxyethyl) amino] propyl} diethylmethoxysilane,
{3- [di (methoxymethyl) amino] propyl} dimethylethoxysilane,
{3- [di (ethoxymethyl) amino] propyl} dimethylethoxysilane,
{3- [di (methoxyethyl) amino] propyl} dimethylethoxysilane,
{3- [di (ethoxyethyl) amino] propyl} dimethylethoxysilane,
{3- [di (methoxymethyl) amino] propyl} diethylethoxysilane,
{3- [di (ethoxymethyl) amino] propyl} diethylethoxysilane,
{3- [di (methoxyethyl) amino] propyl} diethylethoxysilane,
Mention may be made of {3- [di (alkoxyalkyl) amino] propyl} dialkylalkoxysilanes such as {3- [di (ethoxyethyl) amino] propyl} diethylethoxysilane.

As the compound in which the formula (IIa) is a di (alkylene oxide) amino group,
{3- [di (epoxy) amino] propyl} trimethoxysilane,
{3- [di (epoxy) amino] propyl} triethoxysilane,
{3- [di (epoxy) amino] propyl} methyldimethoxysilane,
{3- [di (epoxy) amino] propyl} ethyldimethoxysilane,
{3- [di (epoxy) amino] propyl} methyldiethoxysilane,
{3- [di (epoxy) amino] propyl} ethyldiethoxysilane,
{3- [di (epoxy) amino] propyl} dimethylmethoxysilane,
{3- [di (epoxy) amino] propyl} diethylmethoxysilane,
{3- [di (epoxy) amino] propyl} dimethylethoxysilane,
Compounds in which the formula (IIa) is a di (epoxy) amino group such as {3- [di (epoxy) amino] propyl} diethylethoxysilane;

{3- [di (tetrahydrofuranyl) amino] propyl} trimethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} triethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} methyldimethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} ethyldimethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} methyldiethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} ethyldiethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} dimethylmethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} diethylmethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} dimethylethoxysilane,
Mention may be made of compounds in which the formula (IIa) is a di (tetrahydrofuranyl) amino group such as {3- [di (tetrahydrofuranyl) amino] propyl} diethylethoxysilane.

As the compound in which the formula (IIa) is a di (alkylene oxide alkyl) amino group,
{3- [di (glycidyl) amino] propyl} trimethoxysilane,
{3- [di (glycidyl) amino] propyl} triethoxysilane,
{3- [di (glycidyl) amino] propyl} methyldimethoxysilane,
{3- [di (glycidyl) amino] propyl} ethyldimethoxysilane,
{3- [di (glycidyl) amino] propyl} methyldiethoxysilane,
{3- [di (glycidyl) amino] propyl} ethyldiethoxysilane,
{3- [di (glycidyl) amino] propyl} dimethylmethoxysilane,
{3- [di (glycidyl) amino] propyl} diethylmethoxysilane,
{3- [di (glycidyl) amino] propyl} dimethylethoxysilane,
Compounds in which the formula (IIa) is a di (glycidyl) amino group such as {3- [di (glycidyl) amino] propyl} diethylethoxysilane;

{3- [di (tetrahydrofurfuryl) amino] propyl} trimethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} triethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} methyldimethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} ethyldimethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} methyldiethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} ethyldiethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} dimethylmethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} diethylmethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} dimethylethoxysilane,
Examples include compounds in which the formula (IIa) is a di (tetrahydrofurfuryl) amino group, such as {3- [di (tetrahydrofurfuryl) amino] propyl} diethylethoxysilane.

As a compound in which the formula (IIa) is a trialkylsilyl group,
{3- [di (trimethylsilyl) amino] propyl} trimethoxysilane,
{3- [di (t-butyldimethylsilyl) amino] propyl} trimethoxysilane,
{3- [di (trimethylsilyl) amino] propyl} triethoxysilane,
{3- [di (trialkylsilyl) amino] propyl} trialkoxysilanes such as {3- [di (t-butyldimethylsilyl) amino] propyl} triethoxysilane;

{3- [di (trimethylsilyl) amino] propyl} methyldimethoxysilane,
{3- [di (t-butyldimethylsilyl) amino] propyl} methyldimethoxysilane,
{3- [di (trimethylsilyl) amino] propyl} methyldiethoxysilane,
{3- [di (trialkylsilyl) amino] propyl} alkyldialkoxysilanes such as {3- [di (t-butyldimethylsilyl) amino] propyl} methyldiethoxysilane;

{3- [di (trimethylsilyl) amino] propyl} dimethylmethoxysilane,
{3- [di (t-butyldimethylsilyl) amino] propyl} dimethylmethoxysilane,
{3- [di (trimethylsilyl) amino] propyl} dimethylethoxysilane,
Mention may be made of {3- [di (trialkylsilyl) amino] propyl} dialkylalkoxysilanes such as {3- [di (t-butyldimethylsilyl) amino] propyl} dimethylethoxysilane.

Of these, [3- (dialkylamino) propyl] trialkoxysilane is preferred,
[3- (dimethylamino) propyl] trimethoxysilane,
[3- (diethylamino) propyl] trimethoxysilane,
[3- (dimethylamino) propyl] triethoxysilane,
[3- (Diethylamino) propyl] triethoxysilane is more preferred.

Moreover, as a compound represented by Formula (II), Formula (IIa) is 1-piperidino group, 1-hexamethyleneimino group, 1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1- Examples thereof include compounds that are cyclic amino groups such as piperazinyl group and morpholino group.

As a compound in which the formula (IIa) is a 1-piperidino group,
3- (1-piperidino) propyltrimethoxysilane,
3- (1-piperidino) propyltriethoxysilane,
3- (1-piperidino) propylmethyldimethoxysilane,
3- (1-piperidino) propylethyldimethoxysilane,
3- (1-piperidino) propylmethyldiethoxysilane,
3- (1-piperidino) propylethyldiethoxysilane and the like can be mentioned.

As a compound in which the formula (IIa) is a 1-hexamethyleneimino group,
3- (1-hexamethyleneimino) propyltrimethoxysilane,
3- (1-hexamethyleneimino) propyltriethoxysilane,
3- (1-hexamethyleneimino) propylmethyldimethoxysilane,
3- (1-hexamethyleneimino) propylethyldimethoxysilane,
3- (1-hexamethyleneimino) propylmethyldiethoxysilane,
3- (1-hexamethyleneimino) propylethyldiethoxysilane and the like can be mentioned.

As a compound in which the formula (IIa) is a 1-imidazolyl group,
N- (3-trimethoxysilylpropyl) imidazole,
Examples thereof include N- (3-triethoxysilylpropyl) imidazole.

As a compound in which the formula (IIa) is a 4,5-dihydro-1-imidazolyl group,
N- (3-trimethoxysilylpropyl) -4,5-dihydroimidazole,
Examples thereof include N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole.

As a compound in which the formula (IIa) is a 1-piperazinyl group,
3- (1-piperazinyl) propyltrimethoxysilane,
3- (1-piperazinyl) propyltriethoxysilane,
3- (1-piperazinyl) propylmethyldimethoxysilane,
3- (1-piperazinyl) propylethyldimethoxysilane,
3- (1-piperazinyl) propylmethyldiethoxysilane,
3- (1-piperazinyl) propylethyldiethoxysilane and the like can be mentioned.

As a compound in which the formula (IIa) is a morpholino group,
3-morpholinopropyltrimethoxysilane,
3-morpholinopropyltriethoxysilane,
3-morpholinopropylmethyldimethoxysilane,
3-morpholinopropylethyldimethoxysilane,
3-morpholinopropylmethyldiethoxysilane,
Examples thereof include 3-morpholinopropylethyldiethoxysilane.

In these, the compound whose formula (IIa) is 1-imidazolyl group, the compound whose formula (IIa) is 4,5-dihydro-1-imidazolyl group are preferable,
N- (3-trimethoxysilylpropyl) imidazole,
N- (3-triethoxysilylpropyl) imidazole,
N- (3-trimethoxysilylpropyl) -4,5-dihydroimidazole,
N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole is more preferred.

［式中、ｐは０又は１の整数を表し、Ｔは、炭素原子数が１〜２０のヒドロカルビレン基又は炭素原子数が１〜２０の置換ヒドロカルビレン基を表し、Ａ^２は窒素原子を有する官能基を表す。］ Hereinafter, the compound (modifier 2) having a group represented by the following formula (III) will be described.

[Wherein, p represents an integer of 0 or 1, T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms, and A ² represents nitrogen. A functional group having an atom is represented. ]

p represents an integer of 0 or 1. T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms. A ² represents a functional group having a nitrogen atom, and examples thereof include an amino group, an isocyano group, a cyano group, a pyridyl group, a piperidyl group, a pyrazinyl group, and a morpholino group.

Examples of the compound having a group represented by the formula (III) include a compound having a group represented by the following formula (IIIa) in which p in the formula (III) is 0 and A ² is an amino group. it can.

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the carboxylic acid amide compound represented by the formula (IIIa-1) include formamide compounds such as formamide, N, N-dimethylformamide, N, N-diethylformamide;
Acetamide, N, N-dimethylacetamide, N, N-diethylacetamide, aminoacetamide, N, N-dimethyl-N ′, N′-dimethylaminoacetamide, N, N-dimethylaminoacetamide, N-ethylaminoacetamide, N Acetamide compounds such as N, N-dimethyl-N′-ethylaminoacetamide, N, N-dimethylaminoacetamide, N-phenyldiacetamide;
Propionamide compounds such as propionamide and N, N-dimethylpropionamide;
Pyridylamide compounds such as 4-pyridylamide, N, N-dimethyl-4-pyridylamide;
Benzamide, N, N-dimethylbenzamide, N ′, N ′-(p-dimethylamino) benzamide, N ′, N ′-(p-diethylamino) benzamide, N, N-dimethyl-N ′, N ′-(p Benzamide compounds such as -dimethylamino) benzamide, N, N-dimethyl-N ', N'-(p-diethylamino) benzamide;
Acrylamide compounds such as N, N-dimethylacrylamide and N, N-diethylacrylamide;
Methacrylamide compounds such as N, N-dimethylmethacrylamide and N, N-diethylmethacrylamide;
Nicotinamide compounds such as N, N-dimethylnicotinamide, N, N-diethylnicotinamide;
Phthalamide compounds such as N, N, N ′, N′-tetramethylphthalamide, N, N, N ′, N′-tetraethylphthalamide;
Examples thereof include phthalimide compounds such as N-methylphthalimide and N-ethylphthalimide.

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

［式中、ｆは０〜１０の整数を表し、Ｒ^３６は、炭素原子数が１〜２０のヒドロカルビル基又は炭素原子数が１〜２０の置換ヒドロカルビル基を表す。］ Examples of the cyclic compound having a group represented by the formula (IIIa) include a compound represented by the following formula (IIIa-2) or the following formula (IIIa-3).

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

[Wherein, f represents an integer of 0 to 10, and R ³⁶ represents a hydrocarbyl group having 1 to 20 carbon atoms or a substituted hydrocarbyl group having 1 to 20 carbon atoms. ]

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

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

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

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

E and f of a formula (IIIa-2) and a formula (IIIa-3) represent the integer of 0-10, respectively. From the viewpoint of improving the fuel efficiency, wear resistance and rubber strength in a well-balanced manner, it is preferably 2 or more, and preferably from 7 or less from the viewpoint of improving economy during production.

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

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

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

［式中、Ｔは、炭素原子数が１〜２０のヒドロカルビレン基又は炭素原子数が１〜２０の置換ヒドロカルビレン基を表す。］
式（ＩＩＩｂ）で表される基を有する化合物としては、ベンズアルデヒド化合物、アセトフェノン化合物、ベンゾフェノン化合物をあげることができる。 Examples of the compound having a group represented by the formula (III) include a compound having a group represented by the following formula (IIIb) in which p in the formula (III) is 1 and A ² is an amino group. it can.

[Wherein, T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms. ]
Examples of the compound having a group represented by the formula (IIIb) include benzaldehyde compounds, acetophenone compounds, and benzophenone compounds.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the compound represented by the formula (IIIb-1) include didimethylamino-substituted benzaldehyde compounds such as 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 3,5-bis (dihexylamino) -benzaldehyde; 4-dimethylaminoacetophenone, Dialkylamino-substituted acetophenone compounds such as 4-diethylaminoacetophenone; 4-morpholinoacetophenone, heterocyclic group-substituted acetophenone compounds such as 4′-imidazol-1-yl-acetophenone and 4-pyrazolylacetophenone; 4,4′-bis (dimethylamino) ) -Benzophenone, 4,4'-bis (diethylamino) -benzophenone, 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 3-dimethylaminoben Phenone, dialkylamino-substituted benzophenone compounds such as 3-diethylamino benzophenone; 4-morpholino-benzophenone, 4 '- (imidazol-1-yl) - benzophenone, may be mentioned heterocyclic group-substituted benzophenone compounds such as 4-pyrazolyl benzophenone.

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

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

Wherein, r denotes an integer of 1 or 2, Y ¹ is a substituent on the benzene ring, represents a functional group having a nitrogen atom, if Y ¹ is more, a plurality of Y ¹ are the same But it can be different. ]

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

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

The compound represented by the formula (IIIb-1) is more preferably a heterocyclic group-substituted acetophenone compound, a dialkylamino-substituted benzophenone compound, or a heterocyclic group-substituted benzophenone compound, and particularly preferably 4′-imidazole-1 -Yl-acetophenone, 4-morpholinoacetophenone, 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4,4'-bis (dimethylamino) -benzophenone, 4,4'-bis (diethylamino) -benzophenone, 4-morpholinobenzophenone It is.

［式中、ｇは、１〜１０の整数を表し、Ｒ^２１は、水素原子、炭素原子数が１〜６のヒドロカルビル基又は炭素原子数が１〜６の置換ヒドロカルビル基を表し、Ａ^３は、酸素原子又は−ＮＲ^２２−基（Ｒ^２２は、水素原子又は炭素原子数が１〜１０のヒドロカルビル基を表す。）を表し、Ａ^４は、窒素原子及び／又は酸素原子を有する官能基を表す。］ Hereinafter, the compound (modifier 3) represented by the following formula (IV) will be described.

[Wherein, g represents an integer of 1 to 10, R ²¹ represents a hydrogen atom, a hydrocarbyl group having 1 to 6 carbon atoms, or a substituted hydrocarbyl group having 1 to 6 carbon atoms, and A ³ represents , An oxygen atom or a —NR ²² — group (R ²² represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms), and A ⁴ represents a functional group having a nitrogen atom and / or an oxygen atom. Represent. ]

g represents an integer of 1 to 10. From the viewpoint of improving fuel economy, wear resistance, and rubber strength in a well-balanced manner, it is preferably 2 or more, and from the viewpoint of improving economy during production, it is preferably 4 or less. Particularly preferred is 3.

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

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

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

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

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

A ^{3 in} Formula (IV) represents an oxygen atom or a —NR ²² — group, and R ²² represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms.

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

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

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

A ^{4 in} formula (IV) represents a functional group having a nitrogen atom and / or an oxygen atom. Examples of the functional group having a nitrogen atom include an amino group, isocyano group, cyano group, pyridyl group, piperidyl group, piperazinyl group, morpholino group and the like.

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

［式中、Ｒ^２３及びＲ^２４は、それぞれ独立に、窒素原子、酸素原子及びケイ素原子からなる原子群から選ばれる少なくとも１種の原子を有していてもよい炭素原子数が１〜６の基を表し、Ｒ^２３及びＲ^２４は結合して窒素原子と共に環構造を形成していてもよく、Ｒ^２３及びＲ^２４は窒素に二重結合で結合する同一の基であってもよい。］ A ⁴ is preferably a group or a hydroxyl group represented by the following formula (IVa), more preferably a group represented by the following formula (IVa).

[Wherein R ²³ and R ²⁴ each independently have 1 to 6 carbon atoms which may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. R ²³ and R ²⁴ may be bonded to form a ring structure together with a nitrogen atom, and R ²³ and R ²⁴ may be the same group bonded to nitrogen by a double bond. ]

Examples of R ²³ and R ^{24 in} formula (IVa) include a hydrocarbyl group having 1 to 6 carbon atoms, a substituted hydrocarbyl group having 1 to 6 carbon atoms, and a substituted silyl group.

Examples of the hydrocarbyl group of R ²³ and R ²⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, and an isopentyl group. And alkyl groups such as n-hexyl group; cycloalkyl groups such as cyclohexyl group; phenyl groups and the like.

The substituted hydrocarbyl group of R ²³ and R ^{24 includes} a substituted hydrocarbyl group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom, a group having an oxygen atom, and a group having a silicon atom. I can give you. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl Group, alkoxyalkyl group such as methoxyethyl group, ethoxymethyl group, ethoxyethyl group; alkylene oxide group such as epoxy group, tetrahydrofuranyl group; alkylene oxide alkyl group such as glycidyl group, tetrahydrofurfuryl group, etc. Examples of the group having a group having a silicon atom as a substituent include a trialkylsilylalkyl group such as a trimethylsilylmethyl group.
In the present specification, the alkylene oxide group represents a monovalent group obtained by removing a hydrogen atom from a ring of a cyclic ether compound. The alkylene oxide alkyl group represents a group in which one or more hydrogen atoms of the alkyl group are substituted with an alkylene oxide group.

Examples of the substituted silyl group for R ²³ and R ²⁴ include a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group; a trialkoxysilyl group such as a trimethoxysilyl group.

The group to which R ²³ and R ²⁴ are bonded is a divalent group having 2 to 12 carbon atoms that may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. Group. For example, an alkylene group such as a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; an oxydialkylene group such as an oxydiethylene group and an oxydipropylene group; and —CH ₂ CH ₂ —NH—CH ₂ — And a nitrogen-containing group such as a group represented by —CH ₂ CH ₂ —N═CH—.

The group to which R ²³ and R ²⁴ are bonded is preferably a nitrogen-containing group, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—. Is more preferable.

The same group bonded to the nitrogen of R ²³ and R ^{24 with} a double bond is the number of carbon atoms optionally having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom 2 to 12 divalent groups. Examples thereof include an ethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene group, 1-methylethylidene group, 4-N, N-dimethylaminobenzylidene group.

The hydrocarbyl group of R ²³ and R ²⁴ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group, an ethyl group, or an n-propyl group. , An n-butyl group, and more preferably a methyl group or an ethyl group. The substituted hydrocarbyl group for R ²³ and R ²⁴ is preferably an alkoxyalkyl group, an alkylene oxide group, or an alkylene oxide alkyl group. The substituted silyl group for R ²³ and R ²⁴ is preferably a trialkylsilyl group or a trialkoxysilyl group, more preferably a trialkylsilyl group, still more preferably a trimethylsilyl group or a triethylsilyl group. .

R ²³ and R ²⁴ are preferably a nitrogen-containing group to which R ²³ and R ²⁴ are bonded, an alkyl group, an alkoxyalkyl group, an alkylene oxide group, an alkylene oxide alkyl group, or a substituted silyl group, and more preferably an alkyl group. A group, an alkylene oxide group, an alkylene oxide alkyl group, and a trialkylsilyl group.

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

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

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

The group represented by the formula (IVa) is preferably an acyclic amino group, more preferably a dialkylamino group from the viewpoints of fuel economy, abrasion resistance, rubber strength, long-term stability and availability of the compound. A group, a di (alkylene oxide) amino group, a di (alkylene oxide alkyl) amino group, and a di (trialkylsilyl) amino group.

Examples of the compound represented by the formula (IV) include acrylamide compounds and methacrylamide compounds as compounds in which A ³ is a secondary amino group.

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

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

As the acrylamide compound in which A ⁴ is an oxygen atom-containing group,
N- (3-methoxypropyl) acrylamide,
N- (3-ethoxypropyl) acrylamide,
N- (propoxymethyl) acrylamide,
N- (butoxymethyl) acrylamide,
N-glycidyl acrylamide,
Examples thereof include N-tetrahydrofurfuryl acrylamide.

As the methacrylamide compound in which A ⁴ is an oxygen atom-containing group,
N- (3-methoxypropyl) methacrylamide,
N- (3-ethoxypropyl) methacrylamide,
N- (propoxymethyl) methacrylamide,
N- (butoxymethyl) methacrylamide,
N-glycidyl methacrylamide,
Examples thereof include N-tetrahydrofurfuryl methacrylamide.

As an acrylamide compound in which A ⁴ is a group containing nitrogen and oxygen atoms,
N- (3-di (glycidyl) aminopropyl) acrylamide,
N- (3-di (tetrahyhydrofurfuryl) aminopropyl) acrylamide and the like.

As the methacrylamide compound in which A ⁴ is a group containing a nitrogen atom and an oxygen atom,
N- (3-di (glycidyl) aminopropyl) methacrylamide,
N- (3-di (tetrahyhydrofurfuryl) aminopropyl) methacrylamide and the like.

The compound represented by Formula (IV), a compound A ³ is an oxygen atom, may be mentioned acrylate compounds, methacrylate compounds, and the like.

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

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

As the acrylate compound in which A ⁴ is an oxygen atom-containing group,
2-ethoxyethyl acrylate,
2-propoxyethyl acrylate,
2-butoxyethyl acrylate,
3-methoxypropyl acrylate,
3-ethoxypropyl acrylate,
Glycidyl acrylate,
And tetrahydrofurfuryl acrylate.

As a methacrylate compound in which A ⁴ is an oxygen atom-containing group,
2-ethoxyethyl methacrylate,
2-propoxyethyl methacrylate,
2-butoxyethyl methacrylate,
3-methoxypropyl methacrylate,
3-ethoxypropyl methacrylate,
Glycidyl methacrylate,
And tetrahydrofurfuryl methacrylate.

As the acrylate compound in which A ⁴ is a group containing a nitrogen atom and an oxygen atom,
3-di (glycidyl) aminopropyl acrylate,
Examples include 3-di (tetrahydrofurfuryl) aminopropyl acrylate.
As the methacrylate compound in which A ⁴ is a group containing a nitrogen atom and an oxygen atom,
3-di (glycidyl) aminopropyl methacrylate,
Examples include 3-di (tetrahydrofurfuryl) aminopropyl methacrylate.

As a compound represented by the formula (IV), from the viewpoint of improving fuel economy, wear resistance and rubber strength in a balanced manner,
Preferably, it is a compound in which A ⁴ is a group represented by the formula (IVa),
More preferably, it is a compound in which A ³ is an amino group and A ⁴ is a group represented by the formula (IVa),
More preferably, A ³ is a secondary amino group (—NH—), and A ⁴ is a compound represented by the formula (IVa).

As a compound in which A ³ is a secondary amino group and A ⁴ is a group represented by the formula (IVa),
Preferably,
N- (3-dialkylaminopropyl) acrylamide, N- (3-dialkylaminopropyl) methacrylamide,
More preferably,
N- (3-dimethylaminopropyl) acrylamide,
N- (3-diethylaminopropyl) acrylamide,
N- (3-dimethylaminopropyl) methacrylamide,
N- (3-diethylaminopropyl) methacrylamide.

Hereinafter, the silicon compound (modifier 4) having a group represented by the following formula (V) and / or a group represented by the following formula (VI) will be described.

Examples of the group having a group represented by the formula (V) include an amide group, a carboxylic ester group, a methacryloyl group, and an acryloyl group. Examples of the group having a group represented by the formula (VI) include oxydialkylene groups such as oxydimethylene group and oxydiethylene group; alkylene oxide groups such as epoxy group and tetrahydrofuranyl group.
In the present specification, the alkylene oxide group represents a monovalent group obtained by removing a hydrogen atom from a ring of a cyclic ether compound.

［式中、Ｒ^４１、Ｒ^４２及びＲ^４３は、それぞれ独立に、炭素原子数が１〜４のヒドロカルビル基又は炭素原子数が１〜４のヒドロカルビルオキシ基を表し、Ｒ^４１、Ｒ^４２及びＲ^４３の少なくとも１つがヒドロカルビルオキシ基である。］ The silicon compound preferably has a group represented by the following formula (VIII).

^Wherein, R ^{41, R 42} and ^{R 43} are each independently a hydrocarbyl group or a number of carbon atoms of 1 to 4 carbon atoms represents hydrocarbyloxy group having from 1 to ^4, R ^{41, R 42} and R ^At least one of ⁴³ is a hydrocarbyloxy group. ]

In the formula (VIII), examples of the hydrocarbyl group of R ⁴¹ , R ⁴² and R ⁴³ 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. An alkyl group etc. can be mention | raise | lifted. The hydrocarbyloxy group of R ⁴¹ , R ⁴² and R ^{43 is} an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group or a t-butoxy group. Can give.

The hydrocarbyl group of R ⁴¹ , R ⁴² and R ⁴³ is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group. . Further, the hydrocarbyloxy group of R ⁴¹ , R ⁴² and R ⁴³ is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms, and still more preferably a methoxy group, ethoxy It is a group.

R ⁴¹ , R ⁴² and R ⁴³ are preferably at least two of R ⁴¹ , R ⁴² and R ⁴³ are hydrocarbyloxy groups from the viewpoint of improving fuel economy, wear resistance, and rubber strength in a balanced manner. Preferably, three of R ⁴¹ , R ⁴² and R ⁴³ are hydrocarbyloxy groups.

［式中、ｈは１〜１０の整数を表し、Ｒ^４４、Ｒ^４５及びＲ^４６は、それぞれ独立に、炭素原子数が１〜４のヒドロカルビル基又は炭素原子数が１〜４のヒドロカルビルオキシ基を表し、Ｒ^４４、Ｒ^４５及びＲ^４６の少なくとも１つがヒドロカルビルオキシ基である。］ Examples of the silicon compound having a group represented by the formula (V) and a group represented by the formula (VIII) include a silicon compound having a group represented by the following formula (Va).

[Wherein, h represents an integer of 1 to 10, and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represents a hydrocarbyl group having 1 to 4 carbon atoms or a hydrocarbyloxy group having 1 to 4 carbon atoms. And at least one of R ⁴⁴ , R ⁴⁵ and R ⁴⁶ is a hydrocarbyloxy group. ]

h represents an integer of 1 to 10. From the viewpoint of improving fuel economy, wear resistance, and rubber strength in a well-balanced manner, it is preferably 2 or more, and from the viewpoint of improving economy during production, it is preferably 4 or less. Particularly preferred is 3.

For R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , the exemplified groups and preferred groups are the same as the exemplified groups and preferred groups described above for R ⁴¹ , R ⁴² and R ⁴³ of formula (VIII).

［式中、ｉは１〜１０の整数を表し、Ｒ^４７、Ｒ^４８及びＲ^４９は、それぞれ独立に、炭素原子数が１〜４のヒドロカルビル基又は炭素原子数が１〜４のヒドロカルビルオキシ基を表し、Ｒ^４７、Ｒ^４８及びＲ^４９の少なくとも１つがヒドロカルビルオキシ基であり、Ｒ^５０及びＲ^５１は、それぞれ独立に、炭素原子数が１〜１０のヒドロカルビル基、炭素原子数が１〜１０の置換ヒドロカルビル基、炭素原子数が１〜１０のヒドロカルビルオキシ基又は炭素原子数が１〜１０の置換ヒドロカルビルオキシ基を表し、Ｒ^５０及びＲ^５１は結合していてもよい。］ Examples of the silicon compound having a group represented by the formula (Va) include compounds represented by the following formula (Va-1) or the following formula (Va-2).

[Wherein, i represents an integer of 1 to 10, and R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are each independently a hydrocarbyl group having 1 to 4 carbon atoms or a hydrocarbyloxy group having 1 to 4 carbon atoms. Wherein at least one of R ⁴⁷ , R ⁴⁸ and R ⁴⁹ is a hydrocarbyloxy group, R ⁵⁰ and R ⁵¹ are each independently a hydrocarbyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. A substituted hydrocarbyl group, a hydrocarbyloxy group having 1 to 10 carbon atoms, or a substituted hydrocarbyloxy group having 1 to 10 carbon atoms, and R ⁵⁰ and R ⁵¹ may be bonded to each other. ]

［式中、ｊ、ｋ及びｌは、それぞれ独立に、１〜１０の整数を表し、Ｒ^５２〜Ｒ^６０は、それぞれ独立に、炭素原子数が１〜４のヒドロカルビル基又は炭素原子数が１〜４のヒドロカルビルオキシ基を表し、Ｒ^５２、Ｒ^５３及びＲ^５４の少なくとも１つがヒドロカルビルオキシ基であり、Ｒ^５５、Ｒ^５６及びＲ^５７の少なくとも１つがヒドロカルビルオキシ基であり、Ｒ^５８、Ｒ^５９及びＲ^６０の少なくとも１つがヒドロカルビルオキシ基である。］

[Wherein j, k and l each independently represents an integer of 1 to 10, and R ^{52 to} R ⁶⁰ each independently represents a hydrocarbyl group having 1 to 4 carbon atoms or 1 carbon atom. To 4 hydrocarbyloxy groups, wherein at least one of R ⁵² , R ⁵³ and R ⁵⁴ is a hydrocarbyloxy group, at least one of R ⁵⁵ , R ⁵⁶ and R ⁵⁷ is a hydrocarbyloxy group, and R ⁵⁸ , R ⁵⁹ And at least one of R ⁶⁰ is a hydrocarbyloxy group. ]

I in Formula (Va-1) represents an integer of 1 to 10. From the viewpoint of improving fuel economy, wear resistance, and rubber strength in a well-balanced manner, it is preferably 2 or more, and from the viewpoint of improving economy during production, it is preferably 4 or less. Particularly preferred is 3.

In the formula (Va-1), the hydrocarbyl group of R ⁴⁷ , R ⁴⁸ and R ⁴⁹ includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. And an alkyl group. The hydrocarbyloxy group of R ⁴⁷ , R ⁴⁸ and R ^{49 is} an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group or a t-butoxy group. Can give.

The hydrocarbyl group of R ⁴⁷ , R ⁴⁸ and R ⁴⁹ is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group. . Further, the hydrocarbyloxy group of R ⁴⁷ , R ⁴⁸ and R ⁴⁹ is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms, and still more preferably a methoxy group, ethoxy It is a group.

R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are preferably at least two of R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are hydrocarbyloxy groups from the viewpoint of improving fuel economy, wear resistance and rubber strength in a balanced manner. Preferably, three of R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are hydrocarbyloxy groups.

Examples of the hydrocarbyl group of R ⁵⁰ and R ⁵¹ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group.

The substituted hydrocarbyl group of R ⁵⁰ and R ^{51 is} a substituted hydrocarbyl group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom, a group having an oxygen atom, and a group having a silicon atom. I can give you. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl Group, alkoxyalkyl group such as methoxyethyl group, ethoxymethyl group, ethoxyethyl group and the like. Examples of the group having a silicon atom group as a substituent include trialkylsilyl groups such as trimethylsilylmethyl group and triethylsilylmethyl group. Examples thereof include a silylalkyl group.

Examples of the hydrocarbyloxy group of R ⁵⁰ and R ⁵¹ include alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a t-butoxy group. . Further, examples of the substituted hydrocarbyloxy group for R ⁵⁰ and R ⁵¹ include alkoxyalkoxy groups such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and an ethoxyethoxy group.

The group to which R ⁵⁰ and R ⁵¹ are bonded is a divalent divalent having 2 to 12 carbon atoms that may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. Group. For example, an alkylene group such as a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; an oxydialkylene group such as an oxydiethylene group and an oxydipropylene group; and —CH ₂ CH ₂ —NH—CH ₂ — And a nitrogen-containing group such as a group represented by —CH ₂ CH ₂ —N═CH—.

R ⁵⁰ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group and an ethyl group.

R ⁵¹ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group and an ethyl group.

J, k, and l of Formula (Va-2) each independently represent an integer of 1 to 10. From the viewpoint of improving fuel economy, wear resistance, and rubber strength in a well-balanced manner, it is preferably 2 or more, and from the viewpoint of improving economy during production, it is preferably 4 or less. Particularly preferred is 3.

In the formula (Va-2), examples of the hydrocarbyl group of R ^{52 to} R ⁶⁰ include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group. In addition, examples of the hydrocarbyloxy group of R ^{52 to} R ⁶⁰ include alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a t-butoxy group. Can do.

The hydrocarbyl group of R ^{52 to} R ⁶⁰ is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group or an ethyl group. Further, the hydrocarbyloxy group of R ^{52 to} R ⁶⁰ is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms, and still more preferably a methoxy group or an ethoxy group. .

R ⁵² , R ⁵³ and R ⁵⁴ are preferably at least two of R ⁵² , R ⁵³ and R ⁵⁴ are hydrocarbyloxy groups from the viewpoint of improving fuel economy, wear resistance and rubber strength in a balanced manner. Preferably, three of R ⁵² , R ⁵³ and R ⁵⁴ are hydrocarbyloxy groups. R ⁵⁵ , R ⁵⁶ and R ⁵⁷ are preferably at least two of R ⁵⁵ , R ⁵⁶ and R ⁵⁷ are hydrocarbyloxy groups from the viewpoint of improving fuel economy, wear resistance, and rubber strength in a balanced manner. Preferably, three of R ⁵⁵ , R ⁵⁶ and R ⁵⁷ are hydrocarbyloxy groups. In addition, R ⁵⁸ , R ⁵⁹ and R ⁶⁰ are preferably at least two of R ⁵⁸ , R ⁵⁹ and R ⁶⁰ are hydrocarbyloxy groups from the viewpoint of improving fuel economy, wear resistance and rubber strength in a balanced manner. More preferably, three of R ⁵⁸ , R ⁵⁹ and R ⁶⁰ are hydrocarbyloxy groups.

As the compound represented by the formula (Va-1),
N-methyl-N- (trimethoxysilylmethyl) -acetamide,
N-methyl-N- (triethoxysilylmethyl) -acetamide,
N-methyl-N- (2-trimethoxysilylethyl) -acetamide,
N-methyl-N- (2-triethoxysilylethyl) -acetamide,
N-methyl-N- (3-trimethoxysilylpropyl) -acetamide,
N-alkyl-N-trialkoxysilylalkyl-acetamides such as N-methyl-N- (3-triethoxysilylpropyl) -acetamide;
N-methyl-N- (trimethoxysilylmethyl) -propionamide,
N-methyl-N- (triethoxysilylmethyl) -propionamide,
N-methyl-N- (2-trimethoxysilylethyl) -propionamide,
N-methyl-N- (2-triethoxysilylethyl) -propionamide,
N-methyl-N- (3-trimethoxysilylpropyl) -propionamide,
N-alkyl-N-trialkoxysilylalkyl-propionamide, such as N-methyl-N- (3-triethoxysilylpropyl) -propionamide,
N-alkyl-N-trialkoxysilylalkyl-substituted carboxylic acid amides can be mentioned.

As the compound represented by the formula (Va-1), preferably
N-alkyl-N-trialkoxysilylalkyl-substituted carboxylic acid amide,
More preferably,
N-alkyl-N-trialkoxysilylalkyl-propionamide,
More preferably,
N-methyl-N- (3-trimethoxysilylpropyl) -propionamide,
N-methyl-N- (3-triethoxysilylpropyl) -propionamide.

As the compound represented by the formula (Va-2),
1,3,5-tris (trimethoxysilylmethyl) isocyanurate,
1,3,5-tris (triethoxysilylmethyl) isocyanurate,
1,3,5-tris (trimethoxysilylethyl) isocyanurate,
1,3,5-tris (triethoxysilylethyl) isocyanurate,
1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate,
Mention may be made of 1,3,5-tris (trialkoxysilylalkyl) isocyanurate such as 1,3,5-tris (3-triethoxysilylpropyl) isocyanurate.

As the compound represented by the formula (Va-2), preferably
1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate,
1,3,5-tris (3-triethoxysilylpropyl) isocyanurate.

［式中、ｖは１〜１０の整数を表し、Ｒ^６１、Ｒ^６２及びＲ^６３は、それぞれ独立に、炭素原子数が１〜４のヒドロカルビル基又は炭素原子数が１〜４のヒドロカルビルオキシ基を表し、Ｒ^６１、Ｒ^６２及びＲ^６３の少なくとも１つがヒドロカルビルオキシ基であり、Ｒ^６４は、炭素原子数が１〜１０のヒドロカルビル基又は炭素原子数が１〜１０の置換ヒドロカルビル基を表す。］ Examples of the silicon compound having a group represented by the formula (VI) and a group represented by the formula (VIII) include a silicon compound represented by the following formula (VIa).

[Wherein, v represents an integer of 1 to 10, and R ⁶¹ , R ⁶² and R ⁶³ each independently represents a hydrocarbyl group having 1 to 4 carbon atoms or a hydrocarbyloxy group having 1 to 4 carbon atoms. Wherein at least one of R ⁶¹ , R ⁶² and R ⁶³ is a hydrocarbyloxy group, and R ⁶⁴ represents a hydrocarbyl group having 1 to 10 carbon atoms or a substituted hydrocarbyl group having 1 to 10 carbon atoms. ]

V in the formula (VIa) represents an integer of 1 to 10. From the viewpoint of improving fuel economy, wear resistance, and rubber strength in a well-balanced manner, it is preferably 2 or more, and from the viewpoint of improving economy during production, it is preferably 4 or less. Particularly preferred is 3.

In the formula (VIa), examples of the hydrocarbyl group of R ⁶¹ , R ⁶² and R ⁶³ 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. An alkyl group etc. can be mention | raise | lifted. The hydrocarbyloxy group of R ⁶¹ , R ⁶² and R ^{63 is} an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group or a t-butoxy group. Can give.

The hydrocarbyl group of R ⁶¹ , R ⁶² and R ⁶³ is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group. . Further, the hydrocarbyloxy group of R ⁶¹ , R ⁶² and R ⁶³ is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms, and still more preferably a methoxy group or ethoxy group. It is a group.

R ⁶¹ , R ⁶² and R ⁶³ are preferably at least two of R ⁶¹ , R ⁶² and R ⁶³ are hydrocarbyloxy groups from the viewpoint of improving fuel economy, wear resistance and rubber strength in a balanced manner. Preferably, three of R ⁶¹ , R ⁶² and R ⁶³ are hydrocarbyloxy groups.

^Examples of the hydrocarbyl group of R ⁶⁴ include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups and other alkyl groups.

^Examples of the substituted hydrocarbyl group represented by R ⁶⁴ include a substituted hydrocarbyl group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom, a group having an oxygen atom, and a group having a silicon atom. it can. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl Group, alkoxyalkyl group such as methoxyethyl group, ethoxymethyl group and ethoxyethyl group; alkylene oxide alkyl group such as glycidyl group and tetrahydrofurfuryl group, and the like having a group having a silicon atom as a substituent. Includes a trialkylsilylalkyl group such as a trimethylsilylmethyl group.
In the present specification, the alkylene oxide alkyl group represents a group in which one or more hydrogen atoms of the alkyl group are substituted with an alkylene oxide group.

R ⁶⁴ is preferably an alkylene oxide alkyl group, more preferably a glycidyl group or a tetrahydrofurfuryl group.

As the compound represented by the formula (VIa),
As a compound in which R ⁶⁴ is an alkyl group,
3- (methoxy) propyltrimethoxysilane,
3- (ethoxy) propyltrimethoxysilane,
3- (n-propoxy) propyltrimethoxysilane,
3- (isopropoxy) propyltrimethoxysilane,
3- (n-butoxy) propyltrimethoxysilane,
3- (sec-butoxy) propyltrimethoxysilane,
Mention may be made of 3- (alkoxy) propyltrialkoxysilanes such as 3- (t-butoxy) propyltrimethoxysilane.

As a compound in which R ⁶⁴ is an alkylene oxide alkyl group,
2-glycidoxyethyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane,
2-glycidoxyethyl triethoxysilane,
Glycidoxyalkyltrialkoxysilanes such as 3-glycidoxypropyltriethoxysilane;
2-tetrahydrofurfuryloxyethyltrimethoxysilane,
3-tetrahydrofurfuryloxypropyltrimethoxysilane,
2-tetrahydrofurfuryloxyethyl triethoxysilane,
Mention may be made of tetrahydrofurfuryloxyalkyltrialkoxysilanes such as 3-tetrahydrofurfuryloxypropyltriethoxysilane.

As a compound wherein R ⁶⁴ is an alkoxyalkyl group,
3- (methoxymethoxy) propyltrimethoxysilane,
3- (methoxyethoxy) propyltrimethoxysilane,
3- (ethoxymethoxy) propyltrimethoxysilane,
3- (ethoxyethoxy) propyltrimethoxysilane,
3- (methoxymethoxy) propyltriethoxysilane,
3- (methoxyethoxy) propyltriethoxysilane,
3- (ethoxymethoxy) propyltriethoxysilane,
Mention may be made of 3- (alkoxyalkoxy) propyltrialkoxysilanes such as 3- (ethoxyethoxy) propyltriethoxysilane.

The compound represented by the formula (VIa) is preferably a compound in which R ⁶⁴ is an alkylene oxide alkyl group, more preferably
3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropyltriethoxysilane,
3-tetrahydrofurfuryloxypropyltrimethoxysilane,
3-tetrahydrofurfuryloxypropyltriethoxysilane.

Examples of the silicon compound having a group represented by the formula (V), a group represented by the formula (VI), and a group represented by the formula (VIII) include acryloxyalkyltrialkoxysilane and methacryloxyalkyltrialkoxysilane. I can give you.

Examples of the acryloxyalkyltrialkoxysilane include 3-acryloxypropyltrialkoxysilane such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane.
Examples of the methacryloxyalkyltrialkoxysilane include 3-methacryloxypropyltrialkoxysilane such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.

Examples of the silicon compound having a group represented by the formula (V), a group represented by the formula (VI), and a group represented by the formula (VIII) include trialkoxysilylalkyl succinic anhydride and trialkoxysilylalkyl. Mention may be made of maleic anhydride.

Examples of trialkoxysilylalkyl succinic anhydrides include 3-trialkoxysilylpropyl succinic anhydrides such as 3-trimethoxysilylpropyl succinic anhydride and 3-triethoxysilylpropyl succinic anhydride.
Examples of the trialkoxysilylalkyl maleic anhydride include 3-trialkoxysilylpropyl maleic anhydride such as 3-trimethoxysilylpropyl maleic anhydride and 3-triethoxysilylpropyl maleic anhydride.

［式中、ｗは１〜１１の整数を表し、Ａ^５は窒素原子を有する官能基を表す。］ Hereinafter, the compound (modifier 5) having a group represented by the following formula (VII) will be described.

[Wherein, w represents an integer of 1 to 11, and A ⁵ represents a functional group having a nitrogen atom. ]

w represents an integer of 1 to 11. From the viewpoint of improving fuel economy, wear resistance, and rubber strength in a well-balanced manner, it is preferably 1 or more, and preferably 4 or less from the viewpoint of improving economy during production. A ⁵ is a functional group having a nitrogen atom, and examples thereof include an amino group, an isocyano group, a cyano group, a pyridyl group, a piperidyl group, a pyrazinyl group, and a morpholino group.

［式中、ｚは０〜１０の整数を表し、Ｒ^７１は炭素原子数が１〜５のヒドロカルビル基を表し、Ｒ^７２、Ｒ^７３、Ｒ^７４及びＲ^７５は、それぞれ独立に、水素原子、炭素原子数が１〜５のヒドロカルビル基、炭素原子数が１〜５の置換ヒドロカルビル基又は炭素原子数が１〜５のヒドロカルビルオキシ基を表し、Ｒ^７２及びＲ^７３が複数ある場合は、複数あるＲ^７２及び複数あるＲ^７３はそれぞれ同じであっても異なっていてもよく、Ｒ^７６及びＲ^７７は、それぞれ独立に、窒素原子、酸素原子及びケイ素原子からなる原子群から選ばれる少なくとも１種の原子を有していてもよい炭素原子数が１〜６の基を表し、Ｒ^７６及びＲ^７７は結合して窒素原子と共に環構造を形成していてもよく、Ｒ^７６及びＲ^７７は窒素に二重結合で結合する同一の基であってもよい。］ Examples of the compound having a group represented by the formula (VII) include a compound represented by the following formula (VII-1).

[In the formula, z represents an integer of 0 to 10, R ⁷¹ represents a hydrocarbyl group having 1 to 5 carbon atoms, R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ each independently represent a hydrogen atom, A hydrocarbyl group having 1 to 5 carbon atoms, a substituted hydrocarbyl group having 1 to 5 carbon atoms or a hydrocarbyloxy group having 1 to 5 carbon atoms, and when there are a plurality of R ⁷² and R ⁷³ , there are a plurality R ⁷² and a plurality of R ⁷³ may be the same or different, and R ⁷⁶ and R ⁷⁷ are each independently at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. represents an number of carbon atoms which may have a atom 1-6 groups, R ⁷⁶ and R ⁷⁷ may form a ring structure with a nitrogen atom bonded to, R ⁷⁶ and R ⁷⁷ is a nitrogen With double bond It may be the same group if. ]

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

R ^{71 in} formula (VII-1) represents a hydrocarbyl group having 1 to 5 carbon atoms. ^Examples of the hydrocarbyl group of R ⁷¹ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and t-butyl group.

The hydrocarbyl group for R ⁷¹ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.

R ^{72 to} R ^{75 in the} formula (VII-1) are each independently a hydrogen atom, a hydrocarbyl group having 1 to 5 carbon atoms, a substituted hydrocarbyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. 5 represents a hydrocarbyloxy group, and when there are a plurality of R ⁷² and R ⁷³ , the plurality of R ⁷² and the plurality of R ⁷³ may be the same or different.

Examples of the hydrocarbyl group of R ^{72 to} R ⁷⁵ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and t-butyl group.

Examples of the substituted hydrocarbyl group of R ^{72 to} R ⁷⁵ include a substituted hydrocarbyl group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom and a group having an oxygen atom. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl And alkoxyalkyl groups such as a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group.

Examples of the hydrocarbyloxy group of R ^{72 to} R ⁷⁵ include alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a t-butoxy group. .

The hydrocarbyl group of R ^{72 to} R ⁷⁵ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.

The substituted hydrocarbyl group of R ^{72 to} R ⁷⁵ is preferably an alkoxyalkyl group, more preferably an alkoxyalkyl group having 1 to 4 carbon atoms, and still more preferably a methoxymethyl group or an ethoxyethyl group. .

The hydrocarbyloxy group of R ^{72 to} R ⁷⁵ is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms, and still more preferably a methoxy group or an ethoxy group.

From the viewpoint of improving fuel economy, wear resistance, and rubber strength in a well-balanced manner and economy, it is preferable that one of R ⁷⁴ and R ⁷⁵ is a hydrogen atom. More preferably, one of R ⁷⁴ and R ⁷⁵ is a hydrogen atom, and the other is an alkyl group or an alkoxy group. More preferably, one of R ⁷⁴ and R ⁷⁵ is a hydrogen atom, and the other is an alkoxy group. Particularly preferred are a methoxy group and an ethoxy group.

R ⁷⁶ and R ^{77 in} formula (VII-1) each independently have 1 carbon atom which may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. Represents a group of ˜6, R ⁷⁶ and R ⁷⁷ may combine to form a ring structure with the nitrogen atom, and R ⁷⁶ and R ⁷⁷ may be the same group bonded to the nitrogen by a double bond. Good.

Examples of R ⁷⁶ and R ^{77 in} Formula (VII-1) include a hydrocarbyl group having 1 to 6 carbon atoms, a substituted hydrocarbyl group having 1 to 6 carbon atoms, and a substituted silyl group.

Examples of the hydrocarbyl group of R ⁷⁶ and R ⁷⁷ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, and isopentyl group. And alkyl groups such as n-hexyl group; cycloalkyl groups such as cyclohexyl group; phenyl groups and the like.

The substituted hydrocarbyl group of R ⁷⁶ and R ^{77 is} a substituted hydrocarbyl group having as a substituent at least one group selected from the group consisting of a group having a nitrogen atom, a group having an oxygen atom, and a group having a silicon atom. I can give you. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl Group, alkoxyalkyl group such as methoxyethyl group, ethoxymethyl group, ethoxyethyl group; alkylene oxide group such as epoxy group, tetrahydrofuranyl group; alkylene oxide alkyl group such as glycidyl group, tetrahydrofurfuryl group, etc. Examples of the group having a group having a silicon atom as a substituent include a trialkylsilylalkyl group such as a trimethylsilylmethyl group.
In the present specification, the alkylene oxide group represents a monovalent group obtained by removing a hydrogen atom from a ring of a cyclic ether compound. The alkylene oxide alkyl group represents a group in which one or more hydrogen atoms of the alkyl group are substituted with an alkylene oxide group.

^Examples of the substituted silyl group for R ⁷⁶ and R ⁷⁷ include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group and t-butyldimethylsilyl group; trialkoxysilyl groups such as trimethoxysilyl group.

The group to which R ⁷⁶ and R ⁷⁷ are bonded is a divalent divalent having 2 to 12 carbon atoms that may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. Group. For example, an alkylene group such as a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; an oxydialkylene group such as an oxydiethylene group and an oxydipropylene group; and —CH ₂ CH ₂ —NH—CH ₂ — And a nitrogen-containing group such as a group represented by —CH ₂ CH ₂ —N═CH—.

The group to which R ⁷⁶ and R ⁷⁷ are bonded is preferably a nitrogen-containing group, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—. Is more preferable.

The same group bonded to the nitrogen of R ⁷⁶ and R ^{77 with} a double bond is the number of carbon atoms optionally having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom 2 to 12 divalent groups. Examples thereof include an ethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene group, 1-methylethylidene group, 4-N, N-dimethylaminobenzylidene group.

The hydrocarbyl group of R ⁷⁶ and R ⁷⁷ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group, an ethyl group, or an n-propyl group. , An n-butyl group, and more preferably a methyl group or an ethyl group. The substituted hydrocarbyl group for R ⁷⁶ and R ⁷⁷ is preferably an alkoxyalkyl group, an alkylene oxide group, or an alkylene oxide alkyl group. The substituted silyl group for R ⁷⁶ and R ⁷⁷ is preferably a trialkylsilyl group or a trialkoxysilyl group, more preferably a trialkylsilyl group, still more preferably a trimethylsilyl group or a triethylsilyl group. .

R ⁷⁶ and R ⁷⁷ are preferably an alkyl group, an alkoxyalkyl group, a substituted silyl group, or a nitrogen-containing group to which R ⁷⁶ and R ⁷⁷ are bonded, and more preferably an alkyl group having 1 to 4 carbon atoms. More preferred are a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and even more preferred are a methyl group and an ethyl group.

^Examples of the amino group in which R ⁷⁶ and R ⁷⁷ are bonded to a nitrogen atom include an acyclic amino group and a cyclic amino group.

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

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

The amino group in which R ⁷⁶ and R ⁷⁷ are bonded to the nitrogen atom is preferably an acyclic amino group, more preferably from the viewpoint of low fuel consumption, wear resistance, rubber strength, long-term stability and availability of the compound. Is a dialkylamino group, more preferably a dimethylamino group or a diethylamino group.

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

As the N, N-dialkyl-substituted carboxylic acid amide dialkyl acetal compound,
N, N-dimethylformamide dimethyl acetal, N, N-diethylformamide dimethyl acetal, N, N-di (n-propyl) formamide dimethyl acetal,
N, N-dimethylformamide diethyl acetal, N, N-diethylformamide diethyl acetal, N, N-di (n-propyl) formamide diethyl acetal,
N, N-dialkylformamide dialkyl acetals such as N, N-dimethylformamide ethyl methyl acetal, N, N-diethylformamide ethyl methyl acetal, N, N-di (n-propyl) formamide ethyl methyl acetal;

N, N-dimethylacetamide dimethyl acetal, N, N-diethylacetamide dimethyl acetal, N, N-di (n-propyl) acetamide dimethyl acetal,
N, N-dimethylacetamide diethyl acetal, N, N-diethylacetamide diethyl acetal, N, N-di (n-propyl) acetamide diethyl acetal,
N, N-dialkylacetamido dialkyl acetals such as N, N-dimethylacetamidoethyl methyl acetal, N, N-diethylacetamidoethyl methyl acetal, N, N-di (n-propyl) acetamidoethyl methyl acetal;

N, N-dimethylpropionamide dimethyl acetal, N, N-diethylpropionamide dimethyl acetal, N, N-di (n-propyl) propionamide dimethyl acetal,
N, N-dimethylpropionamide diethyl acetal, N, N-diethylpropionamide diethyl acetal, N, N-di (n-propyl) propionamide diethyl acetal,
N, N-dimethylpropionamidoethyl methyl acetal, N, N-diethylpropionamidoethyl methyl acetal, N, N-di (n-propyl) propionamidoethyl methyl acetal, N, N-dialkylpropionamido dialkyl acetal, etc. can give.

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

Content of the structural unit (conjugated diene unit) based on the conjugated diene in the conjugated diene polymer is preferably 95% by mass or more, and more preferably 97% by mass or more. If it is less than 95% by mass, fuel economy, wear resistance and rubber strength may not be improved in a well-balanced manner.

The vinyl bond amount of the conjugated diene polymer is preferably 80 mol% or less from the viewpoint that the fuel mileage, the wear resistance and the rubber strength are obtained in a well-balanced manner, with the content of the conjugated diene unit being 100 mol%. More preferably, it is 70 mol% or less, More preferably, it is 50 mol% or less, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more, Most preferably, it is 30 mol% or more. It is. The vinyl bond amount is determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

The weight average molecular weight (Mw) of the conjugated diene polymer is preferably 1.0 × 10 ⁵ or more, more preferably 2.0 × 10 ⁵ or more. When Mw is less than 1.0 × 10 ^5, there is a tendency that sufficient fuel efficiency is difficult to obtain. The Mw is preferably 2.5 × 10 ⁶ or less, more preferably 1.0 × 10 ⁶ or less. When Mw exceeds 2.5 × 10 ⁶ , there is a concern about deterioration of workability.
In addition, in this specification, a weight average molecular weight (Mw) can be measured with the method of the below-mentioned Example.

［式中、Ｘ^４、Ｘ^５及びＸ^６は、それぞれ独立に、下式（ＩＸａ）で表される基、ヒドロカルビル基又は置換ヒドロカルビル基を表し、Ｘ^４、Ｘ^５及びＸ^６の少なくとも１つが、下式（ＩＸａ）で表される基である。］

［式中、Ｒ^８１及びＲ^８２は、それぞれ独立に、炭素原子数が１〜６のヒドロカルビル基、炭素原子数が１〜６の置換ヒドロカルビル基、シリル基又は置換シリル基を表し、Ｒ^８１及びＲ^８２は結合して窒素原子と共に環構造を形成していてもよい。］
（工程Ｂ）：工程Ａで得られた重合体と上記変性剤１〜５の少なくとも１つとを反応させる工程。 As a suitable production method of the conjugated diene polymer, there can be mentioned a production method having the following steps A and B.
(Step A): A monomer containing a conjugated diene and a vinyl compound represented by the following formula (IX) is polymerized with an alkali metal catalyst in a hydrocarbon solvent, and the monomer unit based on the conjugated diene A step of obtaining a polymer having an alkali metal derived from the catalyst at at least one end of a polymer chain having a monomer unit based on a vinyl compound represented by the formula (IX).

[Wherein, X ⁴ , X ⁵ and X ⁶ each independently represent a group represented by the following formula (IXa), a hydrocarbyl group or a substituted hydrocarbyl group, wherein at least one of X ⁴ , X ⁵ and X ⁶ is And a group represented by the following formula (IXa). ]

^{Wherein, R 81} and ^{R 82} each independently represent a hydrocarbyl group having 1 to 6 carbon atoms, a substituted hydrocarbyl group having 1-6 carbon atoms, or a substituted silyl ^{group, R 81} and R ⁸² may be bonded to form a ring structure with the nitrogen atom. ]
(Step B): A step of reacting the polymer obtained in Step A with at least one of the modifiers 1 to 5.

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

The hydrocarbon solvent used in (Step A) is a solvent that does not deactivate the organic alkali metal compound catalyst, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Examples of the aliphatic hydrocarbon include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2- Examples include butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and the like. In addition, examples of the aromatic hydrocarbon include benzene, toluene, xylene, and ethylbenzene. Examples of the alicyclic hydrocarbon include cyclopentane and cyclohexane. These may be used alone or in combination of two or more. In these, a C2-C12 hydrocarbon is preferable.

In (Step A), a monomer containing a conjugated diene and a vinyl compound represented by the formula (IX) is polymerized, and a conjugated diene polymer having an alkali metal derived from the above-mentioned alkali metal catalyst at the end of the polymer chain. Manufacturing. Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. Used in combination of more than one species. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of availability. Further, from the viewpoint of low fuel consumption, wear resistance and rubber strength, a monomer having a butadiene unit such as 1,3-butadiene and 2,3-dimethyl-1,3-butadiene is preferable, and 1,3-butadiene is more preferable. preferable. By using the monomer which has a butadiene unit, the structural unit based on a conjugated diene can be made into a butadiene unit.

X ⁴ , X ⁵ and X ⁶ in the formula (IX) each independently represent a group represented by the formula (IXa), a hydrocarbyl group or a substituted hydrocarbyl group, and at least one of X ⁴ , X ⁵ and X ⁶ Is a group represented by the formula (IXa).

R ⁸¹ and R ^{82 in} Formula (IXa) each independently represent a hydrocarbyl group having 1 to 6 carbon atoms, a substituted hydrocarbyl group having 1 to 6 carbon atoms, a silyl group, or a substituted silyl group, and R ⁸¹ And R ⁸² may combine with each other to form a ring structure together with the nitrogen atom.

Examples of the hydrocarbyl group having 1 to 6 carbon atoms of R ⁸¹ and R ⁸² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- Examples thereof include alkyl groups such as pentyl group, neopentyl group, isopentyl group and n-hexyl group; cycloalkyl groups such as cyclohexyl group; phenyl groups and the like.

The substituted hydrocarbyl group having 1 to 6 carbon atoms of R ⁸¹ and R ⁸² is at least one group selected from the group consisting of a group having a nitrogen atom, a group having an oxygen atom, and a group having a silicon atom. The substituted hydrocarbyl group which has as a substituent can be mention | raise | lifted. Examples of the group having a group having a nitrogen atom as a substituent include dialkylaminoalkyl groups such as a dimethylaminoethyl group and a diethylaminoethyl group. Examples of the group having a group having an oxygen atom as a substituent include methoxymethyl Group, alkoxyalkyl group such as methoxyethyl group, ethoxymethyl group, ethoxyethyl group and the like, and groups having a silicon atom as a substituent include trialkylsilylalkyl groups such as trimethylsilylmethyl group, etc. I can give you.

^Examples of the substituted silyl group for R ⁸¹ and R ⁸² include a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group.

The group to which R ⁸¹ and R ⁸² are bonded is a divalent group having 1 to 12 carbon atoms, which may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom. Group. For example, an alkylene group such as a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; an oxydialkylene group such as an oxydiethylene group and an oxydipropylene group; and —CH ₂ CH ₂ —NH—CH ₂ — And a nitrogen-containing group such as a group represented by —CH ₂ CH ₂ —N═CH—.

The group to which R ⁸¹ and R ⁸² are bonded is preferably a nitrogen-containing group, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—. Is more preferable.

The hydrocarbyl group of R ⁸¹ and R ⁸² is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, Group, n-butyl group is particularly preferred. The substituted hydrocarbyl group for R ⁸¹ and R ⁸² is preferably an alkoxyalkyl group, more preferably an alkoxyalkyl group having 1 to 4 carbon atoms. The substituted silyl group for R ⁸¹ and R ⁸² is preferably a trialkylsilyl group, and more preferably a trimethylsilyl group.

R ⁸¹ and R ⁸² are preferably an alkyl group, an alkoxyalkyl group, a substituted silyl group, or a nitrogen-containing group to which R ⁸¹ and R ⁸² are bonded, more preferably an alkyl group, still more preferably carbon. It is an alkyl group having 1 to 4 atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.

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

Examples of the acyclic amino group include dimethylamino group, diethylamino group, di (n-propyl) amino group, di (isopropyl) amino group, di (n-butyl) amino group, di (sec-butyl) amino group, di ( dialkylamino groups such as tert-butyl) amino group, di (neopentyl) amino group, ethylmethylamino group; di (methoxymethyl) amino group, di (methoxyethyl) amino group, di (ethoxymethyl) amino group, di ( And di (alkoxyalkyl) amino groups such as ethoxyethyl) amino group; and di (trialkylsilyl) amino groups such as di (trimethylsilyl) amino group and di (t-butyldimethylsilyl) amino group.

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

The group represented by the formula (IXa) is preferably an acyclic amino group, more preferably a dialkylamino group, and still more preferably 1 to 1 carbon atoms from the viewpoint of economy and availability. A dialkylamino group substituted with 4 alkyl groups, and more preferably a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, and a di (n-butyl) amino group.

Examples of the hydrocarbyl group of X ^{4 to} X ^{6 in} the formula (IX) include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. be able to. Examples of the substituted hydrocarbyl group include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and an ethoxyethyl group.

The hydrocarbyl group of X ^{4 to} X ⁶ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group. Furthermore, the substituted hydrocarbyl group X ⁴ to X ^6, preferably an alkoxyalkyl group, more preferably an alkoxyalkyl group having 1 to 4 carbon atoms.

The hydrocarbyl group and substituted hydrocarbyl group of X ^{4 to} X ⁶ are preferably an alkyl group or an alkoxyalkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. It is an alkoxyalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.

At least one of X ⁴ , X ⁵ and X ^{6 in} the formula (IX) is a group represented by the formula (IXa). Preferably, two or more of X ⁴ , X ⁵ and X ⁶ are groups represented by the formula (IXa), more preferably two of X ⁴ , X ⁵ and X ⁶ are represented by the formula (IXa) It is a group represented.

As the vinyl compound represented by the formula (IX) used in (Step A), one of X ^{4 to} X ⁶ is an acyclic amino group represented by the formula (IXa), and two are hydrocarbyl groups or substituted hydrocarbyls. Examples of the group-containing compound include (dialkylamino) dialkylvinylsilane, {di (trialkylsilyl) amino} dialkylvinylsilane, (dialkylamino) dialkoxyalkylvinylsilane, and the like.

(Dialkylamino) dialkylvinylsilane includes (dimethylamino) dimethylvinylsilane, (ethylmethylamino) dimethylvinylsilane, (diethylamino) dimethylvinylsilane, (ethyl-n-propylamino) dimethylvinylsilane, (ethylisopropylamino) dimethylvinylsilane, ( Di (n-propyl) amino) dimethylvinylsilane, (diisopropylamino) dimethylvinylsilane, (n-butyl-n-propylamino) dimethylvinylsilane, (di (n-butyl) amino) dimethylvinylsilane, (dimethylamino) diethylvinylsilane, (Ethylmethylamino) diethylvinylsilane, (diethylamino) diethylvinylsilane, (ethyl-n-propylamino) diethylvinylsilane, (ethyliso (Propylamino) diethylvinylsilane, (di (n-propyl) amino) diethylvinylsilane, (diisopropylamino) diethylvinylsilane, (n-butyl-n-propylamino) diethylvinylsilane, (di (n-butyl) amino) diethylvinylsilane, ( (Dimethylamino) dipropylvinylsilane, (ethylmethylamino) dipropylvinylsilane, (diethylamino) dipropylvinylsilane, (ethyl-n-propylamino) dipropylvinylsilane, (ethylisopropylamino) dipropylvinylsilane, (di (n-propyl) ) Amino) dipropylvinylsilane, (diisopropylamino) dipropylvinylsilane, (n-butyl-n-propylamino) dipropylvinylsilane, (di (n-butyl) amino) dipropy Vinylsilane, (dimethylamino) dibutylvinylsilane, (ethylmethylamino) dibutylvinylsilane, (diethylamino) dibutylvinylsilane, (ethyl-n-propylamino) dibutylvinylsilane, (ethylisopropylamino) dibutylvinylsilane, (di (n-propyl) amino ) Dibutylvinylsilane, (diisopropylamino) dibutylvinylsilane, (n-butyl-n-propylamino) dibutylvinylsilane, (di (n-butyl) amino) dibutylvinylsilane, and the like.

As {di (trialkylsilyl) amino} dialkylvinylsilane, {di (trimethylsilyl) amino} dimethylvinylsilane, {di (t-butyldimethylsilyl) amino} dimethylvinylsilane, {di (trimethylsilyl) amino} diethylvinylsilane, {di (T-butyldimethylsilyl) amino} diethylvinylsilane and the like.

(Dialkylamino) dialkoxyalkylvinylsilane includes (dimethylamino) dimethoxymethylvinylsilane, (dimethylamino) dimethoxyethylvinylsilane, (dimethylamino) diethoxymethylvinylsilane, (dimethylamino) diethoxyethylvinylsilane, (diethylamino) dimethoxymethyl Examples thereof include vinylsilane, (diethylamino) dimethoxyethylvinylsilane, (diethylamino) diethoxymethylvinylsilane, (diethylamino) diethoxyethylvinylsilane, and the like.

Compounds in which two of X ^{4 to} X ⁶ are acyclic amino groups represented by the formula (IXa) and one is a hydrocarbyl group or a substituted hydrocarbyl group include bis (dialkylamino) alkylvinylsilane, bis {di (trialkyl Silyl) amino} alkylvinylsilane, bis (dialkylamino) alkoxyalkylvinylsilane, and the like.

Examples of bis (dialkylamino) alkylvinylsilane include bis (dimethylamino) methylvinylsilane, bis (ethylmethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (ethyl-n-propylamino) methylvinylsilane, and bis (ethylisopropyl). Amino) methylvinylsilane, bis (di (n-propyl) amino) methylvinylsilane, bis (diisopropylamino) methylvinylsilane, bis (n-butyl-n-propylamino) methylvinylsilane, bis (di (n-butyl) amino) Methylvinylsilane, bis (dimethylamino) ethylvinylsilane, bis (ethylmethylamino) ethylvinylsilane, bis (diethylamino) ethylvinylsilane, bis (ethyl-n-propylamino) ethyl Vinylsilane, bis (ethylisopropylamino) ethylvinylsilane, bis (di (n-propyl) amino) ethylvinylsilane, bis (diisopropylamino) ethylvinylsilane, bis (n-butyl-n-propylamino) ethylvinylsilane, bis (di ( n-butyl) amino) ethylvinylsilane, bis (dimethylamino) propylvinylsilane, bis (ethylmethylamino) propylvinylsilane, bis (diethylamino) propylvinylsilane, bis (ethyl-n-propylamino) propylvinylsilane, bis (ethylisopropylamino) ) Propyl vinyl silane, bis (di (n-propyl) amino) propyl vinyl silane, bis (diisopropylamino) propyl vinyl silane, bis (n-butyl-n-propylamino) Pyrvinylsilane, bis (di (n-butyl) amino) propylvinylsilane, bis (dimethylamino) butylvinylsilane, bis (ethylmethylamino) butylvinylsilane, bis (diethylamino) butylvinylsilane, bis (ethyl-n-propylamino) butyl Vinylsilane, bis (ethylisopropylamino) butylvinylsilane, bis (di (n-propyl) amino) butylvinylsilane, bis (diisopropylamino) butylvinylsilane, bis (n-butyl-n-propylamino) butylvinylsilane, bis (di ( and n-butyl) amino) butylvinylsilane.

As bis {di (trialkylsilyl) amino} alkylvinylsilane, bis {di (trimethylsilyl) amino} methylvinylsilane, bis {di (t-butyldimethylsilyl) amino} methylvinylsilane, bis {di (trimethylsilyl) amino} ethyl Examples include vinyl silane and bis {di (t-butyldimethylsilyl) amino} ethyl vinyl silane.

Bis (dialkylamino) alkoxyalkylvinylsilanes include bis (dimethylamino) methoxymethylvinylsilane, bis (dimethylamino) methoxyethylvinylsilane, bis (dimethylamino) ethoxymethylvinylsilane, bis (dimethylamino) ethoxyethylvinylsilane, and bis (diethylamino). ) Methoxymethylvinylsilane, bis (diethylamino) methoxyethylvinylsilane, bis (diethylamino) ethoxymethylvinylsilane, bis (diethylamino) ethoxyethylvinylsilane, and the like.

Examples of the compound in which three of X ^{4 to} X ⁶ are acyclic amino groups represented by the formula (IXa) include tri (dialkylamino) vinylsilane. For example, tri (dimethylamino) vinylsilane, tri (ethylmethylamino) vinylsilane, tri (diethylamino) vinylsilane, tri (ethylpropylamino) vinylsilane, tri (dipropylamino) vinylsilane, tri (butylpropylamino) vinylsilane Can do.

Compounds in which two of X ^{4 to} X ⁶ are cyclic amino groups represented by the formula (IXa) and one is a hydrocarbyl group or a substituted hydrocarbyl group include bis (morpholino) methylvinylsilane, bis (piperidino) methylvinylsilane, bis (4,5-dihydroimidazolyl) methylvinylsilane, bis (hexamethyleneimino) methylvinylsilane and the like can be mentioned.

X ^4, as ^{X 5} and vinyl compounds represented by formula (IX) is a group represented by 2 Exemplary ethynylphenylbiadamantane derivatives (IXa) of ^{X 6, preferably,} two of the non-cyclic X 4, ^{X 5} and ^{X 6} A vinyl compound that is an amino group, and is preferably bis (dialkylamino) alkylvinylsilane, more preferably bis (dimethylamino) methylvinylsilane, bis, from the viewpoint of low fuel consumption, wear resistance, and rubber strength. (Diethylamino) methylvinylsilane, bis (di (n-propyl) amino) methylvinylsilane, and bis (di (n-butyl) amino) methylvinylsilane. Among these, bis (diethylamino) methylvinylsilane and bis (di (n-butyl) amino) methylvinylsilane are preferable from the viewpoint of availability of the compound.

Polymerization in (Step A) is an agent that adjusts the vinyl bond amount of the conjugated diene unit, and an agent that adjusts the distribution of constituent units based on monomers other than the conjugated diene unit and the conjugated diene in the conjugated diene polymer chain. (Hereinafter collectively referred to as “regulator”) or the like. Examples of such agents include ether compounds, tertiary amines, and phosphine compounds. Examples of the ether compound include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and diethylene glycol diethyl ether. And aliphatic diethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, quinoline and the like. Examples of the phosphine compound include trimethylphosphine, triethylphosphine, triphenylphosphine, and the like. These may be used alone or in combination of two or more.

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

In (Step A), it is preferable to use only a conjugated diene and a vinyl compound represented by the formula (IX) as monomers. Thereby, the polymer which consists of a conjugated diene unit and the structural unit represented by Formula (I) is obtained, and the improvement effect of low fuel consumption, abrasion resistance, and rubber strength can be heightened.

In (Step B), the amount of modifiers 1 to 5 to be brought into contact with the polymer prepared in Step A is usually 0.1 to 3 moles per mole of alkali metal derived from the organic alkali metal catalyst, preferably Is 0.5 to 2 mol, more preferably 0.7 to 1.5 mol, and still more preferably 1 to 1.5 mol.

In (Step B), the temperature at which the polymer prepared in Step A is brought into contact with at least one of the modifiers 1 to 5 is usually 25 to 100 ° C, preferably 35 to 90 ° C. More preferably, it is 50-80 degreeC. The contact time is usually 60 seconds to 5 hours, preferably 5 minutes to 1 hour, more preferably 15 minutes to 1 hour.

In the method for producing the conjugated diene polymer, a coupling agent may be added to the hydrocarbon solution of the conjugated diene polymer in the polymerization termination from the start of polymerization of the monomer using an alkali metal catalyst, if necessary. Good. Examples of the coupling agent include compounds represented by the following formula (X).
R ⁹¹ _a ML _4-a (X)
[Wherein, R ⁹¹ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic residue, M represents a silicon atom or a tin atom, L represents a halogen atom or a hydrocarbyloxy group, and a represents 0 to 2 Represents an integer. ]
Here, the aromatic residue represents a monovalent group obtained by removing hydrogen bonded to an aromatic ring from an aromatic hydrocarbon.

As the coupling agent represented by the formula (X), silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxysilane, methyl Examples include trimethoxysilane, 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, from the viewpoint of processability of the conjugated diene polymer per 1 mol of alkali metal derived from the alkali metal catalyst. is there. Moreover, from a viewpoint of low fuel consumption, Preferably it is 0.4 mol or less, More preferably, it is 0.3 mol or less.

Conjugated diene polymers can be collected by known recovery methods, for example, (1) a method of adding a coagulant to a hydrocarbon solution of a conjugated diene polymer, and (2) adding steam to a hydrocarbon solution of a conjugated diene polymer. By this method, the conjugated diene polymer can be recovered from the hydrocarbon solution. The recovered conjugated diene polymer may be dried by a known dryer such as a band dryer or an extrusion dryer.

Moreover, in the manufacturing method of the said conjugated diene polymer, it is preferable to perform the process which substitutes the group represented by the formula (Ia) of a polymer by a hydroxyl group by hydrolysis etc. The treatment may be performed in the state of the polymer alone or in the state of the composition as described below. Examples of the hydrolysis method include known methods such as a method by steam stripping. The above-described processing, the X ¹ to X ³ in the formula (I) may be a hydroxyl group, fuel economy, abrasion resistance and rubber strength can be further well-balanced improved.

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 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. If the amount is less than 5% by mass, the effect of improving fuel economy tends to be difficult to obtain. The content of the conjugated diene polymer is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and particularly preferably 50% by mass or less. If it exceeds 90% by mass, the wear resistance and rubber strength tend to decrease and the cost tends to increase.

Examples of rubber components that can be used in addition to the conjugated diene polymer include conventional styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), butadiene-isoprene copolymer rubber, and butyl rubber. it can. Moreover, natural rubber (NR), an ethylene-propylene copolymer, an ethylene-octene copolymer, and the like can be given. Two or more of these rubber components may be used in combination. Especially, it is preferable to use NR and / or BR from the point that low-fuel-consumption property can be improved, and it is more preferable to use both components of NR and BR.

The NR is not particularly limited, and for example, those commonly used in the tire industry such as SIR20, RSS # 3, TSR20, deproteinized natural rubber (DPNR), and high-purity natural rubber (HPNR) can be used.

The content of NR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 50% by mass or more. If it is less than 5% by mass, the wear resistance and rubber strength tend to decrease. The NR content is preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less. When it exceeds 90 mass%, there exists a tendency for low-fuel-consumption property to fall.

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.

The content of BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. If it is less than 5% by mass, the fuel efficiency tends to decrease. The BR content is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 25% by mass or less. When it exceeds 60 mass%, there exists a tendency for abrasion resistance to fall.

The rubber composition of the present invention is characterized by compounding silica as a reinforcing agent. As the silica, those generally used in the tire industry such as dry method silica (anhydrous silica) and wet method silica (hydrous silica) can be used. Silica may be used alone or in combination of two or more.

Nitrogen adsorption specific surface area _(N 2 SA) of silica is preferably ^{40 m} 2 / g or more, more preferably ^{60 m} 2 / g or more, still more preferably from 150 meters ² / g or more, preferably 400 meters ² / g or less, more Preferably it is 360 m < ² > / g or less, More preferably, it is 200 m < ² > / g or less. Silica having a nitrogen adsorption specific surface area of less than 40 m ² / g has a small reinforcing effect and tends to decrease the wear resistance and rubber strength, and silica exceeding 400 m ² / g has poor dispersibility and increases hysteresis loss and is low. There is a tendency for fuel efficiency to decrease.
The _N 2 SA of silica is a value determined by the BET method in accordance with ASTM D3037-93.

The content of silica is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 150 parts by mass or less, preferably 100 parts by mass or less, relative to 100 parts by mass of the rubber component. More preferably, it is 60 parts by mass or less. If the silica content is less than 5 parts by mass, the wear resistance and rubber strength tend not to be sufficiently improved. On the other hand, if the silica content exceeds 150 parts by mass, the workability tends to deteriorate.

The rubber composition of the present invention preferably contains a silane coupling agent. Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxy). Silylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarb Moyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilyl Propyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide And dimethoxymethylsilylpropylbenzothiazole tetrasulfide. Of these, bis (3-triethoxysilylpropyl) tetrasulfide and 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide are preferable from the viewpoint of improving reinforcing properties. These silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of silica. If it is less than 1 part by mass, the viscosity of the unvulcanized rubber composition tends to be high and the processability tends to deteriorate. The content of the silane coupling agent is preferably 20 parts by mass or less, more preferably 15 parts by mass or less. When it exceeds 20 parts by mass, there is a tendency that an effect commensurate with the increase in cost cannot be obtained.

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, mica; silane coupling Agents; processing aids such as extender oils and lubricants; anti-aging agents can be exemplified.

Carbon black includes furnace black (furnace carbon black) such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF; acetylene black (acetylene carbon black); FT and MT Thermal black (thermal carbon black) such as: 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.

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 preferably 180 m 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 the carbon black is less than the lower limit of the above range, the reinforcing effect is small and the wear resistance and the rubber strength tend to decrease. If the upper limit of the above range is exceeded, the dispersibility is poor and the hysteresis loss. There is a tendency that the fuel efficiency is lowered due to increase. 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.

The content of carbon black is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, and preferably 100 parts by mass or less, more preferably 50 parts by mass or less with respect to 100 parts by mass of the rubber component. is there. If the carbon black content is less than 5 parts by mass, the wear resistance and rubber strength tend to be insufficient. On the other hand, if the carbon black content exceeds 100 parts by mass, the fuel economy and processability deteriorate. Tend.

The total content of silica and carbon black is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and preferably 160 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the rubber component. Or less. If the total content is less than 10 parts by mass, the wear resistance and rubber strength tend to be insufficient. On the other hand, if the total content exceeds 160 parts by mass, fuel economy and processability tend to deteriorate. is there.

As the extending oil, 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 (VG 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 disulfide Thiuram vulcanization accelerators such as: N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N, Examples thereof include sulfenamide-based vulcanization accelerators such as N′-diisopropyl-2-benzothiazole sulfenamide; guanidine-based vulcanization accelerators such as diphenylguanidine, diortolylguanidine, and orthotolylbiguanidine. Of these, a thiazole vulcanization accelerator is preferable, and N-cyclohexyl-2-benzothiazylsulfenamide is more preferable. The content of the vulcanization accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the rubber component.

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 can be used for a member of a truck / bus tire (heavy load tire), and can be particularly preferably used for a tread.

The truck / bus tire of the present invention is produced by a conventional method using the rubber composition. That is, if necessary, a rubber composition containing various additives is extruded into a desired shape at an unvulcanized stage, molded by a normal method on a tire molding machine, and other tires. Laminate together with the member to form an unvulcanized tire. The unvulcanized tire can be heated and pressurized in a vulcanizer to produce the truck / bus tire of the present invention.

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

1. Weight average molecular weight (Mw)
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) method under the following conditions (1) to (8).
(1) Apparatus: HLC-8020 manufactured by Tosoh Corporation
(2) Separation column: Tosoh GMH-XL (two in series)
(3) Measurement temperature: 40 ° C
(4) Carrier: Tetrahydrofuran (5) Flow rate: 0.6 mL / min (6) Injection volume: 5 μL
(7) Detector: Differential refraction (8) Molecular weight standard: Standard polystyrene

2. Vinyl bond amount (unit: mol%)
The amount of vinyl bonds in the polymer was determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

3. tan δ
A strip-shaped test piece having a width of 1 mm or 2 mm and a length of 40 mm was punched out from the sheet-like vulcanized rubber composition and subjected to the test. Using a spectrometer manufactured by Ueshima Seisakusho, tan δ was measured at a dynamic strain amplitude of 1%, a frequency of 10 Hz, and a temperature of 50 ° C. The reciprocal value of tan δ was expressed as an index with Comparative Example 1 being 100. The larger the value, the lower the rolling resistance and the lower the fuel consumption.

4). Wearing a wear resistance test tire on a domestic 2-D vehicle, measuring the groove depth of the tire tread after a mileage of 50,000 km, calculating the mileage when the tire groove depth is reduced by 1 mm, The index is expressed by the formula of The higher the index, the better the wear resistance.
(Abrasion resistance index) = (travel distance of each formulation) / (travel distance of Comparative Example 1) × 100

5. A tensile test was performed in accordance with JIS K6251 on the rubber test piece cut out from the tread of the tire for rubber strength test, and the elongation at break (breaking strength) was measured. The measurement results were displayed as an index with Comparative Example 1 being 100. The larger the index, the better the rubber strength (breaking strength).

Production Example 1 (Synthesis of Polymer 1)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 11.1 mmol of bis (diethylamino) methylvinylsilane and 13.1 mmol of n-butyllithium were added as a cyclohexane solution and an n-hexane solution, respectively, to initiate polymerization. 1,3-butadiene was polymerized for 3 hours while the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor. The supply amount of 1,3-butadiene in the entire polymerization was 821 g. Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 11.1 mmol of 3-diethylaminopropyltriethoxysilane was added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 1 was recovered. The evaluation results of the polymer 1 are shown in Table 1. In addition, the content of the structural unit represented by the formula (I) in the polymer calculated from the input amount and the supply amount of the raw material into the polymerization reactor is 0.008 mmol / g polymer per polymer unit mass. there were.

Production Example 2 (Synthesis of Polymer 2)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 10.5 mmol of bis (diethylamino) methylvinylsilane and 13.4 mmol of n-butyllithium were added as a cyclohexane solution and an n-hexane solution, respectively, and 1,3-butadiene was polymerized for 1 hour. During the polymerization, the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor.
After the 1-hour polymerization, 10.5 mmol of bis (diethylamino) methylvinylsilane was added as a cyclohexane solution, and the stirring rate was 130 rpm and the polymerization reactor internal temperature was 65 ° C.
Next, the monomer was continuously supplied into the polymerization reactor, and 1,3-butadiene was polymerized for 0.5 hour. During the polymerization, the stirring speed was 130 rpm, and the temperature in the polymerization reactor was 65 ° C.
After the 0.5 hour polymerization, 10.5 mmol of bis (diethylamino) methylvinylsilane was added as a cyclohexane solution, and the mixture was charged into the polymerization reactor under the conditions of a stirring speed of 130 rpm and a polymerization reactor temperature of 65 ° C.
Next, the monomer was continuously supplied into the polymerization reactor, and 1,3-butadiene was polymerized for 0.5 hour. During the polymerization, the stirring speed was 130 rpm, and the temperature in the polymerization reactor was 65 ° C. The supply amount of 1,3-butadiene in the entire polymerization was 821 g.
Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 11.1 mmol of 3-diethylaminopropyltriethoxysilane was added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 2 was recovered. The evaluation results of Polymer 2 are shown in Table 1. In addition, the content of the structural unit represented by the formula (I) in the polymer calculated from the input amount and the supply amount of the raw material into the polymerization reactor is 0.017 mmol / g polymer per polymer unit mass. there were.

Production Example 3 (Synthesis of Polymer 3)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 11.1 mmol of bis (diethylamino) methylvinylsilane and 13.1 mmol of n-butyllithium were added as a cyclohexane solution and an n-hexane solution, respectively, to initiate polymerization. 1,3-butadiene was polymerized for 3 hours while the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor. The supply amount of 1,3-butadiene in the entire polymerization was 821 g. Next, the obtained polymer solution was stirred at a stirring rate of 130 rpm, and 11.3-mmol of 1,3-dimethyl-2-imidazolidinone was added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 3 was recovered. The evaluation results of the polymer 3 are shown in Table 1. In addition, the content of the structural unit represented by the formula (I) in the polymer calculated from the input amount and the supply amount of the raw material into the polymerization reactor is 0.008 mmol / g polymer per polymer unit mass. there were.

Production Example 4 (Synthesis of Polymer 4)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 10.5 mmol of bis (diethylamino) methylvinylsilane and 13.4 mmol of n-butyllithium were added as a cyclohexane solution and an n-hexane solution, respectively, and 1,3-butadiene was polymerized for 1 hour. During the polymerization, the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor.
After the 1-hour polymerization, 10.5 mmol of bis (diethylamino) methylvinylsilane was added as a cyclohexane solution, and the stirring rate was 130 rpm and the polymerization reactor internal temperature was 65 ° C.
Next, the monomer was continuously supplied into the polymerization reactor, and 1,3-butadiene was polymerized for 0.5 hour. During the polymerization, the stirring speed was 130 rpm, and the temperature in the polymerization reactor was 65 ° C.
After the 0.5 hour polymerization, 10.5 mmol of bis (diethylamino) methylvinylsilane was added as a cyclohexane solution, and the mixture was charged into the polymerization reactor under the conditions of a stirring speed of 130 rpm and a polymerization reactor temperature of 65 ° C.
Next, the monomer was continuously supplied into the polymerization reactor, and 1,3-butadiene was polymerized for 0.5 hour. During the polymerization, the stirring speed was 130 rpm, and the temperature in the polymerization reactor was 65 ° C. The supply amount of 1,3-butadiene in the entire polymerization was 821 g.
Next, the obtained polymer solution was stirred at a stirring rate of 130 rpm, and 11.3-mmol of 1,3-dimethyl-2-imidazolidinone was added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 4 was recovered. The evaluation results of the polymer 4 are shown in Table 1. In addition, the content of the structural unit represented by the formula (I) in the polymer calculated from the input amount and the supply amount of the raw material into the polymerization reactor is 0.017 mmol / g polymer per polymer unit mass. there were.

Production Example 5 (Synthesis of Polymer 5)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 11.1 mmol of bis (diethylamino) methylvinylsilane and 13.1 mmol of n-butyllithium were added as a cyclohexane solution and an n-hexane solution, respectively, to initiate polymerization. 1,3-butadiene was polymerized for 3 hours while the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor. The supply amount of 1,3-butadiene in the entire polymerization was 821 g. Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 11.1 mmol of N- (3-dimethylaminopropyl) acrylamide was added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 5 was recovered. The evaluation results of the polymer 5 are shown in Table 1. In addition, the content of the structural unit represented by the formula (I) in the polymer calculated from the input amount and the supply amount of the raw material into the polymerization reactor is 0.008 mmol / g polymer per polymer unit mass. there were.

Production Example 6 (Synthesis of Polymer 6)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 10.5 mmol of bis (diethylamino) methylvinylsilane and 13.4 mmol of n-butyllithium were added as a cyclohexane solution and an n-hexane solution, respectively, and 1,3-butadiene was polymerized for 1 hour. During the polymerization, the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor.
After the 1-hour polymerization, 10.5 mmol of bis (diethylamino) methylvinylsilane was added as a cyclohexane solution, and the stirring rate was 130 rpm and the polymerization reactor internal temperature was 65 ° C.
Next, the monomer was continuously supplied into the polymerization reactor, and 1,3-butadiene was polymerized for 0.5 hour. During the polymerization, the stirring speed was 130 rpm, and the temperature in the polymerization reactor was 65 ° C.
After the 0.5 hour polymerization, 10.5 mmol of bis (diethylamino) methylvinylsilane was added as a cyclohexane solution, and the mixture was charged into the polymerization reactor under the conditions of a stirring speed of 130 rpm and a polymerization reactor temperature of 65 ° C.
Next, the monomer was continuously supplied into the polymerization reactor, and 1,3-butadiene was polymerized for 0.5 hour. During the polymerization, the stirring speed was 130 rpm, and the temperature in the polymerization reactor was 65 ° C. The supply amount of 1,3-butadiene in the entire polymerization was 821 g.
Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 11.1 mmol of N- (3-dimethylaminopropyl) acrylamide was added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 6 was recovered. The evaluation results of the polymer 6 are shown in Table 1. In addition, the content of the structural unit represented by the formula (I) in the polymer calculated from the input amount and the supply amount of the raw material into the polymerization reactor is 0.017 mmol / g polymer per polymer unit mass. there were.

Production Example 7 (Synthesis of Polymer 7)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 11.1 mmol of bis (diethylamino) methylvinylsilane and 13.1 mmol of n-butyllithium were added as a cyclohexane solution and an n-hexane solution, respectively, to initiate polymerization. 1,3-butadiene was polymerized for 3 hours while the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor. The supply amount of 1,3-butadiene in the entire polymerization was 821 g. Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 11.3 mmol of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate was added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 7 was recovered. The evaluation results of the polymer 7 are shown in Table 1. In addition, the content of the structural unit represented by the formula (I) in the polymer calculated from the input amount and the supply amount of the raw material into the polymerization reactor is 0.008 mmol / g polymer per polymer unit mass. there were.

Production Example 8 (Synthesis of Polymer 8)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 10.5 mmol of bis (diethylamino) methylvinylsilane and 13.4 mmol of n-butyllithium were added as a cyclohexane solution and an n-hexane solution, respectively, and 1,3-butadiene was polymerized for 1 hour. During the polymerization, the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor.
After the 1-hour polymerization, 10.5 mmol of bis (diethylamino) methylvinylsilane was added as a cyclohexane solution, and the stirring rate was 130 rpm and the polymerization reactor internal temperature was 65 ° C.
Next, the monomer was continuously supplied into the polymerization reactor, and 1,3-butadiene was polymerized for 0.5 hour. During the polymerization, the stirring speed was 130 rpm, and the temperature in the polymerization reactor was 65 ° C.
After the 0.5 hour polymerization, 10.5 mmol of bis (diethylamino) methylvinylsilane was added as a cyclohexane solution, and the mixture was charged into the polymerization reactor under the conditions of a stirring speed of 130 rpm and a polymerization reactor temperature of 65 ° C.
Next, the monomer was continuously supplied into the polymerization reactor, and 1,3-butadiene was polymerized for 0.5 hour. During the polymerization, the stirring speed was 130 rpm, and the temperature in the polymerization reactor was 65 ° C. The supply amount of 1,3-butadiene in the entire polymerization was 821 g.
Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 11.3 mmol of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate was added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 8 was recovered. The evaluation results of the polymer 8 are shown in Table 1. In addition, the content of the structural unit represented by the formula (I) in the polymer calculated from the input amount and the supply amount of the raw material into the polymerization reactor is 0.017 mmol / g polymer per polymer unit mass. there were.

Production Example 9 (Synthesis of Polymer 9)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 11.1 mmol of bis (diethylamino) methylvinylsilane and 13.1 mmol of n-butyllithium were added as a cyclohexane solution and an n-hexane solution, respectively, to initiate polymerization. 1,3-butadiene was polymerized for 3 hours while the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor. The supply amount of 1,3-butadiene in the entire polymerization was 821 g. Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 11.1 mmol of N, N-dimethylformamide dimethylacetal was added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 9 was recovered. The evaluation results of the polymer 9 are shown in Table 1. In addition, the content of the structural unit represented by the formula (I) in the polymer calculated from the input amount and the supply amount of the raw material into the polymerization reactor is 0.008 mmol / g polymer per polymer unit mass. there were.

Production Example 10 (Synthesis of Polymer 10)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 10.5 mmol of bis (diethylamino) methylvinylsilane and 13.4 mmol of n-butyllithium were added as a cyclohexane solution and an n-hexane solution, respectively, and 1,3-butadiene was polymerized for 1 hour. During the polymerization, the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor.
After the 1-hour polymerization, 10.5 mmol of bis (diethylamino) methylvinylsilane was added as a cyclohexane solution, and the stirring rate was 130 rpm and the polymerization reactor internal temperature was 65 ° C.
Next, the monomer was continuously supplied into the polymerization reactor, and 1,3-butadiene was polymerized for 0.5 hour. During the polymerization, the stirring speed was 130 rpm, and the temperature in the polymerization reactor was 65 ° C.
After the 0.5 hour polymerization, 10.5 mmol of bis (diethylamino) methylvinylsilane was added as a cyclohexane solution, and the mixture was charged into the polymerization reactor under the conditions of a stirring speed of 130 rpm and a polymerization reactor temperature of 65 ° C.
Next, the monomer was continuously supplied into the polymerization reactor, and 1,3-butadiene was polymerized for 0.5 hour. During the polymerization, the stirring speed was 130 rpm, and the temperature in the polymerization reactor was 65 ° C. The supply amount of 1,3-butadiene in the entire polymerization was 821 g.
Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 11.1 mmol of N, N-dimethylformamide dimethylacetal was added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 10 was recovered. The evaluation results of the polymer 10 are shown in Table 1. In addition, the content of the structural unit represented by the formula (I) in the polymer calculated from the input amount and the supply amount of the raw material into the polymerization reactor is 0.017 mmol / g polymer per polymer unit mass. there were.

Production Example 11 (Synthesis of Polymer 11)
Washed 20 liter stainless steel polymerization reactor, and dried, flushed with dry nitrogen, hexane (specific gravity 0.68g ^/ cm 3) 10.2kg, 1,3- butadiene 547 g, tetrahydrofuran 3.0 ml, ethylene 2.0 ml of glycol diethyl ether was charged into the polymerization reactor. Next, 13.1 mmol of n-butyllithium was added as an n-hexane solution to initiate polymerization. 1,3-butadiene was polymerized for 3 hours while the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the monomer was continuously fed into the polymerization reactor. The supply amount of 1,3-butadiene in the entire polymerization was 821 g. Next, 20 ml of hexane solution containing 0.54 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 11 was recovered. The evaluation results of the polymer 11 are shown in Table 1. In addition, since the polymer 11 did not use the compound represented by Formula (IX) at the time of a synthesis | combination, it did not contain the structural unit represented by Formula (I).

Natural rubber: RSS # 3
Butadiene rubber: Ubepol BR150B manufactured by Ube Industries, Ltd.
Polymers 1 to 10 (modified BR): Production Examples 1 to 10 above
Polymer 11 (non-modified BR): Production Example 11 above
Carbon black: Show black N220 manufactured by Showa Cabot Co., Ltd. (N ₂ SA: 120 m ² / g, average particle size: 23 nm, DBP oil absorption: 115 ml / 100 g)
Silica: Ultrasil VN3-G (N ₂ SA: 175 m ² / g) manufactured by Degussa
Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa
Anti-aging agent: NOCRACK 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Industry 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 (N-cyclohexyl-2-benzothiazylsulfenamide)

(Examples and Comparative Examples)
In accordance with the blending contents shown in Tables 2 to 6, 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 150 ° C. for 30 minutes to obtain a vulcanized rubber composition.
Further, the obtained unvulcanized rubber composition is molded into a tread shape and bonded together with other tire members on a tire molding machine to form an unvulcanized tire, which is vulcanized at 150 ° C. for 30 minutes, and tested. Tires (size: 11R22.5) were manufactured.

The obtained vulcanized rubber composition and test tire were used for evaluation by the above test method. Each test result is shown in Tables 2-6.

As shown in Tables 2 to 6, a conjugated diene polymer (polymer) having a structural unit based on a conjugated diene and a structural unit represented by the above formula (I), and having a terminal modified with a specific compound 1-10) and the rubber composition of the Example which mix | blended a predetermined amount each of silica improved the fuel-consumption property, abrasion resistance, and rubber strength with sufficient balance compared with the rubber composition of the comparative example.

Claims (9)

Containing a rubber component and silica,
Of the 100% by mass of the rubber component, a compound having a structural unit based on a conjugated diene and a structural unit represented by the following formula (I), represented by the following formula (II), represented by the following formula (III): A compound represented by the following formula (IV), a silicon compound having a group represented by the following formula (V) and / or a group represented by the following formula (VI), and the following formula ( VII) The content of the conjugated diene polymer obtained by modifying at least one end of the polymer with at least one compound selected from the group consisting of compounds having a group represented by VII) is 5% by mass or more,
The vinyl bond amount of the conjugated diene polymer is 10 mol% or more and 50 mol% or less, with the content of the structural unit based on the conjugated diene being 100 mol%,
The rubber composition for truck and bus tires, wherein the silica content is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

[Wherein, X ¹ , X ² and X ³ each independently represent a group represented by the following formula (Ia), a hydroxyl group, a hydrocarbyl group or a substituted hydrocarbyl group, and at least ^one of X ¹ , X ² and X ³ One is a group or a hydroxyl group represented by the following formula (Ia). ]

[Wherein, R ¹ and R ² independently denote a hydrocarbyl group having 1 to 6 carbon atoms, a substituted hydrocarbyl group having 1-6 carbon atoms, or a substituted silyl group, R ¹ and R ² may be bonded to form a ring structure with the nitrogen atom. ]

[Wherein, n represents an integer of 1 to 10, and R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbyl group having 1 to 4 carbon atoms or a hydrocarbyloxy group having 1 to 4 carbon atoms. Wherein at least one of R ¹¹ , R ¹² and R ¹³ is a hydrocarbyloxy group, and A ¹ represents a functional group having a nitrogen atom. ]

[Wherein, p represents an integer of 0 or 1, T represents a hydrocarbylene group having 1 to 20 carbon atoms or a substituted hydrocarbylene group having 1 to 20 carbon atoms, and A ² represents nitrogen. A functional group having an atom is represented. ]

[Wherein, g represents an integer of 1 to 10, R ²¹ represents a hydrogen atom, a hydrocarbyl group having 1 to 6 carbon atoms, or a substituted hydrocarbyl group having 1 to 6 carbon atoms, and A ³ represents , An oxygen atom or a —NR ²² — group (R ²² represents a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms), and A ⁴ represents a functional group having a nitrogen atom and / or an oxygen atom. Represent. ]

[Wherein, w represents an integer of 1 to 11, and A ⁵ represents a functional group having a nitrogen atom. ] The rubber composition for a truck / bus tire according to claim ^1, wherein R ¹ and R ^{2 in} the formula (Ia) are a hydrocarbyl group having 1 to 6 carbon atoms. The rubber composition for a truck / bus tire according to claim 1 or 2, wherein ^two of X ¹ , X ² and X ^{3 in} the formula (I) are a group or a hydroxyl group represented by the formula (Ia). . The rubber composition for a truck / bus tire according to any one of claims 1 to 3 , comprising natural rubber and / or butadiene rubber. The rubber composition for truck and bus tires according to any one of claims 1 to 4 , wherein the silica has a nitrogen adsorption specific surface area of 40 to 400 m ² / g. The conjugated diene polymer comprises a structural unit based on 1,3-butadiene and a structural unit represented by the formula (I), a compound represented by the formula (II), a group represented by the formula (III) A compound represented by formula (IV), a silicon compound having a group represented by formula (V) and / or a group represented by formula (VI), and a group represented by formula (VII) The truck / bus according to any one of claims 1 to 5, wherein the polymer is a modified butadiene polymer in which at least one end of the polymer is modified with at least one compound selected from the group consisting of compounds having: Rubber composition for tires. The rubber for trucks and bus tires according to claim 4, wherein a content of natural rubber is 50 to 90% by mass and a content of butadiene rubber is 5 to 25% by mass of 100% by mass of the rubber component. Composition. The rubber composition for a truck / bus tire according to any one of claims 1 to 7, wherein the content of carbon black with respect to 100 parts by mass of the rubber component is 20 to 100 parts by mass. Trucks and buses tires produced using the rubber composition according to any one of claims 1-8.