JP6178205B2 - Truck / Bus Tire - Google Patents

Description

The present invention relates to a rubber composition for a cap tread of a truck / bus tire and a truck / bus tire having a cap tread produced using the rubber composition.

In recent years, in the transportation industry, tires with excellent fuel efficiency have been demanded due to soaring fuel costs and increased costs due to the introduction of environmental regulations. For example, Patent Documents 1 to 3 propose a method of imparting affinity to silica by adding a specific polar group to rubber in a compound containing silica for the purpose of improving fuel efficiency. However, in recent years, further improvement in fuel efficiency has been demanded.

Among automobile tires, truck and bus tires are required to have particularly excellent wear resistance and rubber strength, but these performances are in contradiction to low fuel consumption. Furthermore, in recent years, due to high safety considerations, demand for wet grip performance for truck and bus tires has also increased, but wet grip performance is incompatible with low fuel consumption and wear resistance. . Therefore, a method for improving the fuel economy, wear resistance, rubber strength and wet grip performance in a well-balanced manner is required.

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

The present invention solves the above-mentioned problems, and can improve the fuel economy, wear resistance, rubber strength and wet grip performance in a well-balanced manner, and a rubber composition for a truck tread tire cap tread, and a truck manufactured using the same. The object is to provide bus tires.

（式中、ｍは１〜３の数を表し、Ｒ^１は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ｒ^２はヒドロカルビレン基を表し、Ｒ^２が複数ある場合、複数あるＲ^２は同一でも異なっていてもよく、Ａは置換アミノ基を表し、Ａが複数ある場合、複数あるＡは同一でも異なっていてもよく、Ｒ^３はヒドロカルビル基、置換ヒドロカルビル基又は置換アミノ基を表し、Ｒ^３が複数ある場合、複数あるＲ^３は同一でも異なっていてもよい。） The first aspect of the present invention includes a rubber component and silica, and in 100% by mass of the rubber component, a conjugated diene heavy polymer having a structural unit based on a conjugated diene and a structural unit based on a compound represented by the following formula (1). A truck / bus tire comprising a cap tread composed of a rubber composition having a coalescence (A) content of 5% by mass or more and a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component About.

(Wherein, m represents a number of 1 to 3, R ¹ is a polymerizable carbon - represents a hydrocarbyl group having a carbon double bond, R ² represents a hydrocarbylene group, when R ² is plural, R ² may be the same or different, A represents a substituted amino group, and when there are a plurality of A, a plurality of A may be the same or different, and R ³ represents a hydrocarbyl group, a substituted hydrocarbyl group or a substituted amino group. represents a group, if there are a plurality of R ^3, plural R ³ may be the same or different.)

（式中、ｎは０〜２の整数を表し、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に、水素原子又はヒドロカルビル基を表す。） In the formula (1), it is preferable that m is 1, R ¹ is a group represented by the following formula (2), R ² is an alkylene group, and R ³ is an alkyl group.

(In the formula, n represents an integer of 0 to 2, and R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a hydrocarbyl group.)

In the formula (2), it is preferable that R ⁴ , R ⁵ and R ⁶ are hydrogen atoms and n is 0.

The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the conjugated diene polymer (A) is preferably 1 to 3.

The vinyl bond content of the conjugated diene polymer (A) is preferably 20 mol% or more and 70 mol% or less, with the content of the structural unit based on the conjugated diene being 100 mol%.

（式中、ｈは１又は２を表し、ｉは１又は２を表し、ｈ＋ｉは２又は３であり、Ｒ^１１は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ｒ^１２はヒドロカルビル基を表し、Ｒ^１２が複数ある場合、複数あるＲ^１２は同一でも異なっていてもよく、Ｒ^１３は含酸素置換基を有していてもよいアリール基を表し、Ｒ^１３が複数ある場合、複数あるＲ^１３は同一でも異なっていてもよく、Ｒ^１４はアルキル基、又は置換アミノ基を表す。） The second aspect of the present invention includes a rubber component and silica, and a conjugated diene-based polymer having a structural unit based on a conjugated diene and a structural unit based on a compound represented by the following formula (4) in 100% by mass of the rubber component. A truck / bus tire comprising a cap tread composed of a rubber composition having a combined (B) content of 5% by mass or more and a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component About.

(In the formula, h represents 1 or 2, i represents 1 or 2, h + i is 2 or 3, R ¹¹ represents a hydrocarbyl group having a polymerizable carbon-carbon double bond, and R ¹² represents hydrocarbyl. represents a group, if R ¹² is plural, there R ¹² may be the same or different, R ¹³ represents an aryl group which may have an oxygen-containing substituent, if R ¹³ there are a plurality, A plurality of R ¹³ may be the same or different, and R ¹⁴ represents an alkyl group or a substituted amino group.)

（式中、ｐは０又は１であり、Ｒ^１５は水素原子又はヒドロカルビル基を表し、Ｔはヒドロカルビレン基を表す。） In the formula (4), h + i is 3, R ¹¹ is a group represented by the following formula (5), R ¹² is a tertiary alkyl group, and R ¹³ has an alkyl group. A good phenyl group is preferred.

(In the formula, p is 0 or 1, R ¹⁵ represents a hydrogen atom or a hydrocarbyl group, and T represents a hydrocarbylene group.)

In the formula (4), R ¹¹ is preferably a vinyl group.

It is preferable that the molecular weight distribution represented by ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the conjugated diene polymer (B) is 1.0 to 1.5. .

The vinyl bond content of the conjugated diene polymer (B) is preferably 20 mol% or more and 70 mol% or less, with the content of the structural unit based on the conjugated diene being 100 mol%.

（式中、ｊ〜ｌは、独立に、１〜８の整数を表す。） A third aspect of the present invention includes a rubber component and silica, and in a 100% by mass of the rubber component, in a hydrocarbon solvent, in the presence of a Lewis basic compound, a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer. A conjugated diene polymer (C) obtained by reacting a compound represented by the following formula (7) with an active conjugated diene polymer having an alkali metal terminal obtained by polymerizing a polymer with an alkali metal catalyst: ) Is 5 mass% or more, and the present invention relates to a truck / bus tire provided with a cap tread composed of a rubber composition having a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

(Wherein j to l independently represent an integer of 1 to 8)

The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the conjugated diene polymer (C) is preferably 1.0 to 1.5. .

The vinyl bond content of the conjugated diene polymer (C) is preferably 10 to 70 mol%, where the content of conjugated diene units is 100 mol%.

（式中、Ｒ^２１は水素原子又は炭素原子数１〜５のヒドロカルビル基を表し、ｓは０又は１であり、Ｒ^２２はヒドロカルビレン基を表し、Ｒ^２３及びＲ^２４は、それぞれ、ヒドロカルビル基、又は、トリヒドロカルビルシリル基、あるいは、Ｒ^２３とＲ^２４とが結合して、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビレン基、又は、Ｒ^２３とＲ^２４は１つの基であって、窒素原子に二重結合で結合する基を表す。）

（式中、ｔは１〜１０の整数を表し、Ｒ^２５、Ｒ^２６及びＲ^２７は、それぞれ、ヒドロカルビル基又はヒドロカルビルオキシ基を表し、Ｒ^２５、Ｒ^２６及びＲ^２７の少なくとも１つがヒドロカルビルオキシ基であり、Ｒ^２８及びＲ^２９は、それぞれ、水素原子、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビル基、あるいは、Ｒ^２８とＲ^２９とが結合して、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビレン基、又は、Ｒ^２８とＲ^２９は１つの基であって、窒素原子に二重結合で結合する基を表す。） The fourth aspect of the present invention includes a rubber component and silica, and a conjugated diene-based heavy component having a structural unit based on a conjugated diene and a structural unit based on a compound represented by the following formula (8) in 100% by mass of the rubber component. The content of the conjugated diene polymer (D) obtained by reacting the compound represented by the following formula (9) with one end of the coalescence is 5% by mass or more, and the content of the silica with respect to 100 parts by mass of the rubber component The present invention relates to a truck / bus tire provided with a cap tread composed of a rubber composition having an amount of 5 to 150 parts by mass.

(Wherein R ²¹ represents a hydrogen atom or a hydrocarbyl group having 1 to 5 carbon atoms, s is 0 or 1, R ²² represents a hydrocarbylene group, and R ²³ and R ²⁴ are each a hydrocarbyl group. Group, a trihydrocarbylsilyl group, or a hydrocarbylene group in which R ²³ and R ²⁴ are bonded to each other and optionally have a nitrogen atom and / or an oxygen atom, or R ²³ and R ²⁴ are 1 Represents a group which is bonded to a nitrogen atom with a double bond.)

(Wherein t represents an integer of 1 to 10, R ²⁵ , R ²⁶ and R ²⁷ each represents a hydrocarbyl group or a hydrocarbyloxy group, and at least one of R ²⁵ , R ²⁶ and R ²⁷ is a hydrocarbyloxy group. R ²⁸ and R ²⁹ are each a hydrogen atom, a nitrogen atom and / or a hydrocarbyl group optionally having an oxygen atom, or R ²⁸ and R ²⁹ are bonded to form a nitrogen atom and / or (The hydrocarbylene group which may have an oxygen atom, or R ²⁸ and R ²⁹ are one group and represent a group bonded to a nitrogen atom with a double bond.)

（式中、（ＣＨ_２）_ｕはベンゼン環上の置換基であり、ｕは０〜５の整数を表し、ｕが１〜５の整数である場合、（ＣＨ_２）_ｕが式（８）の窒素原子と結合する。） In the formula (8), R ²¹ is preferably a hydrogen atom, s is 1, and R ²² is preferably a group represented by the following formula (10).

(In the formula, (CH ₂ ) _u is a substituent on the benzene ring, u represents an integer of 0 to 5, and when u is an integer of 1 to 5, (CH ₂ ) _u is represented by formula (8). To bond with the nitrogen atom.)

In the formula (9), it is preferable that R ²⁵ , R ²⁶ and R ²⁷ are hydrocarbyloxy groups, and R ²⁸ and R ²⁹ are hydrocarbyl groups.

The content of monomer units based on the compound represented by the formula (8) is 0.01 to 20% by mass, where the total amount of monomer units in the conjugated diene polymer (D) is 100% by mass. It is preferable that

The vinyl bond content of the conjugated diene polymer (D) is preferably 20 mol% or more and 70 mol% or less, where the content of monomer units based on the conjugated diene is 100 mol%.

（式中、Ｒ^３１は水素原子又はヒドロカルビル基を表し、ｗは０又は１であり、Ｒ^３２はヒドロカルビレン基を表し、Ｂは含窒素複素環基を表す。）

（式中、ｘは１〜１０の数を表し、Ｒ^３３、Ｒ^３４及びＲ^３５は、それぞれ、ヒドロカルビル基又はヒドロカルビルオキシ基を表し、Ｒ^３３、Ｒ^３４及びＲ^３５の少なくとも１つがヒドロカルビルオキシ基であり、Ｒ^３６及びＲ^３７は、それぞれ、水素原子、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビル基、あるいは、Ｒ^３６とＲ^３７とが結合して、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビレン基、又は、Ｒ^３６とＲ^３７は１つの基であって、窒素原子に二重結合で結合する基を表す。） A fifth aspect of the present invention is a conjugated diene-based polymer comprising a rubber component and silica and having a structural unit based on a conjugated diene and a structural unit based on a compound represented by the following formula (11) in 100% by mass of the rubber component. The monomer unit content based on the compound represented by the following formula (11) is obtained by reacting one end of the blend with the compound represented by the following formula (12). The content of the conjugated diene polymer (E) that is 0.01 to 20% by mass is 5% by mass or more, with the total amount of the monomer units being 100% by mass, and the silica content relative to 100 parts by mass of the rubber component The present invention relates to a truck / bus tire provided with a cap tread composed of a rubber composition having an amount of 5 to 150 parts by mass.

(In the formula, R ³¹ represents a hydrogen atom or a hydrocarbyl group, w is 0 or 1, R ³² represents a hydrocarbylene group, and B represents a nitrogen-containing heterocyclic group.)

(Wherein x represents a number of 1 to 10, R ³³ , R ³⁴ and R ³⁵ each represent a hydrocarbyl group or a hydrocarbyloxy group, and at least one of R ³³ , R ³⁴ and R ³⁵ is a hydrocarbyloxy group. R ³⁶ and R ³⁷ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or R ³⁶ and R ³⁷ are bonded to form a nitrogen atom and / or (The hydrocarbylene group which may have an oxygen atom, or R ³⁶ and R ³⁷ are one group and represent a group bonded to a nitrogen atom with a double bond.)

In the formula (12), R ³³ , R ³⁴ and R ³⁵ are preferably hydrocarbyloxy groups, and R ³⁶ and R ³⁷ are preferably hydrocarbyl groups.

In the formula (11), it is preferable that R ³¹ is a hydrogen atom and B is a pyridyl group.

The vinyl bond content of the conjugated diene polymer (E) is preferably 20 mol% or more and 70 mol% or less, where the content of monomer units based on the conjugated diene is 100 mol%.

According to the present invention, since it is a rubber composition for truck / bus tire cap treads in which at least one of the conjugated diene polymers (A) to (E) and silica are blended, fuel efficiency and abrasion resistance are improved. It is possible to provide a truck / bus tire with improved balance in performance, rubber strength and wet grip performance.

The conjugated diene polymer (A) according to the first invention has a structural unit based on a conjugated diene and a structural unit based on a compound represented by the following formula (1).

（式中、ｍは１〜３の数を表し、Ｒ^１は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ｒ^２はヒドロカルビレン基を表し、Ｒ^２が複数ある場合、複数あるＲ^２は同一でも異なっていてもよく、Ａは置換アミノ基を表し、Ａが複数ある場合、複数あるＡは同一でも異なっていてもよく、Ｒ^３はヒドロカルビル基、置換ヒドロカルビル基又は置換アミノ基を表し、Ｒ^３が複数ある場合、複数あるＲ^３は同一でも異なっていてもよい。）

(Wherein, m represents a number of 1 to 3, R ¹ is a polymerizable carbon - represents a hydrocarbyl group having a carbon double bond, R ² represents a hydrocarbylene group, when R ² is plural, R ² may be the same or different, A represents a substituted amino group, and when there are a plurality of A, a plurality of A may be the same or different, and R ³ represents a hydrocarbyl group, a substituted hydrocarbyl group or a substituted amino group. represents a group, if there are a plurality of R ^3, plural R ³ may be the same or different.)

The conjugated diene polymer (A) has a structural unit (conjugated diene unit) based on a conjugated diene. Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. One or more of these are used. The conjugated diene is preferably 1,3-butadiene or isoprene.

M in the formula (1) is an integer of 1 to 3, and preferably 1 or 2.

R ¹ of formula (1) polymerizable carbon - represents a hydrocarbyl group having a carbon double bond, R ² represents a hydrocarbylene group, when R ² are a plurality, a plurality of R ² may be the same or different A represents a substituted amino group, and when there are a plurality of A, the plurality of A may be the same or different, R ³ represents a hydrocarbyl group, a substituted hydrocarbyl group or a substituted amino group, and there are a plurality of R ³ In this case, a plurality of R ³ may be the same or different.

As used herein, a hydrocarbyl group represents a hydrocarbon residue. A substituted hydrocarbyl group (hydrocarbyl group having a substituent) represents a group in which one or more hydrogen atoms of a hydrocarbon residue are substituted with a substituent, and a hydrocarbylene group represents a divalent hydrocarbon residue. The substituted amino group represents a group in which one or more hydrogen atoms of the amino group are substituted with a substituent.

（式中、ｎは０〜２の整数を表し、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に、水素原子又はヒドロカルビル基を表す。） Examples of R ^{1 in the} formula (1) include a group represented by the following formula (2).

(In the formula, n represents an integer of 0 to 2, and R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a hydrocarbyl group.)

Examples of the hydrocarbyl group of R ⁴ , R ⁵ and R ⁶ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and neopentyl group. Alkyl groups such as isopentyl group and n-hexyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as methylphenyl group and ethylphenyl group.

As the group represented by the formula (2), a vinyl group (R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, n = 0), an allyl group (R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, n = 1) ), 1-propenyl group (R ⁴ is methyl group, R ⁵ and R ⁶ are hydrogen atoms, n = 0), isopropenyl group (R ⁴ and R ⁵ are hydrogen atoms, R ⁶ is methyl group, n = 0) A crotyl group (R ⁴ is a methyl group, R ⁵ and R ⁶ are hydrogen atoms, n = 1), and a methallyl group (R ⁴ and R ⁵ are hydrogen atoms, R ⁶ is a methyl group, n = 1).

R ⁴ and R ⁵ are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

R ⁶ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.

N of Formula (2) represents the integer of 0-2. Preferably it is 0 or 1, more preferably 0.

The formula (2) is preferably a vinyl group (R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, n = 0) and an allyl group (R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, n = 1). More preferably, it is a vinyl group (R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, n = 0).

Examples of the hydrocarbylene group represented by R ^{2 in} the formula (1) include alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a phenylene group, a tolylene group, and a xylylene group. An arylene group; and an aralkylene group.

The number of carbon atoms of the hydrocarbylene group of R ² is preferably 1 to 10, and more preferably 1 to 4.

The hydrocarbylene group for R ² is preferably an alkylene group, more preferably an alkylene group having 1 to 4 carbon atoms, and still more preferably a methylene group or an ethylene group.

（式中、Ｒ^７及びＲ^８は、窒素原子、酸素原子及びケイ素原子からなる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のヒドロカルビル基、シリル基、置換シリル基、あるいは、Ｒ^７とＲ^８とが結合した炭素原子数が２〜２０の２価基、又は、Ｒ^７とＲ^８は１つの基であって、窒素原子に二重結合で結合する炭素原子数が２〜２０の基を表す。） Examples of the substituted amino group of A in the formula (1) include a group represented by the following formula (3).

(Wherein R ⁷ and R ⁸ are a hydrocarbyl group having 1 to 10 carbon atoms and a silyl group which may have at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a silicon atom) , A substituted silyl group, or a divalent group having 2 to 20 carbon atoms in which R ⁷ and R ⁸ are bonded, or R ⁷ and R ⁸ are one group, and are bonded to a nitrogen atom as a double bond. Represents a group having 2 to 20 carbon atoms to be bonded.)

Examples of the hydrocarbyl group of R ⁷ and R ⁸ 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; aryl groups such as phenyl group, methylphenyl group and ethylphenyl group; and aralkyl groups such as benzyl group. Preferably, it is an alkyl group.

The number of carbon atoms of the hydrocarbyl group of R ⁷ and R ⁸ is preferably 6 or less, more preferably 4 or less, and even more preferably 1 or 2.

Examples of the hydrocarbyl group having a nitrogen atom of R ⁷ and R ⁸ include dialkylaminoalkyl groups such as a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, and a diethylaminoethyl group.

The number of carbon atoms of the hydrocarbyl group having a nitrogen atom of R ⁷ and R ⁸ is preferably 6 or less, more preferably 4 or less. The number of carbon atoms is preferably 3 or more.

Examples of the hydrocarbyl group having an oxygen atom of R ⁷ and R ⁸ include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group and an ethoxyethyl group; an oxacyclo group such as an oxiranyl group and a tetrahydrofuranyl group An alkyl group; an oxacycloalkylalkyl group such as a glycidyl group and a tetrahydrofurfuryl group. Of these, an oxacycloalkyl group and an oxacycloalkylalkyl group are preferable.

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

The number of carbon atoms of the hydrocarbyl group having an oxygen atom of R ⁷ and R ⁸ is preferably 6 or less, more preferably 4 or less. The number of carbon atoms is preferably 2 or more.

Examples of the hydrocarbyl group having a silicon atom of R ⁷ and R ⁸ include a trialkylsilylalkyl group such as a trimethylsilylmethyl group.

The number of carbon atoms of the hydrocarbyl group having a silicon atom of R ⁷ and R ⁸ is preferably 6 or less, more preferably 4 or less. The number of carbon atoms is preferably 4 or more.

Examples of the substituted silyl group for R ⁷ and R ⁸ include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group and t-butyldimethylsilyl group; trialkoxysilyl groups such as trimethoxysilyl group. Preferably, it is a trialkylsilyl group.

The number of carbon atoms of the substituted silyl group of R ⁷ and R ⁸ is preferably 3 to 10, more preferably 3 to 6, and further preferably 3.

Examples of the divalent group having 2 to 20 carbon atoms to which R ⁷ and R ⁸ are bonded include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. An alkylene group such as a decamethylene group or a dodecamethylene group; an alkenylene group such as a group represented by —CH═CH—CH═CH—; a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, = CH-N = CH- group represented _by, -CH ₂ CH ₂ -N = CH- group represented _by, -CH ₂ CH ₂ CH ₂ -NH- group represented by, -CH = CHCH = A nitrogen-containing group such as a group represented by N—, a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ —;
Examples thereof include oxygen-containing groups such as a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ — and a group represented by —CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ CH ₂ —.

The number of carbon atoms of the divalent group to which R ⁷ and R ⁸ are bonded is preferably 2 to 12, and more preferably 2 to 8.

The group having 2 to 20 carbon atoms bonded to the nitrogen atom of R ⁷ and R ^{8 by} a double bond may have at least one atom selected from the group consisting of a nitrogen atom and an oxygen atom. Good group. Examples thereof include an ethylidene group, a propylidene group, a butylidene group, a 1-methylethylidene group, a 1-methylpropylidene group, a 1,3-dimethylbutylidene group, a benzylidene group, and a 4-N, N-dimethylaminobenzylidene group.

The number of carbon atoms of the group bonded to the nitrogen atom of R ⁷ and R ^{8 with} a double bond is preferably 2-12, more preferably 2-8.

Examples of the group represented by the formula (3) 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 (alkoxyalkyl) amino groups such as di (methoxymethyl) amino group, di (methoxyethyl) amino group, di (ethoxymethyl) amino group, di (ethoxyethyl) amino group;
Examples thereof include di (trialkylsilyl) amino groups such as di (trimethylsilyl) amino group and di (t-butyldimethylsilyl) amino group.
In addition, di (oxacycloalkyl) amino groups such as di (oxiranyl) amino group and di (tetrahydrofuranyl) amino group; di (oxacycloalkylalkyl) such as di (glycidyl) amino group and di (tetrahydrofurfuryl) amino group ) Amino group.
Furthermore, an ethylideneamino group, 1-methylpropylideneamino group, 1,3-dimethylbutylideneamino group, 1-methylethylideneamino group, 4-N, N-dimethylaminobenzylideneamino group can be mentioned.

Examples of the cyclic amino group include 1-aziridinyl group, 1-azetidinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1- Examples thereof include 1-polymethyleneimino group such as decamethyleneimino group and 1-dodecamethyleneimino group. Moreover, 1-pyrrolyl group, 1-imidazolidinyl group, 1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1-pyrazolidinyl group, 1-pyrazolyl group, 1-piperazinyl group, morpholino group and the like can be mentioned.

The substituted amino group represented by the formula (3) is preferably a dialkylamino group or a 1-polymethyleneimino group, and more preferably a 1-polymethyleneimino group.

R ^{3 in} formula (1) represents a hydrocarbyl group, a substituted hydrocarbyl group or a substituted amino group.

Examples of the hydrocarbyl group of R ³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, isopentyl group, n- Examples thereof include alkyl groups such as hexyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, methylphenyl group and ethylphenyl group; and aralkyl groups such as benzyl group. The hydrocarbyl group is preferably an alkyl group.

The number of carbon atoms of the hydrocarbyl group of R ³ is preferably 1 to 4, more preferably 1 or 2.

Examples of the substituted hydrocarbyl group for R ³ include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group. The substituted hydrocarbyl group is preferably an alkoxyalkyl group, and more preferably an alkoxyalkyl group having 2 to 4 carbon atoms.

The number of carbon atoms of the substituted hydrocarbyl group of R ³ is preferably 1 to 4.

Examples of the substituted amino group for R ³ include dimethylamino group, diethylamino group, di (n-propyl) amino group, di (isopropyl) amino group, di (n-butyl) amino group, di (sec-butyl) amino group, Dialkylamino groups such as di (tert-butyl) amino group, di (neopentyl) amino group, ethylmethylamino group; aralkylamino groups such as benzylamino group; arylamino groups such as phenylamino group; diaryls such as diphenylamino group Amino group; alkylideneamino group such as ethylideneamino group, 1-methylethylideneamino group, 2-methylpropylideneamino group, 1,3-dimethylbutylideneamino group; 1-aziridinyl group, 1-azetidinyl group, 1-pyrrolidinyl Group, 1-piperidinyl group, 1-hexamethyleneimino group, 1-heptamethyle Cyclic amino such as nimino, 1-pyrrolyl, 1-imidazolidinyl, 1-imidazolyl, 4,5-dihydro-1-imidazolyl, 1-pyrazolidinyl, 1-pyrazolyl, 1-piperazinyl, morpholino Group.

The substituted amino group for R ³ is preferably an acyclic amino group, and more preferably a dialkylamino group.

R ³ is preferably a hydrocarbyl group or a substituted hydrocarbyl group, and more preferably a hydrocarbyl group.

The compound represented by formula (1) is a compound in which R ¹ is a group represented by formula (2), m is 1, and A is an acyclic amino group represented by formula (3). Can be given.
As the compound,
(Dialkylamino) alkyldialkylvinylsilane,
(Dialkylamino) alkyldialkylallylsilane,
(Dialkylamino) alkyldialkyl-1-propenylsilane,
(Dialkylamino) alkyldialkylisopropenylsilane,
(Dialkylamino) alkyldialkylcrotylsilane,
(Dialkylamino) alkyldialkylmethallylsilane.
Specific compounds will be exemplified in the following paragraphs.

[1] (Dialkylamino) alkyldialkylvinylsilane:
(Dimethylamino) methyldimethylvinylsilane, (diethylamino) methyldimethylvinylsilane, (di-n-propylamino) methyldimethylvinylsilane, (di-n-butylamino) methyldimethylvinylsilane, (di-t-butylamino) methyldimethylvinylsilane ,
(Methylethylamino) methyldimethylvinylsilane, (methyl-n-propylamino) methyldimethylvinylsilane, (ethyl-n-propylamino) methyldimethylvinylsilane,
(Dimethylamino) methylmethylethylvinylsilane, (dimethylamino) methylmethyl-n-propylvinylsilane, (dimethylamino) methylethyl-n-propylvinylsilane,

2- (dimethylamino) ethyldimethylvinylsilane, 2- (diethylamino) ethyldimethylvinylsilane, 2- (di-n-propylamino) ethyldimethylvinylsilane, 2- (di-n-butylamino) ethyldimethylvinylsilane, 2- ( Di-t-butylamino) ethyldimethylvinylsilane,
2- (methylethylamino) ethyldimethylvinylsilane, 2- (methyln-propylamino) ethyldimethylvinylsilane, 2- (ethyl-n-propylamino) ethyldimethylvinylsilane,
(Dimethylamino) ethylmethylethylvinylsilane, (dimethylamino) ethylmethyl-n-propylvinylsilane, dimethylamino) ethylethyl-n-propylvinylsilane,

3- (dimethylamino) -n-propyldimethylvinylsilane, 3- (diethylamino) -n-propyldimethylvinylsilane, 3- (di-n-propylamino) -n-propyldimethylvinylsilane, 3- (di-n-butyl) Amino) -n-propyldimethylvinylsilane, 3- (di-t-butylamino) -n-propyldimethylvinylsilane,
3- (methylethylamino) -n-propyldimethylvinylsilane, 3- (methyln-propylamino) -n-propyldimethylvinylsilane, 3- (ethyl-n-propylamino) -n-propyldimethylvinylsilane,
(Dimethylamino) -n-propylmethylethylvinylsilane, (dimethylamino) -n-propylmethyl-n-propylvinylsilane, (dimethylamino) -n-propylethyl-n-propylvinylsilane.

[2] (Dialkylamino) alkyldialkylallylsilane:
(Dimethylamino) methyldimethylallylsilane, (diethylamino) methyldimethylallylsilane, (di-n-propylamino) methyldimethylallylsilane, (di-n-butyl) aminomethyldimethylallylsilane, (di-t-butyl) aminomethyldimethylallylsilane ,
(Methylethylamino) methyldimethylallylsilane, (methyl-n-propylamino) methyldimethylallylsilane, (ethyl-n-propylamino) methyldimethylallylsilane,
(Dimethylamino) methylmethylethylallylsilane, (dimethylamino) methylmethyl-n-propylallylsilane, (dimethylamino) methylethyl-n-propylallylsilane,

2- (dimethylamino) ethyldimethylallylsilane, 2- (diethylamino) ethyldimethylallylsilane, 2- (di-n-propylamino) ethyldimethylallylsilane, 2- (di-n-butylamino) ethyldimethylallylsilane, 2- ( Di-t-butylamino) ethyldimethylallylsilane,
2- (methylethylamino) ethyldimethylallylsilane, 2- (methyln-propylamino) ethyldimethylallylsilane, 2- (ethyl-n-propylamino) ethyldimethylallylsilane,
(Dimethylamino) ethylmethylethylallylsilane, (dimethylamino) ethylmethyl-n-propylallylsilane, (dimethylamino) ethylethyl-n-propylallylsilane,

3- (dimethylamino) -n-propyldimethylallylsilane, 3- (diethylamino) -n-propyldimethylallylsilane, 3- (di-n-propylamino) -n-propyldimethylallylsilane, 3- (di-n-butyl) Amino) -n-propyldimethylallylsilane, 3- (di-t-butylamino) -n-propyldimethylallylsilane,
3- (methylethylamino) -n-propyldimethylallylsilane, 3- (methyln-propylamino) -n-propyldimethylallylsilane, 3- (ethyl-n-propylamino) -n-propyldimethylallylsilane,
(Dimethylamino) -n-propylmethylethylallylsilane, (dimethylamino) -n-propylmethyl-n-propylallylsilane, (dimethylamino) -n-propylethyl-n-propylallylsilane.

[3] (Dialkylamino) alkyldialkyl-1-propenylsilane:
(Dimethylamino) methyldimethyl-1-propenylsilane, (diethylamino) methyldimethyl-1-propenylsilane, (di-n-propylamino) methyldimethyl-1-propenylsilane, (di-n-butyl) aminomethyldimethyl- 1-propenylsilane, (di-t-butyl) aminomethyldimethyl-1-propenylsilane,
(Methylethylamino) methyldimethyl-1-propenylsilane, (methyl-n-propylamino) methyldimethyl-1-propenylsilane, (ethyl-n-propylamino) methyldimethyl-1-propenylsilane,
(Dimethylamino) methylmethylethyl-1-propenylsilane, (dimethylamino) methylmethyl-n-propyl1-propenylsilane, (dimethylamino) methylethyl-n-propyl1-propenylsilane,

2- (dimethylamino) ethyldimethyl-1-propenylsilane, 2- (diethylamino) ethyldimethyl-1-propenylsilane, 2- (di-n-propylamino) ethyldimethyl-1-propenylsilane, 2- (di- n-butylamino) ethyldimethyl-1-propenylsilane, 2- (di-t-butylamino) ethyldimethyl-1-propenylsilane,
2- (methylethylamino) ethyldimethyl-1-propenylsilane, 2- (methyln-propylamino) ethyldimethyl-1-propenylsilane, 2- (ethyl-n-propylamino) ethyldimethyl-1-propenylsilane,
(Dimethylamino) ethylmethylethyl-1-propenylsilane, (dimethylamino) ethylmethyl-n-propyl1-propenylsilane, (dimethylamino) ethylethyl-n-propyl1-propenylsilane,

3- (dimethylamino) -n-propyldimethyl-1-propenylsilane, 3- (diethylamino) -n-propyldimethyl-1-propenylsilane, 3- (di-n-propylamino) -n-propyldimethyl-1 -Propenylsilane, 3- (di-n-butylamino) -n-propyldimethyl-1-propenylsilane, 3- (di-t-butylamino) -n-propyldimethyl-1-propenylsilane,
3- (methylethylamino) -n-propyldimethyl-1-propenylsilane, 3- (methyl-n-propylamino) -n-propyldimethyl-1-propenylsilane, 3- (ethyl-n-propylamino)- n-propyldimethyl-1-propenylsilane,
(Dimethylamino) -n-propylmethylethyl-1-propenylsilane, (dimethylamino) -n-propylmethyl-n-propyl1-propenylsilane, (dimethylamino) -n-propylethyl-n-propyl1-propenyl Silane.

[4] (Dialkylamino) alkyldialkylisopropenylsilane:
(Dimethylamino) methyldimethylisopropenylsilane, (diethylamino) methyldimethylisopropenylsilane, (di-n-propylamino) methyldimethylisopropenylsilane, (di-n-butyl) aminomethyldimethylisopropenylsilane, (di- t-butyl) aminomethyldimethylisopropenylsilane,
(Methylethylamino) methyldimethylisopropenylsilane, (methyl-n-propylamino) methyldimethylisopropenylsilane, (ethyl-n-propylamino) methyldimethylisopropenylsilane,
(Dimethylamino) methylmethylethylisopropenylsilane, (dimethylamino) methylmethyl-n-propylisopropenylsilane, (dimethylamino) methylethyl-n-propylisopropenylsilane,

2- (dimethylamino) ethyldimethylisopropenylsilane, 2- (diethylamino) ethyldimethylisopropenylsilane, 2- (di-n-propylamino) ethyldimethylisopropenylsilane, 2- (di-n-butylamino) ethyl Dimethyl isopropenyl silane, 2- (di-t-butylamino) ethyl dimethyl isopropenyl silane,
2- (methylethylamino) ethyldimethylisopropenylsilane, 2- (methyln-propylamino) ethyldimethylisopropenylsilane, 2- (ethyl-n-propylamino) ethyldimethylisopropenylsilane,
(Dimethylamino) ethylmethylethylisopropenylsilane, (dimethylamino) ethylmethyl-n-propylisopropenylsilane, (dimethylamino) ethylethyl-n-propylisopropenylsilane,

3- (dimethylamino) -n-propyldimethylisopropenylsilane, 3- (diethylamino) -n-propyldimethylisopropenylsilane, 3- (di-n-propylamino) -n-propyldimethylisopropenylsilane, 3- (Di-n-butylamino) -n-propyldimethylisopropenylsilane, 3- (di-t-butylamino) -n-propyldimethylisopropenylsilane,
3- (methylethylamino) -n-propyldimethylisopropenylsilane, 3- (methyln-propylamino) -n-propyldimethylisopropenylsilane, 3- (ethyl-n-propylamino) -n-propyldimethyliso Propenylsilane,
(Dimethylamino) -n-propylmethylethylisopropenylsilane, (dimethylamino) -n-propylmethyl-n-propylisopropenylsilane, (dimethylamino) -n-propylethyl-n-propylisopropenylsilane.

[5] (Dialkylamino) alkyldialkylcrotylsilane:
(Dimethylamino) methyldimethylcrotylsilane, (diethylamino) methyldimethylcrotylsilane, (di-n-propylamino) methyldimethylcrotylsilane, (di-n-butyl) aminomethyldimethylcrotylsilane, (di- t-butyl) aminomethyldimethylcrotylsilane,
(Methylethylamino) methyldimethylcrotylsilane, (methyl-n-propylamino) methyldimethylcrotylsilane, (ethyl-n-propylamino) methyldimethylcrotylsilane,
(Dimethylamino) methylmethylethylcrotylsilane, (dimethylamino) methylmethyl-n-propylcrotylsilane, (dimethylamino) methylethyl-n-propylcrotylsilane,

2- (dimethylamino) ethyldimethylcrotylsilane, 2- (diethylamino) ethyldimethylcrotylsilane, 2- (di-n-propylamino) ethyldimethylcrotylsilane, 2- (di-n-butylamino) ethyl Dimethylcrotylsilane, 2- (di-t-butylamino) ethyldimethylcrotylsilane,
2- (methylethylamino) ethyldimethylcrotylsilane, 2- (methyln-propylamino) ethyldimethylcrotylsilane, 2- (ethyl-n-propylamino) ethyldimethylcrotylsilane,
(Dimethylamino) ethylmethylethylcrotylsilane, (dimethylamino) ethylmethyl-n-propylcrotylsilane, (dimethylamino) ethylethyl-n-propylcrotylsilane,

3- (dimethylamino) -n-propyldimethylcrotylsilane, 3- (diethylamino) -n-propyldimethylcrotylsilane, 3- (di-n-propylamino) -n-propyldimethylcrotylsilane, 3- (Di-n-butylamino) -n-propyldimethylcrotylsilane, 3- (di-t-butylamino) -n-propyldimethylcrotylsilane,
3- (methylethylamino) -n-propyldimethylcrotylsilane, 3- (methyl-n-propylamino) -n-propyldimethylcrotylsilane, 3- (ethyl-n-propylamino) -n-propyldimethyl Crotylsilane,
(Dimethylamino) -n-propylmethylethylcrotylsilane, (dimethylamino) -n-propylmethyl-n-propylcrotylsilane, (dimethylamino) -n-propylethyl-n-propylcrotylsilane.

[6] (Dialkylamino) alkyldialkylmethallylsilane:
(Dimethylamino) methyldimethylmethallylsilane, (diethylamino) methyldimethylmethallylsilane, (di-n-propylamino) methyldimethylmethallylsilane, (di-n-butyl) aminomethyldimethylmethallylsilane, (di- t-butyl) aminomethyldimethylmethallylsilane,
(Methylethylamino) methyldimethylmethallylsilane, (methyl-n-propylamino) methyldimethylmethallylsilane, (ethyl-n-propylamino) methyldimethylmethallylsilane,
(Dimethylamino) methylmethylethylmethallylsilane, (dimethylamino) methylmethyl-n-propylmethallylsilane, (dimethylamino) methylethyl-n-propylmethallylsilane,

2- (dimethylamino) ethyldimethylmethallylsilane, 2- (diethylamino) ethyldimethylmethallylsilane, 2- (diethylamino) ethyldimethylmethallylsilane, 2- (di-n-propylamino) ethyldimethylmethallylsilane, 2- (di-n-butylamino) ethyldimethylmethallylsilane, 2- (di-t-butylamino) ethyldimethylmethallylsilane,
2- (methylethylamino) ethyldimethylmethallylsilane, 2- (methyln-propylamino) ethyldimethylmethallylsilane, 2- (ethyl-n-propylamino) ethyldimethylmethallylsilane,
(Dimethylamino) ethylmethylethylmethallylsilane, (dimethylamino) ethylmethyl-n-propylmethallylsilane, (dimethylamino) ethylethyl-n-propylmethallylsilane,

3- (dimethylamino) -n-propyldimethylmethallylsilane, 3- (diethylamino) -n-propyldimethylmethallylsilane, 3- (di-n-propylamino) -n-propyldimethylmethallylsilane, 3- (Di-n-butylamino) -n-propyldimethylmethallylsilane, 3- (di-t-butylamino) -n-propyldimethylmethallylsilane,
3- (methylethylamino) -n-propyldimethylmethallylsilane, 3- (methyl-n-propylamino) -n-propyldimethylmethallylsilane, 3- (ethyl-n-propylamino) -n-propyldimethyl Methallylsilane,
(Dimethylamino) -n-propylmethylethylmethallylsilane, (dimethylamino) -n-propylmethyl-n-propylmethallylsilane, (dimethylamino) -n-propylethyl-n-propylmethallylsilane.

The compound represented by the formula (1) is a compound in which R ¹ is a group represented by the formula (2), m is 1, and A is a cyclic amino group represented by the formula (3). can give.
As the compound,
1-polymethyleneiminoalkyldialkylvinylsilane,
1-polymethyleneiminoalkyldialkylallylsilane,
1-polymethyleneiminoalkyldialkyl-1-propenylsilane,
1-polymethyleneiminoalkyldialkylisopropenylsilane,
1-polymethyleneiminoalkyldialkylcrotylsilane,
An example is 1-polymethyleneiminoalkyldialkylmethallylsilane.
Specific compounds will be exemplified in the following paragraphs.

[7] 1-polymethyleneiminoalkyldialkylvinylsilane:
1-aziridinylmethyldimethylvinylsilane, 2- (1-aziridinyl) ethyldimethylvinylsilane, 3- (1-aziridinyl) -n-propyldimethylvinylsilane,
1-aziridinylmethyldiethylvinylsilane,
1-aziridinylmethyldi-n-propylvinylsilane,
2- (1-aziridinyl) ethyldiethylvinylsilane,
2- (1-aziridinyl) ethyldi-n-propylvinylsilane,
3- (1-aziridinyl) -n-propyldiethylvinylsilane,
3- (1-aziridinyl) -n-propyldi-n-propylvinylsilane,

1-azeridinylmethyldimethylvinylsilane, 2- (1-azelidinyl) ethyldimethylvinylsilane, 3- (1-azeridinyl) -n-propyldimethylvinylsilane,
1-azeridinylmethyldiethylvinylsilane,
1-azeridinylmethyldi-n-propylvinylsilane,
2- (1-azeridinyl) ethyldiethylvinylsilane,
2- (1-azeridinyl) ethyldi-n-propylvinylsilane,
3- (1-azeridinyl) -n-propyldiethylvinylsilane,
3- (1-azeridinyl) -n-propyldi-n-propylvinylsilane,

Dimethyl-1-pyrrolidinylmethylvinylsilane, dimethyl-2- (1-pyrrolidinyl) ethylvinylsilane, 3dimethyl- (1-pyrrolidinyl) -n-propylvinylsilane,
Diethyl-1-pyrrolidinylmethylvinylsilane,
1-pyrrolidinylmethyldi-n-propylvinylsilane,
Diethyl-2- (1-pyrrolidinyl) ethylvinylsilane,
2- (1-pyrrolidinyl) ethyldi-n-propylvinylsilane,
Diethyl-3- (1-pyrrolidinyl) -n-propylvinylsilane,
3- (1-pyrrolidinyl) -n-propyldi-n-propylvinylsilane,

Dimethyl-1-piperidinylmethylvinylsilane, dimethyl-2- (1-piperidinyl) ethylvinylsilane, dimethyl-3- (1-piperidinyl) -n-propylvinylsilane,
Diethyl-1-piperidinylmethylvinylsilane,
1-piperidinylmethyldi-n-propylvinylsilane,
2- (1-piperidinyl) ethyldiethylvinylsilane,
2- (1-piperidinyl) ethyldi-n-propylvinylsilane,
Diethyl-3- (1-piperidinyl) -n-propylvinylsilane,
3- (1-piperidinyl) -n-propyldi-n-propylvinylsilane,

1-hexamethyleneiminomethyldimethylvinylsilane, 2- (1-hexamethyleneimino) ethyldimethylvinylsilane, 3- (1-hexamethyleneimino) -n-propyldimethylvinylsilane,
Diethyl-1-hexamethyleneiminomethylvinylsilane,
1-hexamethyleneiminomethyldi-n-propylvinylsilane,
Diethyl-2- (1-hexamethyleneimino) ethylvinylsilane,
2- (1-hexamethyleneimino) ethyldi-n-propylvinylsilane,
Diethyl-3- (1-hexamethyleneimino) -n-propylvinylsilane,
3- (1-hexamethyleneimino) -n-propyldi-n-propylvinylsilane,

1-heptamethyleneiminomethyldimethylvinylsilane, 2- (1-heptamethyleneimino) ethyldimethylvinylsilane, 3- (1-heptamethyleneimino) -n-propyldimethylvinylsilane,
Diethyl-1-heptamethyleneiminomethylvinylsilane,
1-heptamethyleneiminomethyldi-n-propylvinylsilane,
Diethyl-2- (1-heptamethyleneimino) ethylvinylsilane,
2- (1-heptamethyleneimino) ethyldi-n-propylvinylsilane,
Diethyl-3- (1-heptamethyleneimino) -n-propylvinylsilane,
3- (1-heptamethyleneimino) -n-propyldi-n-propylvinylsilane,

Dimethyl-1-octamethyleneiminomethylvinylsilane, dimethyl-2- (1-octamethyleneimino) ethylvinylsilane, dimethyl-3- (1-octamethyleneimino) -n-propylvinylsilane,
Diethyl-1-octamethyleneiminomethylvinylsilane,
1-octamethyleneiminomethyldi-n-propylvinylsilane,
Diethyl-2- (1-octamethyleneimino) ethylvinylsilane,
2- (1-octamethyleneimino) ethyldi-n-propylvinylsilane,
Diethyl-3- (1-octamethyleneimino) -n-propylvinylsilane,
3- (1-octamethyleneimino) -n-propyldi-n-propylvinylsilane,

1-decamethyleneiminomethyldimethylvinylsilane, 2- (1-decamethyleneimino) ethyldimethylvinylsilane, 3- (1-decamethyleneimino) -n-propyldimethylvinylsilane,
1-decamethyleneiminomethyldiethylvinylsilane,
1-decamethyleneiminomethyldi-n-propylvinylsilane,
2- (1-decamethyleneimino) ethyldiethylvinylsilane,
2- (1-decamethyleneimino) ethyldi-n-propylvinylsilane,
3- (1-Decamethyleneimino) -n-propyldiethylvinylsilane,
3- (1-decamethyleneimino) -n-propyldi-n-propylvinylsilane,

1-dodecamethyleneiminomethyldimethylvinylsilane, 2- (1-dodecamethyleneimino) ethyldimethylvinylsilane, 3- (1-dodecamethyleneimino) -n-propyldimethylvinylsilane,
1-dodecamethyleneiminomethyldiethylvinylsilane,
1-dodecamethyleneiminomethyldi-n-propylvinylsilane,
2- (1-dodecamethyleneimino) ethyldiethylvinylsilane,
2- (1-dodecamethyleneimino) ethyldi-n-propylvinylsilane,
3- (1-dodecamethyleneimino) -n-propyldiethylvinylsilane,
3- (1-dodecamethyleneimino) -n-propyldi-n-propylvinylsilane.

[8] 1-polymethyleneiminoalkyldialkylallylsilane:
1-aziridinylmethyldimethylallylsilane, 2- (1-aziridinyl) ethyldimethylallylsilane, 3- (1-aziridinyl) -n-propyldimethylallylsilane,
1-aziridinylmethyldiethylallylsilane,
1-aziridinylmethyldi-n-propylallylsilane,
2- (1-aziridinyl) ethyldiethylallylsilane,
2- (1-aziridinyl) ethyldi-n-propylallylsilane,
3- (1-aziridinyl) -n-propyldiethylallylsilane,
3- (1-aziridinyl) -n-propyldi-n-propylallylsilane,

1-azeridinylmethyldimethylallylsilane, 2- (1-azeridinyl) ethyldimethylallylsilane, 3- (1-azeridinyl) -n-propyldimethylallylsilane,
1-azeridinylmethyldiethylallylsilane,
1-azeridinylmethyldi-n-propylallylsilane,
2- (1-azelidinyl) ethyldiethylallylsilane,
2- (1-azeridinyl) ethyldi-n-propylallylsilane,
3- (1-azelidinyl) -n-propyldiethylallylsilane,
3- (1-azelidinyl) -n-propyldi-n-propylallylsilane,

Dimethyl-1-pyrrolidinylmethylallylsilane, dimethyl-2- (1-pyrrolidinyl) ethylallylsilane, 3dimethyl- (1-pyrrolidinyl) -n-propylallylsilane,
Diethyl-1-pyrrolidinylmethylallylsilane,
1-pyrrolidinylmethyldi-n-propylallylsilane,
Diethyl-2- (1-pyrrolidinyl) ethylallylsilane,
2- (1-pyrrolidinyl) ethyldi-n-propylallylsilane,
Diethyl-3- (1-pyrrolidinyl) -n-propylallylsilane,
3- (1-pyrrolidinyl) -n-propyldi-n-propylallylsilane,

Dimethyl-1-piperidinylmethylallylsilane, dimethyl-2- (1-piperidinyl) ethylallylsilane, dimethyl-3- (1-piperidinyl) -n-propylallylsilane,
Diethyl-1-piperidinylmethylallylsilane,
1-piperidinylmethyldi-n-propylallylsilane,
2- (1-piperidinyl) ethyldiethylallylsilane,
2- (1-piperidinyl) ethyldi-n-propylallylsilane,
Diethyl-3- (1-piperidinyl) -n-propylallylsilane,
3- (1-piperidinyl) -n-propyldi-n-propylallylsilane,

1-hexamethyleneiminomethyldimethylallylsilane, 2- (1-hexamethyleneimino) ethyldimethylallylsilane, 3- (1-hexamethyleneimino) -n-propyldimethylallylsilane,
Diethyl-1-hexamethyleneiminomethylallylsilane,
1-hexamethyleneiminomethyldi-n-propylallylsilane,
Diethyl-2- (1-hexamethyleneimino) ethylallylsilane,
2- (1-hexamethyleneimino) ethyldi-n-propylallylsilane,
Diethyl-3- (1-hexamethyleneimino) -n-propylallylsilane,
3- (1-hexamethyleneimino) -n-propyldi-n-propylallylsilane,

1-heptamethyleneiminomethyldimethylallylsilane, 2- (1-heptamethyleneimino) ethyldimethylallylsilane, 3- (1-heptamethyleneimino) -n-propyldimethylallylsilane,
Diethyl-1-heptamethyleneiminomethylallylsilane,
1-heptamethyleneiminomethyldi-n-propylallylsilane,
Diethyl-2- (1-heptamethyleneimino) ethylallylsilane,
2- (1-heptamethyleneimino) ethyldi-n-propylallylsilane,
Diethyl-3- (1-heptamethyleneimino) -n-propylallylsilane,
3- (1-heptamethyleneimino) -n-propyldi-n-propylallylsilane,

Dimethyl-1-octamethyleneiminomethylallylsilane, dimethyl-2- (1-octamethyleneimino) ethylallylsilane, dimethyl-3- (1-octamethyleneimino) -n-propylallylsilane,
Diethyl-1-octamethyleneiminomethylallylsilane,
1-octamethyleneiminomethyldi-n-propylallylsilane,
Diethyl-2- (1-octamethyleneimino) ethylallylsilane,
2- (1-octamethyleneimino) ethyldi-n-propylallylsilane,
Diethyl-3- (1-octamethyleneimino) -n-propylallylsilane,
3- (1-octamethyleneimino) -n-propyldi-n-propylallylsilane,

1-decamethyleneiminomethyldimethylallylsilane, 2- (1-decamethyleneimino) ethyldimethylallylsilane, 3- (1-decamethyleneimino) -n-propyldimethylallylsilane,
1-decamethyleneiminomethyldiethylallylsilane,
1-decamethyleneiminomethyldi-n-propylallylsilane,
2- (1-decamethyleneimino) ethyldiethylallylsilane,
2- (1-decamethyleneimino) ethyldi-n-propylallylsilane,
3- (1-decamethyleneimino) -n-propyldiethylallylsilane,
3- (1-decamethyleneimino) -n-propyldi-n-propylallylsilane,

1-dodecamethyleneiminomethyldimethylallylsilane, 2- (1-dodecamethyleneimino) ethyldimethylallylsilane, 3- (1-dodecamethyleneimino) -n-propyldimethylallylsilane,
1-dodecamethyleneiminomethyldiethylallylsilane,
1-dodecamethyleneiminomethyldi-n-propylallylsilane,
2- (1-dodecamethyleneimino) ethyldiethylallylsilane,
2- (1-dodecamethyleneimino) ethyldi-n-propylallylsilane,
3- (1-dodecamethyleneimino) -n-propyldiethylallylsilane,
3- (1-dodecamethyleneimino) -n-propyldi-n-propylallylsilane.

[9] 1-polymethyleneiminoalkyldialkyl-1-propenylsilane:
1-aziridinylmethyldimethyl-1-propenylsilane, 2- (1-aziridinyl) ethyldimethyl-1-propenylsilane, 3- (1-aziridinyl) -n-propyldimethyl-1-propenylsilane,
1-aziridinylmethyldiethyl-1-propenylsilane,
1-aziridinylmethyldi-n-propyl 1-propenylsilane,
2- (1-aziridinyl) ethyldiethyl-1-propenylsilane,
2- (1-aziridinyl) ethyldi-n-propyl 1-propenylsilane,
3- (1-aziridinyl) -n-propyldiethyl-1-propenylsilane,
3- (1-aziridinyl) -n-propyldi-n-propyl 1-propenylsilane,

1-azeridinylmethyldimethyl-1-propenylsilane, 2- (1-azeridinyl) ethyldimethyl-1-propenylsilane, 3- (1-azeridinyl) -n-propyldimethyl-1-propenylsilane,
1-azeridinylmethyldiethyl-1-propenylsilane,
1-azeridinylmethyldi-n-propyl 1-propenylsilane,
2- (1-azelidinyl) ethyldiethyl-1-propenylsilane,
2- (1-azeridinyl) ethyldi-n-propyl 1-propenylsilane,
3- (1-azelidinyl) -n-propyldiethyl-1-propenylsilane,
3- (1-azelidinyl) -n-propyldi-n-propyl 1-propenylsilane,

Dimethyl-1-pyrrolidinylmethyl-1-propenylsilane, dimethyl-2- (1-pyrrolidinyl) ethyl-1-propenylsilane, 3dimethyl- (1-pyrrolidinyl) -n-propyl 1-propenylsilane,
Diethyl-1-pyrrolidinylmethyl-1-propenylsilane,
1-pyrrolidinylmethyldi-n-propyl 1-propenylsilane,
Diethyl-2- (1-pyrrolidinyl) ethyl-1-propenylsilane,
2- (1-pyrrolidinyl) ethyldi-n-propyl 1-propenylsilane,
Diethyl-3- (1-pyrrolidinyl) -n-propyl 1-propenylsilane,
3- (1-pyrrolidinyl) -n-propyldi-n-propyl 1-propenylsilane,

Dimethyl-1-piperidinylmethyl-1-propenylsilane, dimethyl-2- (1-piperidinyl) ethyl-1-propenylsilane, dimethyl-3- (1-piperidinyl) -n-propyl 1-propenylsilane,
Diethyl-1-piperidinylmethyl-1-propenylsilane,
1-piperidinylmethyldi-n-propyl 1-propenylsilane,
2- (1-piperidinyl) ethyldiethyl-1-propenylsilane,
2- (1-piperidinyl) ethyldi-n-propyl 1-propenylsilane,
Diethyl-3- (1-piperidinyl) -n-propyl 1-propenylsilane,
3- (1-piperidinyl) -n-propyldi-n-propyl 1-propenylsilane,

1-hexamethyleneiminomethyldimethyl-1-propenylsilane, 2- (1-hexamethyleneimino) ethyldimethyl-1-propenylsilane, 3- (1-hexamethyleneimino) -n-propyldimethyl-1-propenylsilane,
Diethyl-1-hexamethyleneiminomethyl-1-propenylsilane,
1-hexamethyleneiminomethyldi-n-propyl 1-propenylsilane,
Diethyl-2- (1-hexamethyleneimino) ethyl-1-propenylsilane,
2- (1-hexamethyleneimino) ethyldi-n-propyl 1-propenylsilane,
Diethyl-3- (1-hexamethyleneimino) -n-propyl 1-propenylsilane,
3- (1-hexamethyleneimino) -n-propyldi-n-propyl1-propenylsilane,

1-heptamethyleneiminomethyldimethyl-1-propenylsilane, 2- (1-heptamethyleneimino) ethyldimethyl-1-propenylsilane, 3- (1-heptamethyleneimino) -n-propyldimethyl-1-propenylsilane,
Diethyl-1-heptamethyleneiminomethyl-1-propenylsilane,
1-heptamethyleneiminomethyldi-n-propyl 1-propenylsilane,
Diethyl-2- (1-heptamethyleneimino) ethyl-1-propenylsilane,
2- (1-heptamethyleneimino) ethyldi-n-propyl 1-propenylsilane,
Diethyl-3- (1-heptamethyleneimino) -n-propyl 1-propenylsilane,
3- (1-heptamethyleneimino) -n-propyldi-n-propyl1-propenylsilane,

Dimethyl-1-octamethyleneiminomethyl-1-propenylsilane, dimethyl-2- (1-octamethyleneimino) ethyl-1-propenylsilane, dimethyl-3- (1-octamethyleneimino) -n-propyl-1-propenyl Silane,
Diethyl-1-octamethyleneiminomethyl-1-propenylsilane,
1-octamethyleneiminomethyldi-n-propyl 1-propenylsilane,
Diethyl-2- (1-octamethyleneimino) ethyl-1-propenylsilane,
2- (1-octamethyleneimino) ethyldi-n-propyl 1-propenylsilane,
Diethyl-3- (1-octamethyleneimino) -n-propyl 1-propenylsilane,
3- (1-octamethyleneimino) -n-propyldi-n-propyl1-propenylsilane,

1-decamethyleneiminomethyldimethyl-1-propenylsilane, 2- (1-decamethyleneimino) ethyldimethyl-1-propenylsilane, 3- (1-decamethyleneimino) -n-propyldimethyl-1-propenylsilane,
1-decamethyleneiminomethyldiethyl-1-propenylsilane,
1-decamethyleneiminomethyldi-n-propyl 1-propenylsilane,
2- (1-decamethyleneimino) ethyldiethyl-1-propenylsilane,
2- (1-decamethyleneimino) ethyldi-n-propyl 1-propenylsilane,
3- (1-decamethyleneimino) -n-propyldiethyl-1-propenylsilane,
3- (1-Decamethyleneimino) -n-propyldi-n-propyl1-propenylsilane,

1-dodecamethyleneiminomethyldimethyl-1-propenylsilane, 2- (1-dodecamethyleneimino) ethyldimethyl-1-propenylsilane, 3- (1-dodecamethyleneimino) -n-propyldimethyl-1-propenylsilane,
1-dodecamethyleneiminomethyldiethyl-1-propenylsilane,
1-dodecamethyleneiminomethyldi-n-propyl 1-propenylsilane,
2- (1-dodecamethyleneimino) ethyldiethyl-1-propenylsilane,
2- (1-dodecamethyleneimino) ethyldi-n-propyl 1-propenylsilane,
3- (1-dodecamethyleneimino) -n-propyldiethyl-1-propenylsilane,
3- (1-dodecamethyleneimino) -n-propyldi-n-propyl 1-propenylsilane.

[10] 1-polymethyleneiminoalkyldialkylisopropenylsilane:
1-aziridinylmethyldimethylisopropenylsilane, 2- (1-aziridinyl) ethyldimethylisopropenylsilane, 3- (1-aziridinyl) -n-propyldimethylisopropenylsilane,
1-aziridinylmethyldiethylisopropenylsilane,
1-aziridinylmethyldi-n-propylisopropenylsilane,
2- (1-aziridinyl) ethyldiethylisopropenylsilane,
2- (1-aziridinyl) ethyldi-n-propylisopropenylsilane,
3- (1-aziridinyl) -n-propyldiethylisopropenylsilane,
3- (1-aziridinyl) -n-propyldi-n-propylisopropenylsilane,

1-azeridinylmethyldimethylisopropenylsilane, 2- (1-azeridinyl) ethyldimethylisopropenylsilane, 3- (1-azeridinyl) -n-propyldimethylisopropenylsilane,
1-azeridinylmethyldiethylisopropenylsilane,
1-azeridinylmethyldi-n-propylisopropenylsilane,
2- (1-azeridinyl) ethyldiethylisopropenylsilane,
2- (1-azelidinyl) ethyldi-n-propylisopropenylsilane,
3- (1-azelidinyl) -n-propyldiethylisopropenylsilane,
3- (1-azelidinyl) -n-propyldi-n-propylisopropenylsilane,

Dimethyl-1-pyrrolidinylmethylisopropenylsilane, dimethyl-2- (1-pyrrolidinyl) ethylisopropenylsilane, 3dimethyl- (1-pyrrolidinyl) -n-propylisopropenylsilane,
Diethyl-1-pyrrolidinylmethylisopropenylsilane,
1-pyrrolidinylmethyldi-n-propylisopropenylsilane,
Diethyl-2- (1-pyrrolidinyl) ethylisopropenylsilane,
2- (1-pyrrolidinyl) ethyldi-n-propylisopropenylsilane,
Diethyl-3- (1-pyrrolidinyl) -n-propylisopropenylsilane,
3- (1-pyrrolidinyl) -n-propyldi-n-propylisopropenylsilane,

Dimethyl-1-piperidinylmethylisopropenylsilane, dimethyl-2- (1-piperidinyl) ethylisopropenylsilane, dimethyl-3- (1-piperidinyl) -n-propylisopropenylsilane,
Diethyl-1-piperidinylmethylisopropenylsilane,
1-piperidinylmethyldi-n-propylisopropenylsilane,
2- (1-piperidinyl) ethyldiethylisopropenylsilane,
2- (1-piperidinyl) ethyldi-n-propylisopropenylsilane,
Diethyl-3- (1-piperidinyl) -n-propylisopropenylsilane,
3- (1-piperidinyl) -n-propyldi-n-propylisopropenylsilane,

1-hexamethyleneiminomethyldimethylisopropenylsilane, 2- (1-hexamethyleneimino) ethyldimethylisopropenylsilane, 3- (1-hexamethyleneimino) -n-propyldimethylisopropenylsilane,
Diethyl-1-hexamethyleneiminomethylisopropenylsilane,
1-hexamethyleneiminomethyldi-n-propylisopropenylsilane,
Diethyl-2- (1-hexamethyleneimino) ethylisopropenylsilane,
2- (1-hexamethyleneimino) ethyldi-n-propylisopropenylsilane,
Diethyl-3- (1-hexamethyleneimino) -n-propylisopropenylsilane,
3- (1-hexamethyleneimino) -n-propyldi-n-propylisopropenylsilane,

1-heptamethyleneiminomethyldimethylisopropenylsilane, 2- (1-heptamethyleneimino) ethyldimethylisopropenylsilane, 3- (1-heptamethyleneimino) -n-propyldimethylisopropenylsilane,
Diethyl-1-heptamethyleneiminomethylisopropenylsilane,
1-heptamethyleneiminomethyldi-n-propylisopropenylsilane,
Diethyl-2- (1-heptamethyleneimino) ethylisopropenylsilane,
2- (1-heptamethyleneimino) ethyldi-n-propylisopropenylsilane,
Diethyl-3- (1-heptamethyleneimino) -n-propylisopropenylsilane,
3- (1-heptamethyleneimino) -n-propyldi-n-propylisopropenylsilane,

Dimethyl-1-octamethyleneiminomethylisopropenylsilane, dimethyl-2- (1-octamethyleneimino) ethylisopropenylsilane, dimethyl-3- (1-octamethyleneimino) -n-propylisopropenylsilane,
Diethyl-1-octamethyleneiminomethylisopropenylsilane,
1-octamethyleneiminomethyldi-n-propylisopropenylsilane,
Diethyl-2- (1-octamethyleneimino) ethylisopropenylsilane,
2- (1-octamethyleneimino) ethyldi-n-propylisopropenylsilane,
Diethyl-3- (1-octamethyleneimino) -n-propylisopropenylsilane,
3- (1-octamethyleneimino) -n-propyldi-n-propylisopropenylsilane,

1-decamethyleneiminomethyldimethylisopropenylsilane, 2- (1-decamethyleneimino) ethyldimethylisopropenylsilane, 3- (1-decamethyleneimino) -n-propyldimethylisopropenylsilane,
1-decamethyleneiminomethyldiethylisopropenylsilane,
1-decamethyleneiminomethyldi-n-propylisopropenylsilane,
2- (1-decamethyleneimino) ethyldiethylisopropenylsilane,
2- (1-decamethyleneimino) ethyldi-n-propylisopropenylsilane,
3- (1-decamethyleneimino) -n-propyldiethylisopropenylsilane,
3- (1-decamethyleneimino) -n-propyldi-n-propylisopropenylsilane,

1-dodecamethyleneiminomethyldimethylisopropenylsilane, 2- (1-dodecamethyleneimino) ethyldimethylisopropenylsilane, 3- (1-dodecamethyleneimino) -n-propyldimethylisopropenylsilane,
1-dodecamethyleneiminomethyldiethylisopropenylsilane,
1-dodecamethyleneiminomethyldi-n-propylisopropenylsilane,
2- (1-dodecamethyleneimino) ethyldiethylisopropenylsilane,
2- (1-dodecamethyleneimino) ethyldi-n-propylisopropenylsilane,
3- (1-dodecamethyleneimino) -n-propyldiethylisopropenylsilane,
3- (1-dodecamethyleneimino) -n-propyldi-n-propylisopropenylsilane.

[11] 1-polymethyleneiminoalkyldialkylcrotylsilane:
1-aziridinylmethyldimethylcrotylsilane, 2- (1-aziridinyl) ethyldimethylcrotylsilane, 3- (1-aziridinyl) -n-propyldimethylcrotylsilane,
1-aziridinylmethyldiethylcrotylsilane,
1-aziridinylmethyldi-n-propylcrotylsilane,
2- (1-aziridinyl) ethyldiethylcrotylsilane,
2- (1-aziridinyl) ethyldi-n-propylcrotylsilane,
3- (1-aziridinyl) -n-propyldiethylcrotylsilane,
3- (1-aziridinyl) -n-propyldi-n-propylcrotylsilane,

1-azeridinylmethyldimethylcrotylsilane, 2- (1-azelidinyl) ethyldimethylcrotylsilane, 3- (1-azelidinyl) -n-propyldimethylcrotylsilane,
1-azeridinylmethyldiethylcrotylsilane,
1-azeridinylmethyldi-n-propylcrotylsilane,
2- (1-azeridinyl) ethyldiethylcrotylsilane,
2- (1-azeridinyl) ethyldi-n-propylcrotylsilane,
3- (1-azelidinyl) -n-propyldiethylcrotylsilane,
3- (1-azelidinyl) -n-propyldi-n-propylcrotylsilane,

Dimethyl-1-pyrrolidinylmethylcrotylsilane, dimethyl-2- (1-pyrrolidinyl) ethylcrotylsilane, 3dimethyl- (1-pyrrolidinyl) -n-propylcrotylsilane,
Diethyl-1-pyrrolidinylmethylcrotylsilane,
1-pyrrolidinylmethyldi-n-propylcrotylsilane,
Diethyl-2- (1-pyrrolidinyl) ethylcrotylsilane,
2- (1-pyrrolidinyl) ethyldi-n-propylcrotylsilane,
Diethyl-3- (1-pyrrolidinyl) -n-propylcrotylsilane,
3- (1-pyrrolidinyl) -n-propyldi-n-propylcrotylsilane,

Dimethyl-1-piperidinylmethylcrotylsilane, dimethyl-2- (1-piperidinyl) ethylcrotylsilane, dimethyl-3- (1-piperidinyl) -n-propylcrotylsilane,
Diethyl-1-piperidinylmethylcrotylsilane,
1-piperidinylmethyldi-n-propylcrotylsilane,
2- (1-piperidinyl) ethyldiethylcrotylsilane,
2- (1-piperidinyl) ethyldi-n-propylcrotylsilane,
Diethyl-3- (1-piperidinyl) -n-propylcrotylsilane,
3- (1-piperidinyl) -n-propyldi-n-propylcrotylsilane,

1-hexamethyleneiminomethyldimethylcrotylsilane, 2- (1-hexamethyleneimino) ethyldimethylcrotylsilane, 3- (1-hexamethyleneimino) -n-propyldimethylcrotylsilane,
Diethyl-1-hexamethyleneiminomethylcrotylsilane,
1-hexamethyleneiminomethyldi-n-propylcrotylsilane,
Diethyl-2- (1-hexamethyleneimino) ethylcrotylsilane,
2- (1-hexamethyleneimino) ethyldi-n-propylcrotylsilane,
Diethyl-3- (1-hexamethyleneimino) -n-propylcrotylsilane,
3- (1-hexamethyleneimino) -n-propyldi-n-propylcrotylsilane,

1-heptamethyleneiminomethyldimethylcrotylsilane, 2- (1-heptamethyleneimino) ethyldimethylcrotylsilane, 3- (1-heptamethyleneimino) -n-propyldimethylcrotylsilane,
Diethyl-1-heptamethyleneiminomethylcrotylsilane,
1-heptamethyleneiminomethyldi-n-propylcrotylsilane,
Diethyl-2- (1-heptamethyleneimino) ethylcrotylsilane,
2- (1-heptamethyleneimino) ethyldi-n-propylcrotylsilane,
Diethyl-3- (1-heptamethyleneimino) -n-propylcrotylsilane,
3- (1-heptamethyleneimino) -n-propyldi-n-propylcrotylsilane,

Dimethyl-1-octamethyleneiminomethylcrotylsilane, dimethyl-2- (1-octamethyleneimino) ethylcrotylsilane, dimethyl-3- (1-octamethyleneimino) -n-propylcrotylsilane,
Diethyl-1-octamethyleneiminomethylcrotylsilane,
1-octamethyleneiminomethyldi-n-propylcrotylsilane,
Diethyl-2- (1-octamethyleneimino) ethylcrotylsilane,
2- (1-octamethyleneimino) ethyldi-n-propylcrotylsilane,
Diethyl-3- (1-octamethyleneimino) -n-propylcrotylsilane,
3- (1-octamethyleneimino) -n-propyldi-n-propylcrotylsilane,

1-decamethyleneiminomethyldimethylcrotylsilane, 2- (1-decamethyleneimino) ethyldimethylcrotylsilane, 3- (1-decamethyleneimino) -n-propyldimethylcrotylsilane,
1-decamethyleneiminomethyldiethylcrotylsilane,
1-decamethyleneiminomethyldi-n-propylcrotylsilane,
2- (1-decamethyleneimino) ethyldiethylcrotylsilane,
2- (1-decamethyleneimino) ethyldi-n-propylcrotylsilane,
3- (1-decamethyleneimino) -n-propyldiethylcrotylsilane,
3- (1-Decamethyleneimino) -n-propyldi-n-propylcrotylsilane,

1-dodecamethyleneiminomethyldimethylcrotylsilane, 2- (1-dodecamethyleneimino) ethyldimethylcrotylsilane, 3- (1-dodecamethyleneimino) -n-propyldimethylcrotylsilane,
1-dodecamethyleneiminomethyldiethylcrotylsilane,
1-dodecamethyleneiminomethyldi-n-propylcrotylsilane,
2- (1-dodecamethyleneimino) ethyldiethylcrotylsilane,
2- (1-dodecamethyleneimino) ethyldi-n-propylcrotylsilane,
3- (1-dodecamethyleneimino) -n-propyldiethylcrotylsilane,
3- (1-dodecamethyleneimino) -n-propyldi-n-propylcrotylsilane.

[12] 1-polymethyleneiminoalkyldialkylmethallylsilane:
1-aziridinylmethyldimethylmethallylsilane, 2- (1-aziridinyl) ethyldimethylmethallylsilane, 3- (1-aziridinyl) -n-propyldimethylmethallylsilane,
1-aziridinylmethyldiethylmethallylsilane,
1-aziridinylmethyldi-n-propylmethallylsilane,
2- (1-aziridinyl) ethyldiethylmethallylsilane,
2- (1-aziridinyl) ethyldi-n-propylmethallylsilane,
3- (1-aziridinyl) -n-propyldiethylmethallylsilane,
3- (1-aziridinyl) -n-propyldi-n-propylmethallylsilane,

1-azeridinylmethyldimethylmethallylsilane, 2- (1-azeridinyl) ethyldimethylmethallylsilane, 3- (1-azeridinyl) -n-propyldimethylmethallylsilane,
1-azeridinylmethyldiethylmethallylsilane,
1-azeridinylmethyldi-n-propylmethallylsilane,
2- (1-azelidinyl) ethyldiethylmethallylsilane,
2- (1-azeridinyl) ethyldi-n-propylmethallylsilane,
3- (1-azeridinyl) -n-propyldiethylmethallylsilane,
3- (1-azelidinyl) -n-propyldi-n-propylmethallylsilane,

Dimethyl-1-pyrrolidinylmethylmethallylsilane, dimethyl-2- (1-pyrrolidinyl) ethylmethallylsilane, 3dimethyl- (1-pyrrolidinyl) -n-propylmethallylsilane,
Diethyl-1-pyrrolidinylmethylmethallylsilane,
1-pyrrolidinylmethyldi-n-propylmethallylsilane,
Diethyl-2- (1-pyrrolidinyl) ethylmethallylsilane,
2- (1-pyrrolidinyl) ethyldi-n-propylmethallylsilane,
Diethyl-3- (1-pyrrolidinyl) -n-propylmethallylsilane,
3- (1-pyrrolidinyl) -n-propyldi-n-propylmethallylsilane,

Dimethyl-1-piperidinylmethylmethallylsilane, dimethyl-2- (1-piperidinyl) ethylmethallylsilane, dimethyl-3- (1-piperidinyl) -n-propylmethallylsilane,
Diethyl-1-piperidinylmethylmethallylsilane,
1-piperidinylmethyldi-n-propylmethallylsilane,
2- (1-piperidinyl) ethyldiethylmethallylsilane,
2- (1-piperidinyl) ethyldi-n-propylmethallylsilane,
Diethyl-3- (1-piperidinyl) -n-propylmethallylsilane,
3- (1-piperidinyl) -n-propyldi-n-propylmethallylsilane,

1-hexamethyleneiminomethyldimethylmethallylsilane, 2- (1-hexamethyleneimino) ethyldimethylmethallylsilane, 3- (1-hexamethyleneimino) -n-propyldimethylmethallylsilane,
Diethyl-1-hexamethyleneiminomethylmethallylsilane,
1-hexamethyleneiminomethyldi-n-propylmethallylsilane,
Diethyl-2- (1-hexamethyleneimino) ethylmethallylsilane,
2- (1-hexamethyleneimino) ethyldi-n-propylmethallylsilane,
Diethyl-3- (1-hexamethyleneimino) -n-propylmethallylsilane,
3- (1-hexamethyleneimino) -n-propyldi-n-propylmethallylsilane,

1-heptamethyleneiminomethyldimethylmethallylsilane, 2- (1-heptamethyleneimino) ethyldimethylmethallylsilane, 3- (1-heptamethyleneimino) -n-propyldimethylmethallylsilane,
Diethyl-1-heptamethyleneiminomethylmethallylsilane,
1-heptamethyleneiminomethyldi-n-propylmethallylsilane,
Diethyl-2- (1-heptamethyleneimino) ethylmethallylsilane,
2- (1-heptamethyleneimino) ethyldi-n-propylmethallylsilane,
Diethyl-3- (1-heptamethyleneimino) -n-propylmethallylsilane,
3- (1-heptamethyleneimino) -n-propyldi-n-propylmethallylsilane,

Dimethyl-1-octamethyleneiminomethylmethallylsilane, dimethyl-2- (1-octamethyleneimino) ethylmethallylsilane, dimethyl-3- (1-octamethyleneimino) -n-propylmethallylsilane,
Diethyl-1-octamethyleneiminomethylmethallylsilane,
1-octamethyleneiminomethyldi-n-propylmethallylsilane,
Diethyl-2- (1-octamethyleneimino) ethylmethallylsilane,
2- (1-octamethyleneimino) ethyldi-n-propylmethallylsilane,
Diethyl-3- (1-octamethyleneimino) -n-propylmethallylsilane,
3- (1-octamethyleneimino) -n-propyldi-n-propylmethallylsilane,

1-decamethyleneiminomethyldimethylmethallylsilane, 2- (1-decamethyleneimino) ethyldimethylmethallylsilane, 3- (1-decamethyleneimino) -n-propyldimethylmethallylsilane,
1-decamethyleneiminomethyldiethylmethallylsilane,
1-decamethyleneiminomethyldi-n-propylmethallylsilane,
2- (1-decamethyleneimino) ethyldiethylmethallylsilane,
2- (1-decamethyleneimino) ethyldi-n-propylmethallylsilane,
3- (1-decamethyleneimino) -n-propyldiethylmethallylsilane,
3- (1-Decamethyleneimino) -n-propyldi-n-propylmethallylsilane,

1-dodecamethyleneiminomethyldimethylmethallylsilane, 2- (1-dodecamethyleneimino) ethyldimethylmethallylsilane, 3- (1-dodecamethyleneimino) -n-propyldimethylmethallylsilane,
1-dodecamethyleneiminomethyldiethylmethallylsilane,
1-dodecamethyleneiminomethyldi-n-propylmethallylsilane,
2- (1-dodecamethyleneimino) ethyldiethylmethallylsilane,
2- (1-dodecamethyleneimino) ethyldi-n-propylmethallylsilane,
3- (1-dodecamethyleneimino) -n-propyldiethylmethallylsilane,
3- (1-dodecamethyleneimino) -n-propyldi-n-propylmethallylsilane.

The compound represented by formula (1) is a compound in which R ¹ is a group represented by formula (2), m is 2, and A is an acyclic amino group represented by formula (3). Can be given.
As the compound,
Bis (dialkylamino) alkylalkylvinylsilane,
Bis (dialkylamino) alkyldialkylallylvinylsilane,
Bis (dialkylamino) alkylalkyl-1-propenylsilane,
Bis (dialkylamino) alkylalkylisopropenylsilane.
Specific compounds will be exemplified in the following paragraphs.

[13] Bis (dialkylamino) alkylalkylvinylsilane:
Bis (dimethylamino) methylmethylvinylsilane, bis (diethylamino) methylmethylvinylsilane, bis (di-n-propylamino) methylmethylvinylsilane, bis (dimethylamino) methylethylvinylsilane, bis (diethylamino) methylethylvinylsilane, bis (di -N-propylamino) methylethylvinylsilane,

2-bis (dimethylamino) ethylmethylvinylsilane, 2-bis (diethylamino) ethylmethylvinylsilane, 2-bis (di-n-propylamino) ethylmethylvinylsilane, 2-bis (dimethylamino) ethylethylvinylsilane, 2-bis (Diethylamino) ethylethylvinylsilane, 2-bis (di-n-propylamino) ethylethylvinylsilane,

3-bis (dimethylamino) -n-propylmethylvinylsilane, 3-bis (diethylamino) -n-propylmethylvinylsilane, 3-bis (di-n-propylamino) -n-propylmethylvinylsilane, 3-bis (dimethyl) Amino) -n-propylethylvinylsilane, 3-bis (diethylamino) -n-propylethylvinylsilane, 3-bis (di-n-propylamino) -n-propylethylvinylsilane.

[14] Bis (dialkylamino) alkylalkylallylsilane:
Bis (dimethylamino) methylmethylallylsilane, bis (diethylamino) methylmethylallylsilane, bis (di-n-propylamino) methylmethylallylsilane, bis (dimethylamino) methylethylallylsilane, bis (diethylamino) methylethylallylsilane, bis (di -N-propylamino) methylethylallylsilane,

2-bis (dimethylamino) ethylmethylallylsilane, 2-bis (diethylamino) ethylmethylallylsilane, 2-bis (di-n-propylamino) ethylmethylallylsilane, 2-bis (dimethylamino) ethylethylallylsilane, 2-bis (Diethylamino) ethylethylallylsilane, 2-bis (di-n-propylamino) ethylethylallylsilane,

3-bis (dimethylamino) -n-propylmethylallylsilane, 3-bis (diethylamino) -n-propylmethylallylsilane, 3-bis (di-n-propylamino) -n-propylmethylallylsilane, 3-bis (dimethyl) Amino) -n-propylethylallylsilane, 3-bis (diethylamino) -n-propylethylallylsilane, 3-bis (di-n-propylamino) -n-propylethylallylsilane.

[15] Bis (dialkylamino) alkylalkyl-1-propenylsilane:
Bis (dimethylamino) methylmethyl-1-propenylsilane, bis (diethylamino) methylmethyl-1-propenylsilane, bis (di-n-propylamino) methylmethyl-1-propenylsilane, bis (dimethylamino) methylethyl- 1-propenylsilane, bis (diethylamino) methylethyl-1-propenylsilane, bis (di-n-propylamino) methylethyl-1-propenylsilane,

2-bis (dimethylamino) ethylmethyl-1-propenylsilane, 2-bis (diethylamino) ethylmethyl-1-propenylsilane, 2-bis (di-n-propylamino) ethylmethyl-1-propenylsilane, 2- Bis (dimethylamino) ethylethyl-1-propenylsilane, 2-bis (diethylamino) ethylethyl-1-propenylsilane, 2-bis (di-n-propylamino) ethylethyl-1-propenylsilane,

3-bis (dimethylamino) -n-propylmethyl-1-propenylsilane, 3-bis (diethylamino) -n-propylmethyl-1-propenylsilane, 3-bis (di-n-propylamino) -n-propyl Methyl-1-propenylsilane, 3-bis (dimethylamino) -n-propylethyl-1-propenylsilane, 3-bis (diethylamino) -n-propylethyl-1-propenylsilane, 3-bis (di-n- Propylamino) -n-propylethyl-1-propenylsilane.

[16] Bis (dialkylamino) alkylalkylisopropenylsilane:
Bis (dimethylamino) methylmethylisopropenylsilane, bis (diethylamino) methylmethylisopropenylsilane, bis (di-n-propylamino) methylmethylisopropenylsilane, bis (dimethylamino) methylethylisopropenylsilane, bis (diethylamino) ) Methyl ethyl isopropenyl silane, bis (di-n-propylamino) methyl ethyl isopropenyl silane,

2-bis (dimethylamino) ethylmethylisopropenylsilane, 2-bis (diethylamino) ethylmethylisopropenylsilane, 2-bis (di-n-propylamino) ethylmethylisopropenylsilane, 2-bis (dimethylamino) ethyl Ethylisopropenylsilane, 2-bis (diethylamino) ethylethylisopropenylsilane, 2-bis (di-n-propylamino) ethylethylisopropenylsilane,

3-bis (dimethylamino) -n-propylmethylisopropenylsilane, 3-bis (diethylamino) -n-propylmethylisopropenylsilane, 3-bis (di-n-propylamino) -n-propylmethylisopropenylsilane 3-bis (dimethylamino) -n-propylethylisopropenylsilane, 3-bis (diethylamino) -n-propylethylisopropenylsilane, 3-bis (di-n-propylamino) -n-propylethylisopropenyl Silane.

The compound represented by formula (1) is a compound in which R ¹ is a group represented by formula (2), m is 2, and A is a cyclic amino group represented by formula (3). can give.
As the compound,
Di (1-polymethyleneimino) alkylalkylvinylsilane,
Di (1-polymethyleneimino) alkylalkylallylsilane,
Di (1-polymethyleneimino) alkylalkyl-1-propenylsilane,
Examples include di (1-polymethyleneimino) alkylalkylisopropenylsilane.
Specific compounds will be exemplified in the following paragraphs.

[17] Di (1-polymethyleneimino) alkylalkylvinylsilane:
Di (1-pyrrolidinyl) methylmethylvinylsilane, 2,2′-di (1-pyrrolidinyl) ethylmethylvinylsilane, 3,3′-di (1-pyrrolidinyl) -n-propylmethylvinylsilane,
2-di (1-pyrrolidinyl) ethylethylvinylsilane,
2-di (1-pyrrolidinyl) ethyl-n-propylvinylsilane,
3-di (1-pyrrolidinyl) -n-propylethylvinylsilane,
3-di (1-pyrrolidinyl) -n-propyl n-propylvinylsilane,

Di (1-piperidinyl) methylmethylvinylsilane, 2,2′-di (1-piperidinyl) ethylmethylvinylsilane, 3,3′-di (1-piperidinyl) -n-propylmethylvinylsilane,
2-di (1-piperidinyl) ethylethylvinylsilane,
2-di (1-piperidinyl) ethyl-n-propylvinylsilane,
3-di (1-piperidinyl) -n-propylethylvinylsilane,
3-di (1-piperidinyl) -n-propyl n-propylvinylsilane,

Di (1-hexamethyleneimino) methylmethylvinylsilane, 2,2′-di (1-hexamethyleneimino) ethylmethylvinylsilane, 3,3′-di (1-hexamethyleneimino) -n-propylmethylvinylsilane,
2-di (1-hexamethyleneimino) ethylethylvinylsilane,
2-di (1-hexamethyleneimino) ethyl-n-propylvinylsilane,
3-di (1-hexamethyleneimino) -n-propylethylvinylsilane,
3-di (1-hexamethyleneimino) -n-propyl n-propylvinylsilane,

Di (1-heptamethyleneimino) methylmethylvinylsilane, 2,2′-di (1-heptamethyleneimino) ethylmethylvinylsilane, 3,3′-di (1-heptamethyleneimino) -n-propylmethylvinylsilane,
2-di (1-heptamethyleneimino) ethylethylvinylsilane,
2-di (1-heptamethyleneimino) ethyl-n-propylvinylsilane,
3-di (1-heptamethyleneimino) -n-propylethylvinylsilane,
3-di (1-heptamethyleneimino) -n-propyl n-propylvinylsilane.

[18] Di (1-polymethyleneimino) alkylalkylallylsilane:
Di (1-pyrrolidinyl) methylmethylallylsilane, 2,2′-di (1-pyrrolidinyl) ethylmethylallylsilane, 3,3′-di (1-pyrrolidinyl) -n-propylmethylallylsilane,
2-di (1-pyrrolidinyl) ethylethylallylsilane,
2-di (1-pyrrolidinyl) ethyl-n-propylallylsilane,
3-di (1-pyrrolidinyl) -n-propylethylallylsilane,
3-di (1-pyrrolidinyl) -n-propyl n-propylallylsilane,

Di (1-piperidinyl) methylmethylallylsilane, 2,2′-di (1-piperidinyl) ethylmethylallylsilane, 3,3′-di (1-piperidinyl) -n-propylmethylallylsilane,
2-di (1-piperidinyl) ethylethylallylsilane,
2-di (1-piperidinyl) ethyl-n-propylallylsilane,
3-di (1-piperidinyl) -n-propylethylallylsilane,
3-di (1-piperidinyl) -n-propyl n-propylallylsilane,

Di (1-hexamethyleneimino) methylmethylallylsilane, 2,2′-di (1-hexamethyleneimino) ethylmethylallylsilane, 3,3′-di (1-hexamethyleneimino) -n-propylmethylallylsilane,
2-di (1-hexamethyleneimino) ethylethylallylsilane,
2-di (1-hexamethyleneimino) ethyl-n-propylallylsilane,
3-di (1-hexamethyleneimino) -n-propylethylallylsilane,
3-di (1-hexamethyleneimino) -n-propyl n-propylallylsilane,

Di (1-heptamethyleneimino) methylmethylallylsilane, 2,2′-di (1-heptamethyleneimino) ethylmethylallylsilane, 3,3′-di (1-heptamethyleneimino) -n-propylmethylallylsilane,
2-di (1-heptamethyleneimino) ethylethylallylsilane,
2-di (1-heptamethyleneimino) ethyl-n-propylallylsilane,
3-di (1-heptamethyleneimino) -n-propylethylallylsilane,
3-di (1-heptamethyleneimino) -n-propyl n-propylallylsilane.

[19] Di (1-polymethyleneimino) alkylalkyl-1-propenylsilane:
Di (1-pyrrolidinyl) methylmethyl-1-propenylsilane, 2,2′-di (1-pyrrolidinyl) ethylmethyl-1-propenylsilane, 3,3′-di (1-pyrrolidinyl) -n-propylmethyl- 1-propenylsilane,
2-di (1-pyrrolidinyl) ethylethyl-1-propenylsilane,
2-di (1-pyrrolidinyl) ethyl-n-propyl 1-propenylsilane,
3-di (1-pyrrolidinyl) -n-propylethyl-1-propenylsilane,
3-di (1-pyrrolidinyl) -n-propyl n-propyl 1-propenylsilane,

Di (1-piperidinyl) methylmethyl-1-propenylsilane, 2,2′-di (1-piperidinyl) ethylmethyl-1-propenylsilane, 3,3′-di (1-piperidinyl) -n-propylmethyl- 1-propenylsilane,
2-di (1-piperidinyl) ethylethyl-1-propenylsilane,
2-di (1-piperidinyl) ethyl-n-propyl 1-propenylsilane,
3-di (1-piperidinyl) -n-propylethyl-1-propenylsilane,
3-di (1-piperidinyl) -n-propyl n-propyl 1-propenylsilane,

Di (1-hexamethyleneimino) methylmethyl-1-propenylsilane, 2,2′-di (1-hexamethyleneimino) ethylmethyl-1-propenylsilane, 3,3′-di (1-hexamethyleneimino) -N-propylmethyl-1-propenylsilane,
2-di (1-hexamethyleneimino) ethylethyl-1-propenylsilane,
2-di (1-hexamethyleneimino) ethyl-n-propyl 1-propenylsilane,
3-di (1-hexamethyleneimino) -n-propylethyl-1-propenylsilane,
3-di (1-hexamethyleneimino) -n-propyl n-propyl 1-propenylsilane,

Di (1-heptamethyleneimino) methylmethyl-1-propenylsilane, 2,2′-di (1-heptamethyleneimino) ethylmethyl-1-propenylsilane, 3,3′-di (1-heptamethyleneimino) -N-propylmethyl-1-propenylsilane,
2-di (1-heptamethyleneimino) ethylethyl-1-propenylsilane,
2-di (1-heptamethyleneimino) ethyl-n-propyl 1-propenylsilane,
3-di (1-heptamethyleneimino) -n-propylethyl-1-propenylsilane,
3-di (1-heptamethyleneimino) -n-propyl n-propyl 1-propenylsilane.

[20] Di (1-polymethyleneimino) alkylalkylisopropenylsilane:
Di (1-pyrrolidinyl) methylmethylisopropenylsilane, 2,2′-di (1-pyrrolidinyl) ethylmethylisopropenylsilane, 3,3′-di (1-pyrrolidinyl) -n-propylmethylisopropenylsilane,
2-di (1-pyrrolidinyl) ethylethylisopropenylsilane,
2-di (1-pyrrolidinyl) ethyl-n-propylisopropenylsilane,
3-di (1-pyrrolidinyl) -n-propylethylisopropenylsilane,
3-di (1-pyrrolidinyl) -n-propyl n-propylisopropenylsilane,

Di (1-piperidinyl) methylmethylisopropenylsilane, 2,2′-di (1-piperidinyl) ethylmethylisopropenylsilane, 3,3′-di (1-piperidinyl) -n-propylmethylisopropenylsilane,
2-di (1-piperidinyl) ethylethylisopropenylsilane,
2-di (1-piperidinyl) ethyl-n-propylisopropenylsilane,
3-di (1-piperidinyl) -n-propylethylisopropenylsilane,
3-di (1-piperidinyl) -n-propyl n-propylisopropenylsilane,

Di (1-hexamethyleneimino) methylmethylisopropenylsilane, 2,2′-di (1-hexamethyleneimino) ethylmethylisopropenylsilane, 3,3′-di (1-hexamethyleneimino) -n-propyl Methyl isopropenyl silane,
2-di (1-hexamethyleneimino) ethylethylisopropenylsilane,
2-di (1-hexamethyleneimino) ethyl-n-propylisopropenylsilane,
3-di (1-hexamethyleneimino) -n-propylethylisopropenylsilane,
3-di (1-hexamethyleneimino) -n-propyl n-propylisopropenylsilane,

Di (1-heptamethyleneimino) methylmethylisopropenylsilane, 2,2′-di (1-heptamethyleneimino) ethylmethylisopropenylsilane, 3,3′-di (1-heptamethyleneimino) -n-propyl Methyl isopropenyl silane,
2-di (1-heptamethyleneimino) ethylethylisopropenylsilane,
2-di (1-heptamethyleneimino) ethyl-n-propylisopropenylsilane,
3-di (1-heptamethyleneimino) -n-propylethylisopropenylsilane,
3-di (1-heptamethyleneimino) -n-propyl n-propylisopropenylsilane.

The compound represented by the formula (1) is a compound in which R ¹ is a group represented by the formula (2), m is 3, and A is a substituted amino group represented by the formula (3). can give.
As the compound,
Tri (dialkylamino) alkylvinylsilane,
Examples include tri (1-polymethyleneimino) alkylvinylsilane.

[21] Tri (dialkylamino) alkylvinylsilane:
Tri (dimethylamino) methylvinylsilane, tri (diethylamino) methylvinylsilane, 2,2 ′, 2 ″ -tri (dimethylamino) ethylvinylsilane, 2,2 ′, 2 ″ -tri (diethylamino) ethylvinylsilane.

[22] Tri (1-polymethyleneimino) alkylvinylsilane:
Tri (1-pyrrolidinyl) methylvinylsilane, tri (1-pyrrolidinyl) methylvinylsilane, 2,2 ′, 2 ″ -tri (1-pyrrolidinyl) ethylvinylsilane, 2,2 ′, 2 ″ -tri (1-pyrrolidinyl) ) Ethyl vinyl silane.

As the compound represented by the formula (1), preferably, m is 1, R ¹ is a group represented by the formula (2), R ² is an alkylene group, and R ³ is an alkyl group. More preferably, m is 1, R ¹ is a group represented by the formula (2), R ² is an alkylene group, R ³ is an alkyl group, and A is a formula ( 3), and more preferably (dialkylamino) alkyldialkylvinylsilane and 1-polymethyleneiminoalkyldialkylvinylsilane. (Dialkylamino) alkyldialkylvinylsilane is preferably dimethyl (dimethylaminomethyl) vinylsilane, and 1-polymethyleneiminoalkyldialkylvinylsilane is preferably dimethyl-1-piperidinylmethylvinylsilane.

The compound represented by the formula (1) is particularly preferably 1-polymethyleneiminoalkyldialkylvinylsilane.

The content of the structural unit based on the monomer represented by the formula (1) in the conjugated diene polymer (A) is preferably 0.001 mmol per unit weight of the polymer in order to increase the wear resistance. / G polymer or more, more preferably 0.002 mmol / g polymer or more, and still more preferably 0.003 mmol / g polymer or more. Moreover, it is preferably 0.1 mmol / g polymer or less, more preferably 0.07 mmol / g polymer or less, and still more preferably 0.05 mmol / g polymer or less.

In the conjugated diene polymer (A), the total amount of the conjugated diene unit and the structural unit based on the monomer represented by the formula (1) is 100 masses of the total amount of the monomer unit in the conjugated diene polymer. % Is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and still more preferably 100% by mass in order to increase rubber strength.

The vinyl bond content of the conjugated diene polymer (A) is preferably 80 mol% or less, more preferably 70 mol% or less, in order to improve fuel efficiency, with the content of the conjugated diene unit being 100 mol%. It is. Moreover, in order to improve grip property, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more, Most preferably, it is 40 mol% or more. The vinyl bond amount is determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

The Mooney viscosity (ML _{1 + 4} ) of the conjugated diene polymer (A) is preferably 10 or more, more preferably 20 or more, in order to increase rubber strength. Moreover, in order to improve workability, Preferably it is 200 or less, More preferably, it is 150 or less. The Mooney viscosity (ML _{1 + 4} ) is measured at 100 ° C. according to JIS K6300 (1994).

The molecular weight distribution of the conjugated diene polymer (A) is preferably 1 to 5 and more preferably 1 to 3 in order to improve fuel efficiency. The molecular weight distribution is obtained by measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) method and dividing Mw by Mn.

[Production Method of Conjugated Diene Polymer (A)]
A suitable method for producing the conjugated diene polymer (A) is a method in which a monomer containing a conjugated diene and a compound represented by the formula (1) is polymerized with an alkali metal catalyst in a hydrocarbon solvent. . For example, the following method A, method B, and method C can be mentioned.

<Method A>
The manufacturing method which has the following process (a1) and (a2).
Step (a1): A step of preparing a reaction product of the alkali metal catalyst and the compound by bringing the alkali metal catalyst and the compound represented by the formula (1) into contact with each other in a hydrocarbon solvent.
Step (a2): A step of polymerizing a monomer containing a conjugated diene in a hydrocarbon solvent using the reaction product prepared in step (a1) as a polymerization initiator.

<Method B>
The manufacturing method which has the following process (b1).
Step (b1): A step of copolymerizing a monomer containing a conjugated diene and a compound represented by the formula (1) by an alkali metal catalyst in a hydrocarbon solvent.

<Method C>
The manufacturing method which has the following process (c1) and (c2).
Step (c1): A monomer containing a conjugated diene is polymerized with an alkali metal catalyst in a hydrocarbon solvent, and the catalyst is derived from at least one terminal of a polymer chain having a monomer unit based on the conjugated diene. A step of obtaining a polymer having an alkali metal.
Step (c2): A step of reacting the compound represented by the formula (1) with the polymer terminal having an alkali metal of the polymer obtained in the step (c1).

In Method A, in addition to the conjugated diene, the compound represented by the formula (1) may be used as the monomer in the step (a2), or other monomers described later may be used. Moreover, you may provide the process (process (a3)) with which the compound represented by Formula (1) is made to react with the polymer terminal which has the alkali metal of the polymer obtained at the process (a2).

In Method B, in addition to the conjugated diene and the compound represented by the formula (1), other monomers described later may be used as the monomer in the step (b1). Moreover, you may provide the process (process (b2)) of making the compound represented by Formula (1) react with the polymer terminal which has the alkali metal of the polymer obtained at the process (b1).

In Method C, in addition to the conjugated diene, the compound represented by the formula (1) may be used as the monomer in the step (c1), or other monomers described later may be used.

Examples of the alkali metal catalyst include alkali metals, organic alkali metal compounds, complexes of alkali metals and polar compounds, and oligomers having alkali metals.

Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium.

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 pyrrolidide , Lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, 1,4-dilithio-2-butene, sodium naphthalenide, sodium Fenirido, potassium naphthalenide the like.

Examples of the complex of an alkali metal and a polar compound include a potassium-tetrahydrofuran complex and a potassium-diethoxyethane complex.

Examples of the oligomer having an alkali metal include sodium salt of α-methylstyrene tetramer.

The alkali metal catalyst is preferably an organic lithium compound or an organic sodium compound, and more preferably an organic lithium compound or an organic sodium compound having 2 to 20 carbon atoms.

The hydrocarbon solvent used in the above production method is a solvent that does not deactivate the organic alkali metal compound catalyst, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Aliphatic hydrocarbons include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene 1-pentene, 2-pentene, 1-hexene and 2-hexene. Aromatic hydrocarbons include benzene, toluene, xylene, and ethylbenzene. Examples of the alicyclic hydrocarbon include cyclopentane and cyclohexane. One or more of these may be used, and the hydrocarbon solvent may be a mixture of various components such as industrial hexane. The hydrocarbon solvent is preferably a hydrocarbon having 2 to 12 carbon atoms.

Examples of the conjugated diene used in the above production method include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. One or more of these are used. The conjugated diene is preferably 1,3-butadiene or isoprene.

Examples of the other monomer used in the step (a2), the step (b1), and the step (c1) include aromatic vinyl, vinyl nitrile, and unsaturated carboxylic acid ester. Examples of the aromatic vinyl include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene. Examples of the vinyl nitrile include acrylonitrile, and examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.

In the polymerization step of the above production method, an agent for adjusting the vinyl bond amount of the conjugated diene unit and / or a distribution of constituent units based on monomers other than the conjugated diene unit and the conjugated diene in the conjugated diene polymer chain May be carried out in the presence of an agent that adjusts (hereinafter collectively referred to as “regulator”). Examples of such a regulator include ether compounds, tertiary amines, and phosphine compounds. Examples of ether compounds 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, diethylene glycol diethyl ether, Aliphatic ethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole. Tertiary amines include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, and quinoline. Examples of the phosphine compound include trimethylphosphine, triethylphosphine, and triphenylphosphine. One or more of these are used.

The polymerization temperature in the polymerization step of the above production method 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.

（式中、ｈは１又は２を表し、ｉは１又は２を表し、ｈ＋ｉは２又は３であり、Ｒ^１１は重合性炭素−炭素二重結合を有するヒドロカルビル基を表し、Ｒ^１２はヒドロカルビル基を表し、Ｒ^１２が複数ある場合、複数あるＲ^１２は同一でも異なっていてもよく、Ｒ^１３は含酸素置換基を有していてもよいアリール基を表し、Ｒ^１３が複数ある場合、複数あるＲ^１３は同一でも異なっていてもよく、Ｒ^１４はアルキル基、又は置換アミノ基を表す。） The conjugated diene polymer (B) according to the second present invention has a monomer unit based on a conjugated diene and a monomer unit based on a monomer represented by the following formula (4).

(In the formula, h represents 1 or 2, i represents 1 or 2, h + i is 2 or 3, R ¹¹ represents a hydrocarbyl group having a polymerizable carbon-carbon double bond, and R ¹² represents hydrocarbyl. represents a group, if R ¹² is plural, there R ¹² may be the same or different, R ¹³ represents an aryl group which may have an oxygen-containing substituent, if R ¹³ there are a plurality, A plurality of R ¹³ may be the same or different, and R ¹⁴ represents an alkyl group or a substituted amino group.)

As used herein, a hydrocarbyl group represents a hydrocarbon residue. The hydrocarbyloxy group represents a group in which a hydrogen atom of a hydroxyl group is substituted with a hydrocarbyl group. The hydrocarbylene group represents a divalent hydrocarbon residue.

Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene and the like, and one or more of these are used. . The conjugated diene is preferably 1,3-butadiene or isoprene.

R ¹¹ is a hydrocarbyl group having a polymerizable carbon-carbon double bond, and R ¹¹ is preferably a group represented by the following formula (5).

（式中、ｐは０又は１であり、Ｒ^１５は水素原子又はヒドロカルビル基を表し、Ｔはヒドロカルビレン基を表す。）

(In the formula, p is 0 or 1, R ¹⁵ represents a hydrogen atom or a hydrocarbyl group, and T represents a hydrocarbylene group.)

In the formula (5), p represents 0 or 1.

Examples of the hydrocarbyl group for R ¹⁵ include an alkyl group and an alkenyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group is preferable. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group, and a vinyl group is preferable.

R ¹⁵ is preferably a hydrogen atom, a methyl group, or a vinyl group, and more preferably a hydrogen atom.

Examples of the hydrocarbylene group for T include an alkylene group, an arylene group, and a group in which an arylene group and an alkylene group are bonded.

Examples of the alkylene group include a methylene group, an ethylene group, and a trimethylene group. Preferably, it is a methylene group or an ethylene group. Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. A phenylene group is preferred.

Examples of the group in which an arylene group and an alkylene group are bonded include a group in which a phenylene group and an alkylene group are bonded, a group in which a naphthylene group and an alkylene group are bonded, and a group in which a biphenylene group and an alkylene group are bonded. . In a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), depending on the position of the carbon atom on the benzene ring from which the hydrogen atom is removed and the position of the carbon atom on the benzene ring to which the alkylene group is bonded, A para-phenylene-alkylene group (for example, a group represented by the following formula (5a)), a meta-phenylene-alkylene group (for example, a group represented by the following formula (5b)), an ortho-phenylene-alkylene group. (For example, a group represented by the following formula (5c)).

Moreover, as the group in which the arylene group and the alkylene group are bonded, it is preferable that the carbon atom of the arylene group of the group is bonded to the carbon atom to which R ¹⁵ of the formula (5) is bonded.

（式中、ｒは、１〜１０の整数を表す。）

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

The group in which an arylene group and an alkylene group are bonded (phenylene-alkylene group) is preferably a group in which a phenylene group and an alkylene group are bonded, more preferably a group represented by the above formula (5a), A group represented by the above formula (5b), more preferably a para-phenylene-methylene group (a group represented by the formula (5a) where r = 1), a meta-phenylene-methylene group (r = 1). A group represented by the formula (5b), a para-phenylene-ethylene group (a group represented by the formula (5a) where r = 2), a meta-phenylene-ethylene group (a formula where r = 2) Group represented by 5b).

When R ¹⁵ is a methyl group, p is preferably 1, and T is preferably a group in which an arylene group and an alkylene group are bonded or an arylene group, and more preferably a phenylene group and an alkylene group. A bonded group (phenylene-alkylene group) or a phenylene group, more preferably a phenylene group, a para-phenylene-methylene group, a meta-phenylene-methylene group, a para-phenylene-ethylene group, or a meta-phenylene-ethylene group. is there.

When R ¹⁵ is a vinyl group and p is 1, T is preferably an alkylene group, more preferably a methylene group or an ethylene group.

The group represented by the formula (5) is preferably a group in which R ¹⁵ is a hydrogen atom, such as vinyl group, vinylmethyl group, vinylethyl group, 4-vinylphenyl group, 3-vinylphenyl group, (4- Vinylphenyl) methyl group, 2- (4-vinylphenyl) ethyl group, (3-vinylphenyl) methyl group, 2- (3-vinylphenyl) ethyl group, and R ¹⁵ is a methyl group, 4-isopropenylphenyl group, 3-isopropenylphenyl group, (4-isopropenylphenyl) methyl group, 2- (4-isopropenylphenyl) ethyl group, (3-isopropenylphenyl) methyl group, 2- (3 - isopropenyl phenyl) ethyl group and the ^like, as the base ^{R 15} is a vinyl group, 1-methylene-2-propenyl group, 2-methylene-3 Buteni Group, and the like.

R ¹¹ is preferably a vinyl group, a 4-vinylphenyl group, or a 3-vinylphenyl group, and more preferably a vinyl group.

Examples of the hydrocarbyl group for R ¹² include an alkyl group and an aryl group.

As the alkyl group for R ¹² , a methyl group; a primary alkyl group such as an ethyl group, an n-propyl group, or an n-pentyl group (an alkyl group in which a carbon atom from which a hydrogen atom has been removed is a primary carbon atom); Secondary alkyl groups such as isopropyl group, sec-butyl group and 2-ethylhexyl group (alkyl groups in which a carbon atom from which a hydrogen atom has been removed is a secondary carbon atom); tert-butyl group, tert-pentyl group and the like A tertiary alkyl group (an alkyl group in which a carbon atom from which a hydrogen atom has been removed is a tertiary carbon atom) can be mentioned.

Examples of the aryl group for R ¹² include a phenyl group, a tolyl group, and a xylyl group.

The number of carbon atoms of the hydrocarbyl group of R ¹² is preferably 3 to 10, more preferably 4 to 8.

The hydrocarbyl group for R ¹² is preferably a secondary alkyl group or a tertiary alkyl group, more preferably a tertiary alkyl group, and still more preferably a tert-butyl group.

R ¹³ is an aryl group which may have an oxygen-containing substituent. Here, the aryl group having an oxygen-containing substituent represents a group in which a hydrogen atom of the aryl group is substituted with an oxygen-containing substituent.

The aryl group represented by R ¹³ includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenyl group substituted with an alkyl group, a 1-naphthyl group substituted with an alkyl group, and a 2-naphthyl substituted with an alkyl group. You can raise a group.

Examples of the alkyl group include: methyl group; primary alkyl group such as ethyl group, n-propyl group and n-butyl group; secondary alkyl group such as isopropyl group, sec-butyl group and 2-ethylhexyl group; And tertiary alkyl groups such as a tert-pentyl group.

Examples of the phenyl group substituted with an alkyl group include methylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, and tert-pentyl. A phenyl group, a (2-ethylhexyl) phenyl group, etc. can be mentioned.

Examples of 1-naphthyl group substituted with an alkyl group include methyl-1-naphthyl group, ethyl-1-naphthyl group, n-propyl-1-naphthyl group, isopropyl-1-naphthyl group, and n-butyl-1-naphthyl group. Group, sec-butyl-1-naphthyl group, tert-butyl-1-naphthyl group, tert-pentyl-1-naphthyl group, (2-ethylhexyl) -1-naphthyl group, and the like.

Examples of the 2-naphthyl group substituted with an alkyl group include methyl-2-naphthyl group, ethyl-2-naphthyl group, n-propyl-2-naphthyl group, isopropyl-2-naphthyl group, and n-butyl-2-naphthyl group. Group, sec-butyl-2-naphthyl group, tert-butyl-2-naphthyl group, tert-pentyl-2-naphthyl group, (2-ethylhexyl) -2-naphthyl group and the like.

The aryl group having an oxygen-containing substituent is an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group or a tert-butoxy group; an alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group or an ethoxyethyl group An aryl group having an alkoxyalkoxy group such as a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, or an ethoxyethoxy group.

Examples of the phenyl group having an alkoxy group include a methoxyphenyl group, an ethoxyphenyl group, an isopropoxyphenyl group, and a tert-butoxyphenyl group. Examples of the phenyl group having an alkoxyalkyl group include (methoxymethyl) phenyl group, (ethoxymethyl) phenyl group, (methoxyethyl) phenyl group, and (ethoxyethyl) phenyl group. Examples of the phenyl group having an alkoxyalkoxy group include (methoxymethoxy) phenyl group, (ethoxymethoxy) phenyl group, (methoxyethoxy) phenyl group, and (ethoxyethoxy) phenyl group.

Examples of the 1-naphthyl group having an alkoxy group include a methoxy-1-naphthyl group, an ethoxy-1-naphthyl group, an isopropoxy-1-naphthyl group, and a tert-butoxy-1-naphthyl group. Examples of the 1-naphthyl group having an alkoxyalkyl group include (methoxymethyl) -1-naphthyl group, (ethoxymethyl) -1-naphthyl group, (methoxyethyl) -1-naphthyl group, and (ethoxyethyl) -1-naphthyl. You can raise a group. Examples of the 1-naphthyl group having an alkoxyalkoxy group include (methoxymethoxy) -1-naphthyl group, (ethoxymethoxy) -1-naphthyl group, (methoxyethoxy) -1-naphthyl group, and (ethoxyethoxy) -1-naphthyl. You can raise a group.

Examples of the 2-naphthyl group having an alkoxy group include a methoxy-2-naphthyl group, an ethoxy-2-naphthyl group, an isopropoxy-2-naphthyl group, and a tert-butoxy-2-naphthyl group. Examples of the 2-naphthyl group having an alkoxyalkyl group include (methoxymethyl) -2-naphthyl group, (ethoxymethyl) -2-naphthyl group, (methoxyethyl) -2-naphthyl group, and (ethoxyethyl) -2-naphthyl. You can raise a group. Examples of the 2-naphthyl group having an alkoxyalkoxy group include (methoxymethoxy) -2-naphthyl group, (ethoxymethoxy) -2-naphthyl group, (methoxyethoxy) -2-naphthyl group, and (ethoxyethoxy) -2-naphthyl. You can raise a group.

Examples of the mono-substituted phenyl group include a 2-substituted phenyl group, a 3-substituted phenyl group, and a 4-substituted phenyl group depending on the substitution position. The phenyl group substituted with the above alkyl group or oxygen-containing substituent may be a disubstituted or trisubstituted product, and depending on the substitution position and the number of substitutions, a 2,3-disubstituted phenyl group, 2, 4-disubstituted phenyl group, 2,5-disubstituted phenyl group, 2,6-disubstituted phenyl group, 3,4-disubstituted phenyl group, 3,5-disubstituted phenyl group, 2,3,4-tri Substituted phenyl group, 2,3,5-trisubstituted phenyl group, 2,4,5-trisubstituted phenyl group, 2,4,6-trisubstituted phenyl group, 3,4,5-trisubstituted phenyl group, etc. It is done.

The mono-substituted 1-naphthyl group may be a 2-substituted 1-naphthyl group, a 3-substituted 1-naphthyl group, a 4-substituted 1-naphthyl group, a 5-substituted 1-naphthyl group, or a 6-substituted, depending on the substitution position. A 1-naphthyl group can be mentioned. Further, the 1-naphthyl group substituted with the above alkyl group or oxygen-containing substituent may be a di- or 3-substituent, and may be a 4,5-disubstituted 1-naphthyl group, 4,8-di- Substituted 1-naphthyl group, 5,8-disubstituted 1-naphthyl group, 6,7-disubstituted 1-naphthyl group, 3,8-disubstituted 1-naphthyl group, 6,8-disubstituted 1-naphthyl group, 4,5,8-trisubstituted 1-naphthyl group and the like.

The mono-substituted 2-naphthyl group may be a 1-substituted 2-naphthyl group, a 3-substituted 2-naphthyl group, a 4-substituted 2-naphthyl group, a 5-substituted 2-naphthyl group, or a 6-substituted, depending on the substitution position. A 2-naphthyl group can be mentioned. Further, the 1-naphthyl group substituted with the above alkyl group or oxygen-containing substituent may be a di- or 3-substituent, such as a 3,5-disubstituted 2-naphthyl group, 3,8-di- Examples thereof include a substituted 2-naphthyl group, a 4,5-disubstituted 2-naphthyl group, and a 1,4,5-trisubstituted 2-naphthyl group.

The number of carbon atoms of R ¹³ is preferably 6 to 10, and more preferably 6 to 8.

R ¹³ is preferably a phenyl group or a phenyl group substituted with an alkyl group. The phenyl group substituted with an alkyl group is preferably a 4-alkylphenyl group, more preferably a 4-methylphenyl group, a 4-ethylphenyl group, a 4-n-propylphenyl group, a 4-n- It is a butylphenyl group.

R ¹³ is more preferably a phenyl group, a 4-methylphenyl group or a 4-ethylphenyl group, and even more preferably a phenyl group.

Examples of the alkyl group for R ¹⁴ include a methyl group and an ethyl group.

（式中、Ｒ^１６及びＲ^１７は、それぞれ、ヒドロカルビル基、又は、トリヒドロカルビルシリル基を表し、あるいは、Ｒ^１６とＲ^１７は結合して、窒素原子及び／又は酸素原子をヘテロ原子として有していてもよいヒドロカルビレン基、又は、Ｒ^１６とＲ^１７は１つの基であって、窒素原子に二重結合で結合する基を表す。） Examples of the substituted amino group for R ¹⁴ include a group represented by the following formula (6).

(Wherein R ¹⁶ and R ¹⁷ each represent a hydrocarbyl group or a trihydrocarbylsilyl group, or R ¹⁶ and R ¹⁷ are bonded to each other and have a nitrogen atom and / or an oxygen atom as a hetero atom. And an optional hydrocarbylene group, or R ¹⁶ and R ¹⁷ are one group and represent a group bonded to a nitrogen atom by a double bond.)

Examples of the hydrocarbyl group of R ¹⁶ and R ¹⁷ include an alkyl group and an aryl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. A phenyl group etc. can be mention | raise | lifted as an aryl group. Preferably it is an alkyl group, More preferably, it is a C1-C4 alkyl group.

Examples of the trihydrocarbylsilyl group of R ¹⁶ and R ¹⁷ include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group. A trialkylsilyl group having 3 to 9 carbon atoms is preferable, and a trialkylsilyl group in which an alkyl group bonded to a silicon atom is an alkyl group having 1 to 3 carbon atoms is more preferable.

Examples of the hydrocarbylene group which may have a nitrogen atom and / or oxygen atom to which R ¹⁶ and R ¹⁷ are bonded as a hetero atom include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and the like An alkylene group; a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, and a group represented by —CH═CH—N═CH—. Group, a hydrocarbylene group having a nitrogen atom such as a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ —; a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —, etc. And a hydrocarbylene group having an oxygen atom.

In the present specification, the hydrocarbylene group having an X atom as a hetero atom represents a group having a structure in which a hydrogen atom and / or a carbon atom of the hydrocarbylene group is replaced with an X atom. For example, examples of the hydrocarbylene group having a nitrogen atom as a hetero atom include a group having a structure in which CH in the hydrocarbylene group is replaced with N. Examples of the hydrocarbylene group having an oxygen atom as a hetero atom include a group having a structure in which CH ₂ is replaced with O and a group having a structure in which two hydrogen atoms are replaced with O.

Examples of one group in which R ¹⁶ and R ¹⁷ are bonded to the nitrogen atom with a double bond include ethylidene group, propylidene group, butylidene group, 1-methylethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene Group.

R ¹⁴ is preferably an alkyl group such as a methyl group or an ethyl group, or a dialkylamino group such as a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, or a di (n-butyl) amino group.

In Formula (4), i represents 1 or 2, and h + i is 2 or 3. Preferably h + i is 3. More preferably, h is 1 and i is 2.

As the compound represented by the formula (4), as a compound in which R ¹⁵ is a hydrogen atom and p = 0,
tert-butoxydiphenylvinylsilane,
tert-pentoxydiphenylvinylsilane,
Di (tert-butoxy) phenylvinylsilane,
Di (tert-pentoxy) phenylvinylsilane,
tert-butoxymethylphenylvinylsilane,
tert-butoxyethylphenylvinylsilane,
Dimethylamino tert-butoxyphenylvinylsilane,
Examples thereof include diethylamino tert-butoxyphenylvinylsilane.

In addition, as a compound represented by the formula (4), as a compound in which R ¹⁵ is a hydrogen atom and p = 1,
tert-butoxydiphenyl-4-vinylphenylsilane,
tert-butoxydiphenyl-3-vinylphenylsilane,
Di (tert-butoxy) phenyl-4-vinylphenylsilane,
Di (tert-butoxy) phenyl-3-vinylphenylsilane,
tert-butoxymethylphenyl-4-vinylphenylsilane,
tert-butoxymethylphenyl-3-vinylphenylsilane,
tert-butoxyethylphenyl-4-vinylphenylsilane,
tert-butoxyethylphenyl-3-vinylphenylsilane,
Dimethylamino tert-butoxyphenyl-4-vinylphenylsilane,
Dimethylamino tert-butoxyphenyl-3-vinylphenylsilane,
Diethylamino tert-butoxyphenyl-4-vinylphenylsilane,
Diethylamino tert-butoxyphenyl-3-vinylphenylsilane,
Etc.

As the compound represented by the formula (4), as a compound in which R ¹⁵ is a methyl group and p = 1,
tert-butoxydiphenyl-4-isopropenylphenylsilane,
tert-butoxydiphenyl-3-isopropenylphenylsilane,
Di (tert-butoxy) phenyl-4-isopropenylphenylsilane,
Di (tert-butoxy) phenyl-3-isopropenylphenylsilane,
tert-butoxymethylphenyl-4-isopropenylphenylsilane,
tert-butoxymethylphenyl-3-isopropenylphenylsilane,
tert-butoxyethylphenyl-4-isopropenylphenylsilane,
tert-butoxyethylphenyl-3-isopropenylphenylsilane,
Dimethylamino tert-butoxyphenyl-4-isopropenylphenylsilane,
Dimethylamino tert-butoxyphenyl-3-isopropenylphenylsilane,
Diethylamino tert-butoxyphenyl-4-isopropenylphenylsilane,
Diethylamino tert-butoxyphenyl-3-isopropenylphenylsilane,
Etc.

The compound represented by formula (4) is preferably a compound in which R ¹⁵ is a hydrogen atom and p = 0.
More preferably,
tert-butoxydiphenylvinylsilane,
Di (tert-butoxy) phenylvinylsilane,
tert-butoxymethylphenylvinylsilane,
Dimethylamino-tert-butoxyphenylvinylsilane,
Diethylamino-tert-butoxyphenylvinylsilane;
More preferably, tert-butoxydiphenylvinylsilane,
Di (tert-butoxy) phenylvinylsilane,
Particularly preferred is tert-butoxydiphenylvinylsilane.

In the conjugated diene polymer (B), the content of the monomer unit based on the compound represented by the formula (4) is preferably 0 in order to increase the rubber strength per 100% by mass of the conjugated diene polymer. 0.01% by mass or more, more preferably 0.02% by mass or more. Moreover, in order to improve economical efficiency, Preferably it is 2 mass% or less, More preferably, it is 1 mass% or less.

In the conjugated diene polymer (B), the total amount of conjugated diene units and monomer units based on the compound represented by the formula (4) is 100 masses of the total amount of monomer units in the conjugated diene polymer. % Is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and still more preferably 100% by mass in order to increase rubber strength.

In the conjugated diene polymer (B), a monomer unit based on the monomer represented by the formula (4) is present in the chain, that is, a partial chain having a monomer unit based on the conjugated diene ( The partial chain does not have a monomer unit based on the monomer represented by the formula (4).) And a partial chain having a monomer unit based on a conjugated diene (the partial chain includes The monomer unit based on the monomer represented by the formula (4) or the formula (4). It is preferable to have a partial chain consisting of monomer units based on the monomer represented by 4).

The Mooney viscosity (ML _{1 + 4} ) of the conjugated diene polymer (B) is preferably 10 or more, more preferably 20 or more, in order to increase rubber strength. Moreover, in order to improve workability, Preferably it is 200 or less, More preferably, it is 150 or less. The Mooney viscosity (ML _{1 + 4} ) is measured at 100 ° C. according to JIS K6300 (1994).

The vinyl bond content of the conjugated diene polymer (B) is preferably 80 mol% or less, more preferably 70 mol% or less, in order to improve fuel efficiency, with the content of the conjugated diene unit being 100 mol%. It is. Moreover, in order to improve grip property, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more, Most preferably, it is 40 mol% or more. The vinyl bond amount is determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

The molecular weight distribution of the conjugated diene polymer (B) is preferably 1.0 to 5.0, and more preferably 1.0 to 1.5, in order to improve fuel economy. The molecular weight distribution is determined by measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) method and dividing Mw by Mn.

As a suitable method for producing the conjugated diene polymer (B), a monomer component containing the conjugated diene and the compound represented by the above formula (4) is polymerized in a hydrocarbon solvent with an alkali metal catalyst. I can give you a way.

Examples of the alkali metal catalyst 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. An organic lithium compound or an organic sodium compound is preferable, and an organic lithium compound having 2 to 20 carbon atoms or an organic sodium compound having 2 to 20 carbon atoms is more preferable.

The hydrocarbon solvent is a solvent that does not deactivate the organic alkali metal compound catalyst, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Examples of the aliphatic hydrocarbon include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2- Examples include butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and the like. In addition, examples of the aromatic hydrocarbon include benzene, toluene, xylene, and ethylbenzene. Examples of the alicyclic hydrocarbon include cyclopentane and cyclohexane. One or more of these may be used, and the hydrocarbon solvent may be a mixture of various components such as industrial hexane. Preferably, it is a hydrocarbon having 2 to 12 carbon atoms.

In a hydrocarbon solvent, a monomer component containing a conjugated diene and a compound represented by the above formula (4) is polymerized with an alkali metal catalyst, and the monomer unit based on the conjugated diene and the above formula (4) A polymer having a monomer unit based on the represented compound is produced. Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. One or more of these are used. 1,3-butadiene and isoprene are preferred.

The amount of the compound represented by formula (4) is preferably 0.01% by mass or more in order to increase the rubber strength, with the total amount of monomer components used in the polymerization being 100% by mass, More preferably, it is 0.02 mass% or more. Moreover, in order to improve economical efficiency, Preferably it is 2 mass% or less, More preferably, it is 1 mass% or less.

In the polymerization reaction, the total amount of the conjugated diene and the compound represented by the formula (4) is 100% by mass based on the total amount of the monomer components used in the polymerization, in order to increase the rubber strength. Preferably it is 99.9 mass% or more, More preferably, it is 99.95 mass% or more, More preferably, it is 100 mass%.

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

The polymerization temperature is usually 25 to 100 ° C, preferably 35 to 90 ° C, more preferably 50 to 80 ° C. The polymerization time is usually 10 minutes to 5 hours.

（式中、ｊ〜ｌは、独立に、１〜８の整数を表す。） The conjugated diene polymer (C) according to the third aspect of the present invention comprises an alkali metal catalyst containing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of a Lewis basic compound in a hydrocarbon solvent. It is obtained by reacting a compound represented by the following formula (7) with an active conjugated diene polymer having an alkali metal terminal obtained by polymerization.

(Wherein j to l independently represent an integer of 1 to 8)

Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene (piperine), 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, and the like. Then, 1,3-butadiene and isoprene are preferred from the viewpoint of the physical properties of the resulting polymer and the availability for industrial implementation.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, divinyl naphthalene and the like. Among these, the physical properties of the resulting polymer, industrial Styrene is preferable from the viewpoint of availability in carrying out.

The hydrocarbon solvent is one that does not deactivate the alkali metal catalyst, and the suitable hydrocarbon solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons, particularly having 3 to 12 carbon atoms. Propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, cyclohexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1 -Pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These solvents can be used as a mixture of two or more.

Examples of the alkali metal catalyst include metals such as lithium, sodium, potassium, rubidium, and cesium, hydrocarbon compounds containing these metals, and complexes of the metals with polar compounds. Preferred examples of the alkali metal catalyst include lithium or sodium compounds having 2 to 20 carbon atoms. Specific examples thereof include ethyl lithium, n-propyl lithium, and iso-propyl lithium. N-butyl lithium, sec-butyl lithium, t-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium 4-cyclopentyl lithium, Examples include 1,4-dilithio-butene-2, sodium naphthalene, sodium biphenyl, potassium-tetrahydrofuran complex, potassium diethoxyethane complex, and sodium salt of α-methylstyrene tetramer.

As the modifying compound to be reacted with the active diene polymer used in the present invention, a compound represented by the above formula (7) is used, and j to l are independently preferably an integer of 1 to 8, and low fuel consumption. For improvement, triglycidyl isocyanurate in which j to l are all 1 is most preferable.

As the polymerization monomer, only a conjugated diene monomer may be used, or a conjugated diene monomer and an aromatic vinyl monomer may be used in combination, but it is preferable to use only a conjugated diene monomer. The ratio of the conjugated diene monomer to the aromatic vinyl monomer is preferably 99/1, more preferably 99.9 / 0.1, and still more preferably 100/0 in terms of the mass ratio of conjugated diene monomer / aromatic vinyl monomer.

In the polymerization, it is possible to use commonly used materials such as an alkali metal catalyst, a hydrocarbon solvent, a reagent for improving random polymerizability, and a vinyl bond content regulator for conjugated diene units. The polymerization temperature in the production of the copolymer is not particularly limited, but is usually −80 ° C. to 150 ° C., and preferably 20 to 110 ° C. from the viewpoint of the reaction rate and the stability of the alkali metal catalyst. The polymerization time is not particularly limited, but the alkali metal catalyst is completed within at least 24 hours.

In order to adjust the vinyl bond content of the conjugated diene part, various compounds can be used as the Lewis basic compound. However, ether compounds or tertiary amines are easily available in industrial implementation. preferable. Examples of ether compounds 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, diethylene glycol diethyl ether, Aliphatic diethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole. Examples of tertiary amine compounds include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N-diethylaniline, pyridine, quinoline and the like. be able to.

The amount used when the modified compound represented by the general formula (7) of the present invention is added to the active conjugated diene polymer having an alkali metal terminal is used for the alkali used when adding the alkali metal. It is 0.06-10 mol normally per 1 mol of metal catalysts, Preferably it is 0.1-5 mol, More preferably, it is 0.2-2 mol. If the amount used is too small, the effect of improving fuel economy is small, and if it is too large, it remains in the polymerization solvent. Therefore, when the solvent is recycled, a separation step from the solvent is required. Etc., not economically desirable.

Since the reaction between the modifying compound and the active conjugated diene polymer having an alkali metal terminal occurs rapidly, the reaction temperature and reaction time can be selected in a wide range, but generally room temperature to 100 ° C., several seconds to A few hours. The reaction may be performed by bringing the alkali metal-containing diene polymer and the modified compound into contact with each other. For example, an alkali metal catalyst is used to polymerize the diene polymer, and the modified compound is placed in the polymer solution. Although the method of adding quantitatively can be illustrated as a preferred embodiment, it is not limited to this method.

A modified diene polymer rubber is reacted with an active conjugated diene polymer having an alkali metal terminal by adding a coagulant from a reaction solvent by reacting with the modifying compound represented by the general formula (7). Alternatively, the coagulation method used in the production of rubber by ordinary solution polymerization such as steam coagulation is used as it is, and the coagulation temperature is not limited at all.

For drying the crumb separated from the reaction system, a band drier, an extrusion drier or the like used in the production of ordinary synthetic rubber can be used, and the drying temperature is not limited at all.

The Mooney viscosity (ML _{1 + 4} ) of the conjugated diene polymer (C) is preferably 10 to 200, more preferably 20 to 150. If the Mooney viscosity is too low, mechanical properties such as the tensile strength of the vulcanizate may be reduced. On the other hand, if the viscosity is too high, miscibility will be poor when used in combination with other rubbers, making processing difficult. In some cases, the mechanical properties of the vulcanizate of the obtained rubber composition are lowered.

The vinyl bond content of the conjugated diene part of the conjugated diene polymer (C) is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, where the content of the conjugated diene unit is 100 mol%. is there. If it is less than 10 mol%, the grip performance may be inferior, and if it exceeds 70 mol%, the fuel efficiency may be inferior.

The molecular weight distribution of the conjugated diene polymer (C) is preferably 1.0 to 5.0, and more preferably 1.0 to 1.5, in order to improve fuel efficiency. The molecular weight distribution is determined by measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) method and dividing Mw by Mn.

（式中、Ｒ^２１は水素原子又は炭素原子数１〜５のヒドロカルビル基を表し、ｓは０又は１であり、Ｒ^２２はヒドロカルビレン基を表し、Ｒ^２３及びＲ^２４は、それぞれ、ヒドロカルビル基、又は、トリヒドロカルビルシリル基、あるいは、Ｒ^２３とＲ^２４とが結合して、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビレン基、又は、Ｒ^２３とＲ^２４は１つの基であって、窒素原子に二重結合で結合する基を表す。）

（式中、ｔは１〜１０の整数を表し、Ｒ^２５、Ｒ^２６及びＲ^２７は、それぞれ、ヒドロカルビル基又はヒドロカルビルオキシ基を表し、Ｒ^２５、Ｒ^２６及びＲ^２７の少なくとも１つがヒドロカルビルオキシ基であり、Ｒ^２８及びＲ^２９は、それぞれ、水素原子、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビル基、あるいは、Ｒ^２８とＲ^２９とが結合して、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビレン基、又は、Ｒ^２８とＲ^２９は１つの基であって、窒素原子に二重結合で結合する基を表す。） The conjugated diene polymer (D) according to the fourth aspect of the present invention is a conjugated diene system having a monomer unit based on a conjugated diene and a monomer unit based on a monomer represented by the following formula (8). It can be obtained by reacting one end of the polymer with a compound represented by the following formula (9).

(Wherein R ²¹ represents a hydrogen atom or a hydrocarbyl group having 1 to 5 carbon atoms, s is 0 or 1, R ²² represents a hydrocarbylene group, and R ²³ and R ²⁴ are each a hydrocarbyl group. Group, a trihydrocarbylsilyl group, or a hydrocarbylene group in which R ²³ and R ²⁴ are bonded to each other and optionally have a nitrogen atom and / or an oxygen atom, or R ²³ and R ²⁴ are 1 Represents a group which is bonded to a nitrogen atom with a double bond.)

(Wherein t represents an integer of 1 to 10, R ²⁵ , R ²⁶ and R ²⁷ each represents a hydrocarbyl group or a hydrocarbyloxy group, and at least one of R ²⁵ , R ²⁶ and R ²⁷ is a hydrocarbyloxy group. R ²⁸ and R ²⁹ are each a hydrogen atom, a nitrogen atom and / or a hydrocarbyl group optionally having an oxygen atom, or R ²⁸ and R ²⁹ are bonded to form a nitrogen atom and / or (The hydrocarbylene group which may have an oxygen atom, or R ²⁸ and R ²⁹ are one group and represent a group bonded to a nitrogen atom with a double bond.)

As used herein, a hydrocarbyl group represents a hydrocarbon residue. The hydrocarbyloxy group represents a group in which a hydrogen atom of a hydroxyl group is substituted with a hydrocarbyl group. The hydrocarbylene group represents a divalent hydrocarbon residue. Moreover, the hydrocarbyl group having an X atom represents a group having a structure in which a hydrogen atom and / or a carbon atom of the hydrocarbyl group is replaced with an X atom, and the hydrocarbylene group having an X atom is a hydrocarbylene group This represents a group having a structure in which a hydrogen atom and / or a carbon atom is replaced with an X atom. For example, examples of the group having a nitrogen atom include a group having a structure in which CH is replaced by N. Examples of the group having an oxygen atom include a group having a structure in which CH ₂ is replaced with O, and a group having a structure in which two hydrogen atoms are replaced with O.

Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene and the like, and one or more of these are used. . The conjugated diene is preferably 1,3-butadiene or isoprene.

R ²¹ represents a hydrogen atom or a hydrocarbyl group having 1 to 5 carbon atoms.

Examples of the hydrocarbyl group for R ²¹ include an alkyl group and an alkenyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group is preferable. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group, and a vinyl group is preferable.

R ²¹ is preferably a hydrogen atom, a methyl group, or a vinyl group.

Examples of the hydrocarbylene group for R ²² include an alkylene group, an arylene group, and a group in which an arylene group and an alkylene group are bonded.

Examples of the alkylene group include a methylene group, an ethylene group, and a trimethylene group. Preferably, it is a methylene group or an ethylene group.

Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. A phenylene group is preferred.

Examples of the group in which an arylene group and an alkylene group are bonded include a group in which a phenylene group and an alkylene group are bonded, a group in which a naphthylene group and an alkylene group are bonded, and a group in which a biphenylene group and an alkylene group are bonded. . A group in which a phenylene group and an alkylene group are bonded is preferable.

Further, as the group in which the arylene group and the alkylene group are bonded, it is preferable that the carbon atom of the arylene group of the group is bonded to the carbon atom to which R ^{21 in} the formula (8) is bonded.

In a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), depending on the position of the carbon atom on the benzene ring from which the hydrogen atom is removed and the position of the carbon atom on the benzene ring to which the alkylene group is bonded, Para-phenylene-alkylene group (for example, group represented by the following formula (8a)), meta-phenylene-alkylene group (for example, group represented by the following formula (8b)), ortho-phenylene-alkylene group. (For example, a group represented by the following formula (8c)).

（式中、ｖは１〜５の整数を表す。）

(In the formula, v represents an integer of 1 to 5.)

The group in which an arylene group and an alkylene group are bonded is preferably a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), more preferably a group represented by the above formula (8a), A group represented by the above formula (8b), a group represented by the above formula (8c), and more preferably a group represented by the above formula (8a) and a group represented by the above formula (8b). And particularly preferably a para-phenylene-methylene group (a group represented by the formula (8a) in which v = 1) and a meta-phenylene-methylene group (a group represented by the formula (8b) in which v = 1). ), Para-phenylene-ethylene group (group represented by formula (8a) where v = 2), and meta-phenylene-ethylene group (group represented by formula (8b) where v = 2).

When R ²¹ is a hydrogen atom or an alkyl group, preferably s = 1. The hydrocarbylene group for R ²² is preferably a group represented by the following formula (10), more preferably a group represented by the following formula (10a) or a group represented by the following formula (10b). Group. Moreover, in formula, u is an integer of 0-5, Preferably it is an integer of 0-2.

（式中、（ＣＨ_２）_ｕはベンゼン環上の置換基であり、ｕは０〜５の整数を表し、ｕが１〜５の整数である場合、（ＣＨ_２）_ｕが式（８）の窒素原子と結合する。）

（式中、ｕは０〜５の整数を表し、ｕが１〜５の整数である場合、（ＣＨ_２）_ｕが式（８）の窒素原子と結合する。）

(In the formula, (CH ₂ ) _u is a substituent on the benzene ring, u represents an integer of 0 to 5, and when u is an integer of 1 to 5, (CH ₂ ) _u is represented by formula (8). To bond with the nitrogen atom.)

(In the formula, u represents an integer of 0 to 5, and when u is an integer of 1 to 5, (CH ₂ ) _u is bonded to the nitrogen atom of formula (8).)

When R ²¹ is an alkenyl group and s = 1, the hydrocarbylene group of R ²² is preferably an alkylene group, more preferably a methylene group or an ethylene group.

R ²³ and R ²⁴ are each a hydrocarbyl group, a trihydrocarbyl silyl group, or a hydrocarbylene group that may have a nitrogen atom and / or an oxygen atom by bonding R ²³ and R ^24. Alternatively, R ²³ and R ²⁴ are one group and represent a group bonded to a nitrogen atom with a double bond.

Examples of the hydrocarbyl group of R ²³ and R ²⁴ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group. Examples of the alkynyl group include an ethynyl group and a propargyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group.

The number of carbon atoms of the hydrocarbyl group of R ²³ and R ²⁴ is preferably 1 to 10, more preferably 1 to 4.

The hydrocarbyl group of R ²³ and R ²⁴ is preferably an alkyl group or an alkenyl group, more preferably a linear alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms. More preferably, they are a methyl group, an ethyl group, and an allyl group.

The trihydrocarbyl silyl group R ²³ and R ^24, may be mentioned trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, a trialkylsilyl group such as tert- butyldimethylsilyl group.

The trihydrocarbylsilyl group of R ²³ and R ²⁴ is preferably a trialkylsilyl group having 3 to 9 carbon atoms, more preferably an alkyl group bonded to a silicon atom having 1 to 3 carbon atoms. It is a trialkylsilyl group which is an alkyl group.

Examples of the hydrocarbylene group optionally having a nitrogen atom and / or an oxygen atom to which R ²³ and R ²⁴ are bonded include a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and a hydrocarbylene having an oxygen atom. Group. Examples of the hydrocarbylene group include an alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. As the hydrocarbylene group having a nitrogen atom, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH—N A group represented by ═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified. Examples of the hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the group to which R ²³ and R ²⁴ are bonded is preferably 2 to 20, more preferably 2 to 7, and still more preferably 4 to 6.

The hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom to which R ²³ and R ²⁴ are bonded as a hetero atom is preferably a hydrocarbylene group, more preferably an alkylene group, A polymethylene group is preferred.

Examples of one group in which R ²³ and R ²⁴ are bonded to the nitrogen atom with a double bond include ethylidene group, propylidene group, butylidene group, 1-methylethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene And hydrocarbylidene groups such as groups.

The number of carbon atoms of one group in which R ²³ and R ²⁴ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 6.

R ²³ and R ²⁴ are preferably a hydrocarbyl group, a trihydrocarbyl silyl group, or a hydrocarbylene group in which R ²³ and R ²⁴ are bonded, more preferably 4 carbon atoms in which R ²³ and R ²⁴ are bonded. -6 polymethylene groups.

Examples of the compound represented by the formula (8) include the following compounds in which R ²¹ is a hydrogen atom and s = 1.

Compound in which R ²² is a group represented by formula (10) and u = 0:
4-N, N-dimethylaminostyrene,
3-N, N-dimethylaminostyrene,
4-N, N-diethylaminostyrene,
3-N, N-diethylaminostyrene,
4-N, N-di-n-propylaminostyrene,
3-N, N-di-n-propylaminostyrene,
4-N, N-di-n-butylaminostyrene,
3-N, N-di-n-butylaminostyrene,
4-N, N-diallylaminostyrene,
3-N, N-diallylaminostyrene,
4-N, N-bis (trimethylsilyl) aminostyrene,
3-N, N-bis (trimethylsilyl) aminostyrene,
4-N, N-bis (tert-butyldimethylsilyl) aminostyrene,
3-N, N-bis (tert-butyldimethylsilyl) aminostyrene,
4-aziridinyl styrene,
3-aziridinyl styrene,
4-pyrrolidinylstyrene,
3-pyrrolidinylstyrene,
4-piperidinylstyrene,
3-piperidinylstyrene,
4-hexamethyleneiminostyrene,
3-hexamethyleneiminostyrene.

Compound wherein R ²² is a group represented by formula (10) and u = 1:
4-N, N-dimethylaminomethylstyrene,
3-N, N-dimethylaminomethylstyrene,
4-N, N-diethylaminomethylstyrene,
3-N, N-diethylaminomethylstyrene,
4-N, N-di-n-propylaminomethylstyrene,
3-N, N-di-n-propylaminomethylstyrene,
4-N, N-di-n-butylaminomethylstyrene,
3-N, N-di-n-butylaminomethylstyrene,
4-N, N-diallylaminomethylstyrene,
3-N, N-diallylaminomethylstyrene,
4-N, N-bis (trimethylsilyl) aminomethylstyrene,
3-N, N-bis (trimethylsilyl) aminomethylstyrene,
4-N, N-bis (tert-butyldimethylsilyl) aminomethylstyrene,
3-N, N-bis (tert-butyldimethylsilyl) aminomethylstyrene,
4-aziridinylmethylstyrene,
3-aziridinylmethylstyrene,
4-pyrrolidinylmethylstyrene,
3-pyrrolidinylmethylstyrene,
4-piperidinylmethylstyrene,
3-piperidinylmethylstyrene,
4-hexamethyleneiminomethylstyrene,
3-hexamethyleneiminomethylstyrene.

Compound wherein R ²² is a group represented by formula (10) and u = 2:
4-N, N-dimethylaminoethylstyrene,
3-N, N-dimethylaminoethylstyrene,
4-N, N-diethylaminoethylstyrene,
3-N, N-diethylaminoethylstyrene,
4-N, N-di-n-propylaminoethylstyrene,
3-N, N-di-n-propylaminoethylstyrene,
4-N, N-di-n-butylaminoethylstyrene,
3-N, N-di-n-butylaminoethylstyrene,
4-N, N-diallylaminoethylstyrene,
3-N, N-diallylaminoethylstyrene,
4-N, N-bis (trimethylsilyl) aminoethylstyrene,
3-N, N-bis (trimethylsilyl) aminoethylstyrene,
4-N, N-bis (tert-butyldimethylsilyl) aminoethylstyrene,
3-N, N-bis (tert-butyldimethylsilyl) aminoethylstyrene,
4-aziridinylethylstyrene,
3-aziridinylethylstyrene,
4-pyrrolidinylethylstyrene,
3-pyrrolidinylethylstyrene,
4-piperidinylethylstyrene,
3-piperidinylethylstyrene,
4-hexamethyleneiminoethylstyrene,
3-hexamethyleneiminoethylstyrene.

Examples of the compound represented by the formula (8) include the following compounds in which R ²¹ is a methyl group and s = 1.

Compound in which R ²² is a group represented by formula (10) and u = 0:
4-N, N-dimethylaminoisopropenylbenzene,
3-N, N-dimethylaminoisopropenylbenzene,
4-N, N-diethylaminoisopropenylbenzene,
3-N, N-diethylaminoisopropenylbenzene,
4-N, N-di-n-propylaminoisopropenylbenzene,
3-N, N-di-n-propylaminoisopropenylbenzene,
4-N, N-di-n-butylaminoisopropenylbenzene,
3-N, N-di-n-butylaminoisopropenylbenzene,
4-N, N-diallylaminoisopropenylbenzene,
3-N, N-diallylaminoisopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminoisopropenylbenzene,
3-N, N-bis (trimethylsilyl) aminoisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminoisopropenylbenzene,
3-N, N-bis (tert-butyldimethylsilyl) aminoisopropenylbenzene,
4-aziridinyl isopropenylbenzene,
3-aziridinyl isopropenylbenzene,
4-pyrrolidinylisopropenylbenzene,
3-pyrrolidinylisopropenylbenzene,
4-piperidinylisopropenylbenzene,
3-piperidinylisopropenylbenzene,
4-hexamethyleneiminoisopropenylbenzene,
3-hexamethyleneiminoisopropenylbenzene.

Compound wherein R ²² is a group represented by formula (10) and u = 1:
4-N, N-dimethylaminomethylisopropenylbenzene,
3-N, N-dimethylaminomethylisopropenylbenzene,
4-N, N-diethylaminomethylisopropenylbenzene,
3-N, N-diethylaminomethylisopropenylbenzene,
4-N, N-di-n-propylaminomethylisopropenylbenzene,
3-N, N-di-n-propylaminomethylisopropenylbenzene,
4-N, N-di-n-butylaminomethylisopropenylbenzene,
3-N, N-di-n-butylaminomethylisopropenylbenzene,
4-N, N-diallylaminomethylisopropenylbenzene,
3-N, N-diallylaminomethylisopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminomethylisopropenylbenzene,
3-N, N-bis (trimethylsilyl) aminomethylisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminomethylisopropenylbenzene,
3-N, N-bis (tert-butyldimethylsilyl) aminomethylisopropenylbenzene,
4-aziridinylmethyl isopropenylbenzene,
3-aziridinylmethyl isopropenylbenzene,
4-pyrrolidinylmethylisopropenylbenzene,
3-pyrrolidinylmethylisopropenylbenzene,
4-piperidinylmethylisopropenylbenzene,
3-piperidinylmethyl isopropenylbenzene,
4-hexamethyleneiminomethylisopropenylbenzene,
3-hexamethyleneiminomethylisopropenylbenzene.

Compound wherein R ²² is a group represented by formula (10) and u = 2:
4-N, N-dimethylaminoethylisopropenylbenzene,
3-N, N-dimethylaminoethylisopropenylbenzene,
4-N, N-diethylaminoethylisopropenylbenzene,
3-N, N-diethylaminoethylisopropenylbenzene,
4-N, N-di-n-propylaminoethylisopropenylbenzene,
3-N, N-di-n-propylaminoethylisopropenylbenzene,
4-N, N-di-n-butylaminoethylisopropenylbenzene,
3-N, N-di-n-butylaminoethyl isopropenylbenzene,
4-N, N-diallylaminoethyl isopropenylbenzene,
3-N, N-diallylaminoethylisopropenylbenzene,
4-N, N-bis (trimethylsilyl) aminoethylisopropenylbenzene,
3-N, N-bis (trimethylsilyl) aminoethylisopropenylbenzene,
4-N, N-bis (tert-butyldimethylsilyl) aminoethylisopropenylbenzene,
3-N, N-bis (tert-butyldimethylsilyl) aminoethylisopropenylbenzene,
4-aziridinylethyl isopropenylbenzene,
3-aziridinylethyl isopropenylbenzene,
4-pyrrolidinylethyl isopropenylbenzene,
3-pyrrolidinylethyl isopropenylbenzene,
4-piperidinylethyl isopropenylbenzene,
3-piperidinylethyl isopropenylbenzene,
4-hexamethyleneiminoethyl isopropenylbenzene,
3-hexamethyleneiminoethyl isopropenylbenzene.

Examples of the compound represented by the formula (8) include the following compounds in which R ²¹ is a vinyl group and s = 0.
2-N, N-dimethylamino-1,3-butadiene,
2-N, N-diethylamino-1,3-butadiene,
2-N, N-di-n-propylamino-1,3-butadiene,
2-N, N-di-n-butylamino-1,3-butadiene,
2-N, N-diallylamino-1,3-butadiene,
2-N, N-bis (trimethylsilyl) amino-1,3-butadiene,
2-N, N-bis (tert-butyldimethylsilyl) amino-1,3-butadiene,
2-aziridinyl-1,3-butadiene,
2-pyrrolidinyl-1,3-butadiene,
2-piperidinyl-1,3-butadiene,
2-Hexamethyleneimino-1,3-butadiene.

Examples of the compound represented by the formula (8) include the following compounds in which R ²¹ is a vinyl group and s = 1.
2-N, N-dimethylaminomethyl-1,3-butadiene,
2-N, N-diethylaminomethyl-1,3-butadiene,
2-N, N-di-n-propylaminomethyl-1,3-butadiene,
2-N, N-di-n-butylaminomethyl-1,3-butadiene,
2-N, N-diallylaminomethyl-1,3-butadiene,
2-N, N-bis (trimethylsilyl) aminomethyl-1,3-butadiene,
2-N, N-bis (tert-butyldimethylsilyl) aminomethyl-1,3-butadiene,
2-aziridinylmethyl-1,3-butadiene,
2-pyrrolidinylmethyl-1,3-butadiene,
2-piperidinylmethyl-1,3-butadiene,
2-Hexamethyleneiminomethyl-1,3-butadiene.

5-N, N-dimethylamino-3-methylene-1-pentene,
5-N, N-diethylamino-3-methylene-1-pentene,
5-N, N-di-n-propylamino-3-methylene-1-pentene,
5-N, N-di-n-butylamino-3-methylene-1-pentene,
5-N, N-diallylamino-3-methylene-1-pentene,
5-N, N-bis (trimethylsilyl) amino-3-methylene-1-pentene,
5-N, N-bis (tert-butyldimethylsilyl) amino-3-methylene-1-pentene,
5-aziridinyl-3-methylene-1-pentene,
5-pyrrolidinyl-3-methylene-1-pentene,
5-piperidinyl-3-methylene-1-pentene,
5-Hexamethyleneimino-3-methylene-1-pentene.

The compound represented by the formula (8) is preferably a compound in which R ²¹ is a hydrogen atom and s is 1. More ^{preferably, R 23} and ^{R 24,} respectively a methyl group or an ethyl group ^{compounds, R 23} and ^{R 24,} the compound is a trimethylsilyl ^group, is bonded to the ^{R 23} and ^{R 24, R 23} and R ²⁴ is a compound in which the group bonded to ²⁴ is a polymethylene group having 4 to 6 carbon atoms.

Compounds in which R ²³ and R ²⁴ are each a methyl group or an ethyl group:
4-N, N-dimethylaminostyrene,
3-N, N-dimethylaminostyrene,
4-N, N-diethylaminostyrene,
3-N, N-diethylaminostyrene,
4-N, N-dimethylaminomethylstyrene,
3-N, N-dimethylaminomethylstyrene,
4-N, N-diethylaminomethylstyrene,
3-N, N-diethylaminomethylstyrene,
4-N, N-dimethylaminoethylstyrene,
3-N, N-dimethylaminoethylstyrene,
4-N, N-diethylaminoethylstyrene,
3-N, N-diethylaminoethylstyrene.

Compounds in which R ²³ and R ²⁴ are trimethylsilyl groups:
4-N, N-bis (trimethylsilyl) aminostyrene,
3-N, N-bis (trimethylsilyl) aminostyrene,
4-N, N-bis (trimethylsilyl) aminomethylstyrene,
3-N, N-bis (trimethylsilyl) aminomethylstyrene,
4-N, N-bis (trimethylsilyl) aminoethylstyrene,
3-N, N-bis (trimethylsilyl) aminoethylstyrene.

And R ²³ and ^{R 24} are ^bonded, compound group and ^{R 23} and ^{R 24} are bonded is a polymethylene group of 4 to 6 carbon atoms:
4-pyrrolidinylstyrene,
3-pyrrolidinylstyrene,
4-piperidinylstyrene,
3-piperidinylstyrene,
4-hexamethyleneiminostyrene,
3-hexamethyleneiminostyrene,
4-pyrrolidinylmethylstyrene,
3-pyrrolidinylmethylstyrene,
4-piperidinylmethylstyrene,
3-piperidinylmethylstyrene,
4-hexamethyleneiminomethylstyrene,
3-hexamethyleneiminomethylstyrene,
4-pyrrolidinylethylstyrene,
3-pyrrolidinylethylstyrene,
4-piperidinylethylstyrene,
3-piperidinylethylstyrene,
4-hexamethyleneiminoethylstyrene,
3-hexamethyleneiminoethylstyrene.

The compound represented by formula (8), more ^preferably, the ^{R 23} and ^{R 24} are ^bonded, compound group and ^{R 23} and ^{R 24} are bonded is a polymethylene group of 4 to 6 carbon atoms It is.

As the compound represented by the formula (8), 4-pyrrolidinylethylstyrene and 3-pyrrolidinylethylstyrene are particularly preferable.

R ²⁵ , R ²⁶ and R ²⁷ each represent a hydrocarbyl group or a hydrocarbyloxy group.

Examples of the hydrocarbyl group of R ²⁵ , R ²⁶ , and R ²⁷ 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. The number of carbon atoms of the hydrocarbyl group is preferably 1 to 10, more preferably 1 to 3.

The hydrocarbyl group of R ²⁵ , R ²⁶ , and R ²⁷ is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably 1 to 3 carbon atoms. And particularly preferably a methyl group or an ethyl group.

Examples of the hydrocarbyloxy group for R ²⁵ , R ²⁶ , and R ²⁷ include alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group; An aryloxy group such as a phenoxy group can be exemplified. The number of carbon atoms of the hydrocarbyloxy group is preferably 1 to 10, more preferably 1 to 3.

The hydrocarbyloxy group for R ²⁵ , R ²⁶ , and R ²⁷ is preferably an alkoxy group, more preferably an alkoxy group having 1 to 10 carbon atoms, and still more preferably 1 to 1 carbon atom. 3 is particularly preferably a methoxy group or an ethoxy group.

At least one of R ²⁵ , R ²⁶ , and R ²⁷ is a hydrocarbyloxy group, and in order to improve fuel economy, preferably at least two of R ²⁵ , R ²⁶ , and R ²⁷ are hydrocarbyloxy groups, More preferably, three of R ²⁵ , R ²⁶ and R ²⁷ are hydrocarbyloxy groups.

R ²⁸ and R ²⁹ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or R ²⁸ and R ²⁹ are bonded to form a nitrogen atom and / or an oxygen atom. It has optionally also hydrocarbylene group, or, R ²⁸ and R ²⁹ form one group represents a group which bonds to a nitrogen atom with a double bond.

Examples of the hydrocarbyl group of R ²⁸ and R ²⁹ 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, a tert-butyl group; a vinyl group, an allyl group, Examples thereof include alkenyl groups such as 1-propenyl group and 1-methylethenyl group; alkynyl groups such as ethynyl group and propargyl group; aryl groups such as phenyl group, tolyl group and xylyl group; and aralkyl groups such as benzyl group.

Examples of the hydrocarbyl group having a nitrogen atom of R ²⁸ and R ²⁹ include dialkylaminoalkyl groups such as dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, diethylaminomethyl group, diethylaminoethyl group, and diethylaminopropyl group. Can do.

Examples of the hydrocarbyl group having an oxygen atom of R ²⁸ and R ²⁹ include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, and an ethoxypropyl group; a 2-oxiranyl group, 2 A monooxacycloalkyl group such as an oxetanyl group or 2-tetrahydrofuranyl group; a dioxacycloalkyl group such as a 2-dioxolanyl group; an alkyl group substituted with a monooxacycloalkyl group such as a glycidyl group or a tetrahydrofurfuryl group; A 3,4-epoxycyclohexyl group can be mentioned.

In this specification, the monooxacycloalkyl group represents a group in which one CH ₂ of the cycloalkyl group is replaced with an oxygen atom. The dioxacycloalkyl group represents a group in which _two CH ₂ of the cycloalkyl group are replaced with an oxygen atom.

The number of carbon atoms of the hydrocarbyl group which may have a nitrogen atom and / or an oxygen atom of R ²⁸ and R ²⁹ is preferably 1 to 10, and more preferably 1 to 6.

Examples of the group in which R ²⁸ and R ²⁹ are bonded include a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and a hydrocarbylene group having an oxygen atom. Examples of the hydrocarbylene group include alkylene groups such as trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group. As the hydrocarbylene group having a nitrogen atom, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH—N A group represented by ═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified. Examples of the hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the group to which R ²⁸ and R ²⁹ are bonded is preferably 2 to 20, and more preferably 2 to 12.

One group in which R ²⁸ and R ²⁹ are bonded to the nitrogen atom with a double bond is an ethylidene group, a propylidene group, a butylidene group, a 1-methylethylidene group, a 1-methylpropylidene group, or 1,3-dimethylbutylidene. A hydrocarbylidene group such as a group; 4-N, N-dimethylaminobenzylidene group and the like.

The number of carbon atoms of one group in which R ²⁸ and R ²⁹ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 12.

R ²⁸ and R ²⁹ are preferably a hydrocarbyl group, or a hydrocarbylene group in which R ²⁸ and R ²⁹ are bonded, or R ²⁸ and R ²⁹ are one group, and a nitrogen atom Is a hydrocarbylidene group which is a group bonded by a double bond, more preferably a hydrocarbyl group, and still more preferably an alkyl group. The alkyl group is preferably a methyl group or an ethyl group.

t is a number of 1 to 10, preferably 2 to 4, and more preferably 3.

As a compound represented by the formula (9), as a compound in which R ²⁸ and R ²⁹ are alkyl groups,
[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 a compound represented by the formula (9), as a compound in which R ²⁸ and R ²⁹ are alkoxyalkyl groups,
{3- [bis (methoxymethyl) amino] propyl} trimethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} trimethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} trimethoxysilane,
{3- [bis (ethoxyethyl) amino] propyl} trimethoxysilane,
{3- [bis (methoxymethyl) amino] propyl} triethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} triethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} triethoxysilane,
{3- [bis (alkoxyalkyl) amino] propyl} trialkoxysilanes such as {3- [bis (ethoxyethyl) amino] propyl} triethoxysilane;

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

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

As the compound represented by the formula (9), as a compound in which R ²⁸ and R ²⁹ are oxiranyl groups,
{3- [di (oxiranyl) amino] propyl} trimethoxysilane,
{3- [di (oxiranyl) amino] propyl} triethoxysilane,
{3- [di (oxiranyl) amino] propyl} methyldimethoxysilane,
{3- [di (oxiranyl) amino] propyl} ethyldimethoxysilane,
{3- [di (oxiranyl) amino] propyl} methyldiethoxysilane,
{3- [di (oxiranyl) amino] propyl} ethyldiethoxysilane,
{3- [di (oxiranyl) amino] propyl} dimethylmethoxysilane,
{3- [di (oxiranyl) amino] propyl} diethylmethoxysilane,
{3- [di (oxiranyl) amino] propyl} dimethylethoxysilane,
Examples include {3- [di (oxiranyl) amino] propyl} diethylethoxysilane.

As the compound represented by the formula (9), as a compound in which R ²⁸ and R ²⁹ are tetrahydrofuranyl groups,
{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,
Examples include {3- [di (tetrahydrofuranyl) amino] propyl} diethylethoxysilane.

As a compound represented by Formula (9), as a compound in which R ²⁸ and R ²⁹ are glycidyl groups,
{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,
Examples include {3- [di (glycidyl) amino] propyl} diethylethoxysilane.

As a compound represented by the formula (9), as a compound in which R ²⁸ and R ²⁹ are tetrahydrofurfuryl groups,
{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 {3- [di (tetrahydrofurfuryl) amino] propyl} diethylethoxysilane.

As the compound represented by the formula (9), as a compound in which R ²⁸ and R ²⁹ are bonded,
3- (1-piperidinyl) propyltrimethoxysilane,
3- (1-piperidinyl) propyltriethoxysilane,
3- (1-piperidinyl) propylmethyldimethoxysilane,
3- (1-piperidinyl) propylethyldimethoxysilane,
3- (1-piperidinyl) propylmethyldiethoxysilane,
3- (1-piperidinyl) propylethyldiethoxysilane,
3- (1-hexamethyleneimino) propyltrimethoxysilane,
3- (1-hexamethyleneimino) propyltriethoxysilane,
3- (1-hexamethyleneimino) propylmethyldimethoxysilane,
3- (1-hexamethyleneimino) propylethyldimethoxysilane,
3- (1-hexamethyleneimino) propylmethyldiethoxysilane,
3- (1-hexamethyleneimino) propylethyldiethoxysilane,
3-morpholinopropyltrimethoxysilane,
3-morpholinopropyltriethoxysilane,
3-morpholinopropylmethyldimethoxysilane,
3-morpholinopropylethyldimethoxysilane,
3-morpholinopropylmethyldiethoxysilane,
There may be mentioned 3-morpholinopropylethyldiethoxysilane.

As the compound represented by the formula (9), as a compound in which R ²⁸ and R ²⁹ are one group bonded to a nitrogen atom by a double bond,
N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine,
N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine can be mentioned.

The compound represented by the formula (9) is preferably [3- (dialkylamino) propyl] trialkoxysilane.
More preferably,
[3- (dimethylamino) propyl] trimethoxysilane,
[3- (diethylamino) propyl] trimethoxysilane,
[3- (dimethylamino) propyl] triethoxysilane,
[3- (diethylamino) propyl] triethoxysilane,
More preferably,
[3- (Diethylamino) propyl] trimethoxysilane.

In the conjugated diene polymer (D), the content of monomer units based on the compound represented by the formula (8) is preferably 100% by mass based on the total amount of monomer units in the conjugated diene polymer. Is 0.01% by mass or more, more preferably 0.02% by mass or more, and still more preferably 0.05% by mass or more. In order to increase rubber strength, it is preferably 20% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less.

In the conjugated diene polymer (D), the total amount of the conjugated diene unit and the monomer unit based on the compound represented by the formula (8) is 100 masses of the total monomer unit in the conjugated diene polymer. % Is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and still more preferably 100% by mass in order to increase rubber strength.

The Mooney viscosity (ML _{1 + 4} ) of the conjugated diene polymer (D) is preferably 10 or more, more preferably 20 or more, in order to increase rubber strength. Moreover, in order to improve workability, Preferably it is 200 or less, More preferably, it is 150 or less. The Mooney viscosity (ML _{1 + 4} ) is measured at 100 ° C. according to JIS K6300 (1994).

The vinyl bond content of the conjugated diene polymer (D) is preferably 80 mol% or less, more preferably 70 mol% or less in order to improve fuel efficiency, with the content of the conjugated diene unit being 100 mol%. It is. Moreover, in order to improve grip property, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more, Most preferably, it is 40 mol% or more. The vinyl bond amount is determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

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

As a suitable manufacturing method of a conjugated diene polymer (D), the manufacturing method which has following process A1 and B1 can be mention | raise | lifted.
(Step A1): In a hydrocarbon solvent, a monomer component containing a conjugated diene and a compound represented by the above formula (8) is polymerized with an alkali metal catalyst, and a monomer unit based on the conjugated diene is obtained. The process of obtaining the polymer which has an alkali metal derived from an alkali metal catalyst in at least one end of the polymer chain which has a monomer unit based on the compound represented by the said Formula (8).
(Step B1): A step of reacting the polymer obtained in Step A1 with the compound represented by the above formula (9).

Examples of the alkali metal catalyst used in Step A1 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. An organic lithium compound or an organic sodium compound is preferable, and an organic lithium compound having 2 to 20 carbon atoms or an organic sodium compound having 2 to 20 carbon atoms is more preferable.

The hydrocarbon solvent used in step A1 is a solvent that does not deactivate the organic alkali metal compound catalyst, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Examples of the aliphatic hydrocarbon include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2- Examples include butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and the like. Examples of the aromatic hydrocarbon include benzene, toluene, xylene, and ethylbenzene. Examples of the alicyclic hydrocarbon include cyclopentane and cyclohexane. One or more of these may be used, and the hydrocarbon solvent may be a mixture of various components such as industrial hexane. Preferably, it is a hydrocarbon having 2 to 12 carbon atoms.

In step A1, a monomer component containing a conjugated diene and a compound represented by the above formula (8) is polymerized with an alkali metal catalyst in a hydrocarbon solvent, and the monomer unit based on the conjugated diene, A polymer having a monomer unit based on the compound represented by the formula (8) is produced. Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. One or more of these are used. 1,3-butadiene and isoprene are preferred.

The amount of the compound represented by the formula (8) is preferably 0.01% by mass or more in order to improve the fuel efficiency by setting the total amount of the monomer components used in the polymerization to 100% by mass. More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. Further, in order to increase rubber strength, it is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

In the polymerization, the total amount of the conjugated diene and the compound represented by the formula (8) is preferably 99.9% in order to increase the rubber strength with the total amount of the monomer used being 100% by mass. % Or more, more preferably 99.95% by mass or more, and still more preferably 100% by mass.

Polymerization in step A1 is an agent that adjusts the vinyl bond amount of the conjugated diene unit, an agent that adjusts the distribution of monomer units based on the conjugated diene unit and monomers other than the conjugated diene in the conjugated diene polymer chain. (Hereinafter collectively referred to as “regulator”) or the like. Examples of such a regulator 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 ethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, quinoline and the like. Examples of the phosphine compound include trimethylphosphine, triethylphosphine, triphenylphosphine, and the like. One or more of these are used.

The polymerization temperature in the step A1 is usually 25 to 100 ° C, preferably 35 to 90 ° C, more preferably 50 to 80 ° C. The polymerization time is usually 10 minutes to 5 hours.

In step B1, the amount of the compound represented by formula (9) to be reacted with the polymer prepared in step A1 is usually 0.1 to 3 mol per 1 mol of the alkali metal derived from the organic alkali metal catalyst. , Preferably, it is 0.5-2 mol, More preferably, it is 0.7-1.5 mol.

In step B1, the temperature at which the polymer prepared in step A1 reacts with the compound represented by formula (9) is usually 25 to 100 ° C., preferably 35 to 90 ° C., more preferably 50 ~ 80 ° C. The reaction time is usually 60 seconds to 5 hours, preferably 5 minutes to 1 hour, more preferably 15 minutes to 1 hour.

（式中、Ｒ^３１は水素原子又はヒドロカルビル基を表し、ｗは０又は１であり、Ｒ^３２はヒドロカルビレン基を表し、Ｂは含窒素複素環基を表す。）

（式中、ｘは１〜１０の数を表し、Ｒ^３３、Ｒ^３４及びＲ^３５は、それぞれ、ヒドロカルビル基又はヒドロカルビルオキシ基を表し、Ｒ^３３、Ｒ^３４及びＲ^３５の少なくとも１つがヒドロカルビルオキシ基であり、Ｒ^３６及びＲ^３７は、それぞれ、水素原子、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビル基、あるいは、Ｒ^３６とＲ^３７とが結合して、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビレン基、又は、Ｒ^３６とＲ^３７は１つの基であって、窒素原子に二重結合で結合する基を表す。） The conjugated diene polymer (E) according to the fifth aspect of the present invention is a conjugated diene polymer having a monomer unit based on a conjugated diene and a monomer unit based on a compound represented by the following formula (11). It is obtained by reacting one end of the compound represented by the following formula (12).

(In the formula, R ³¹ represents a hydrogen atom or a hydrocarbyl group, w is 0 or 1, R ³² represents a hydrocarbylene group, and B represents a nitrogen-containing heterocyclic group.)

(Wherein x represents a number of 1 to 10, R ³³ , R ³⁴ and R ³⁵ each represent a hydrocarbyl group or a hydrocarbyloxy group, and at least one of R ³³ , R ³⁴ and R ³⁵ is a hydrocarbyloxy group. R ³⁶ and R ³⁷ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or R ³⁶ and R ³⁷ are bonded to form a nitrogen atom and / or (The hydrocarbylene group which may have an oxygen atom, or R ³⁶ and R ³⁷ are one group and represent a group bonded to a nitrogen atom with a double bond.)

As used herein, a hydrocarbyl group represents a hydrocarbon residue. The hydrocarbyloxy group represents a group in which a hydrogen atom of a hydroxyl group is substituted with a hydrocarbyl group. The hydrocarbylene group represents a divalent hydrocarbon residue. The nitrogen-containing heterocyclic group represents a group obtained by removing one hydrogen atom from a carbon atom of a heterocyclic ring of a compound having a nitrogen-containing heterocyclic ring. In addition, a nitrogen-containing heterocyclic ring represents the heterocyclic ring which has a nitrogen atom as a hetero atom which comprises a ring.

Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene and the like, and one or more of these are used. . The conjugated diene is preferably 1,3-butadiene or isoprene.

R ³¹ represents a hydrogen atom or a hydrocarbyl group.

Examples of the hydrocarbyl group for R ³¹ include an alkyl group and an alkenyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group is preferable. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group, and a vinyl group is preferable.

R ³¹ is preferably a hydrogen atom, a methyl group, or a vinyl group.

Examples of the hydrocarbylene group for R ³² include an alkylene group, an arylene group, and a group in which an arylene group and an alkylene group are bonded.

Examples of the alkylene group include a methylene group, an ethylene group, and a trimethylene group. Preferably, it is a methylene group or an ethylene group.

Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group. A phenylene group is preferred.

Examples of the group in which an arylene group and an alkylene group are bonded include a group in which a phenylene group and an alkylene group are bonded, a group in which a naphthylene group and an alkylene group are bonded, and a group in which a biphenylene group and an alkylene group are bonded. . A group in which a phenylene group and an alkylene group are bonded is preferable.

Further, as the group in which the arylene group and the alkylene group are bonded, it is preferable that the carbon atom of the arylene group of the group is bonded to the carbon atom to which R ³¹ of the formula (11) is bonded.

In a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), depending on the position of the carbon atom on the benzene ring from which the hydrogen atom is removed and the position of the carbon atom on the benzene ring to which the alkylene group is bonded, A para-phenylene-alkylene group (for example, a group represented by the following formula (11a)), a meta-phenylene-alkylene group (for example, a group represented by the following formula (11b)), an ortho-phenylene-alkylene group. (For example, a group represented by the following formula (11c)).

（式中、ｙは１〜５の整数を表す。）

(In the formula, y represents an integer of 1 to 5.)

The group in which an arylene group and an alkylene group are bonded is preferably a group in which a phenylene group and an alkylene group are bonded (phenylene-alkylene group), more preferably a group represented by the above formula (11a), A group represented by the above formula (11b), a group represented by the above formula (11c), and more preferably a group represented by the above formula (11a) and a group represented by the above formula (11b). And particularly preferably a para-phenylene-methylene group (a group represented by the formula (11a) in which y = 1) and a meta-phenylene-methylene group (a group represented by the formula (11b) in which y = 1). ), Para-phenylene-ethylene group (group represented by formula (11a) where y = 2), and meta-phenylene-ethylene group (group represented by formula (11b) where y = 2).

Examples of the nitrogen-containing heterocyclic group for B include a nitrogen-containing alicyclic heterocyclic group and a nitrogen-containing aromatic heterocyclic group.

As the nitrogen-containing alicyclic heterocyclic group of B, a group having only a nitrogen atom as a hetero atom constituting the ring, a group having a nitrogen atom and an oxygen atom as a hetero atom constituting the ring, and a hetero atom constituting the ring Examples thereof include a group having a nitrogen atom and a sulfur atom.

As the nitrogen-containing alicyclic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring, a group having an aziridine ring, a group having an azetidine ring, a group having a pyrrolidine ring, a group having a piperidine ring, hexamethyleneimine Examples thereof include a group having a ring, a group having an imidazolidine ring, a group having a piperazine ring, and a group having a pyrazolidine ring.

Examples of the group having an aziridine ring include an N-alkyl-2-aziridinyl group.
Examples of the group having an azetidine ring include an N-alkyl-2-azetidinyl group and an N-alkyl-3-azetidinyl group.
Examples of the group having a pyrrolidine ring include an N-alkyl-2-pyrrolidinyl group and an N-alkyl-3-pyrrolidinyl group.
Examples of the group having a piperidine ring include an N-alkyl-2-piperidinyl group, an N-alkyl-3-piperidinyl group, and an N-alkyl-4-piperidinyl group.
Examples of the group having a hexamethyleneimine ring include an N-alkyl-2-hexamethyleneimino group, an N-alkyl-3-hexamethyleneimino group, and an N-alkyl-4-hexamethyleneimino group.
Examples of the group having an imidazolidine ring include a 1,3-dialkyl-2-imidazolidyl group and a 1,3-dialkyl-4-imidazolidyl group.
Examples of the group having a piperazine ring include a 1,4-dialkyl-2-piperazinyl group.
Examples of the group having a pyrazolidine ring include a 1,2-dialkyl-3-pyrazolidyl group and a 1,2-dialkyl-4-pyrazolidyl group.

Examples of the nitrogen-containing alicyclic heterocyclic group having a nitrogen atom and an oxygen atom as a hetero atom constituting the ring include a group having a morpholine ring and a group having an isoxazolidine ring.

Examples of the group having a morpholine ring include an N-alkyl-2-morpholino group and an N-alkyl-3-morpholino group.
Examples of the group having an isoxazolidine ring include an N-alkyl-3-isoxazolidinyl group, an N-alkyl-4-isoxazolidinyl group, and an N-alkyl-5-isoxazolidinyl group. Can do.

Examples of the nitrogen-containing alicyclic heterocyclic group having a nitrogen atom and a sulfur atom as hetero atoms constituting the ring include a group having a thiomorpholine ring and a group having an isothiazolidine ring.

Examples of the group having a thiomorpholine ring include an N-alkyl-2-thiomorpholino group and an N-alkyl-3-thiomorpholino group.
Examples of the group having an isothiazolidine ring include an N-alkyl-3-isothiazolidinyl group, an N-alkyl-4-isothiazolidinyl group, and an N-alkyl-5-isothiazolidinyl group.

The nitrogen-containing aromatic heterocyclic group of B includes a group having only a nitrogen atom as a hetero atom constituting the ring, a group having a nitrogen atom and an oxygen atom as a hetero atom constituting the ring, and nitrogen as a hetero atom constituting the ring. Examples thereof include a group having an atom and a sulfur atom.

The nitrogen-containing aromatic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring includes a group having a pyrrole ring, a group having an imidazole ring, a group having a pyrazole ring, a group having a pyridine ring, and a pyridazine ring. A group having a pyrimidine ring, a group having a pyrazine ring, a group having a quinoline ring, a group having an isoquinoline ring, a group having a cinnoline ring, a group having a quinazoline ring, a group having a phthalazine ring, and the like.

Examples of the group having a pyrrole ring include a 2-pyrrolyl group, a 3-pyrrolyl group, a 2- (N-methylpyrrolyl) group, and a 3- (N-methylpyrrolyl) group.
Examples of the group having an imidazole ring include 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 2- (N-methylimidazolyl) group, 4- (N-methylimidazolyl) group, and 5- (N-methylimidazolyl). ) Group.
Examples of the group having a pyrazole ring include 3-pyrazolyl group, 4-pyrazolyl group, 5-pyrazolyl group, 3- (N-methylpyrazolyl) group, 4- (N-methylpyrazolyl) group, and 5- (N-methylpyrazolyl). ) Group.
Examples of the group having a pyridine ring include a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group.
Examples of the group having a pyridazine ring include a 3-pyridazyl group and a 4-pyridazyl group.
Examples of the group having a pyrimidine ring include a 2-pyrimidyl group, a 4-pyrimidyl group, and a 5-pyrimidyl group.
Examples of the group having a pyrazine ring include a 2-pyrazyl group.
Examples of the group having a quinoline ring include a 2-quinolyl group, a 3-quinolyl group, a 4-quinolyl group, a 5-quinolyl group, a 6-quinolyl group, a 7-quinolyl group, and an 8-quinolyl group.
Examples of the group having an isoquinoline ring include a 1-isoquinolyl group, a 3-isoquinolyl group, a 4-isoquinolyl group, a 5-isoquinolyl group, a 6-isoquinolyl group, a 7-isoquinolyl group, and an 8-isoquinolyl group.
Examples of the group having a cinnoline ring include a 3-cinnolinyl group, a 4-cinnolinyl group, a 5-cinnolinyl group, a 6-cinnolinyl group, a 7-cinnolinyl group, and an 8-cinnolinyl group.
Examples of the group having a quinazoline ring include a 2-quinazolinyl group, a 4-quinazolinyl group, a 5-quinazolinyl group, a 6-quinazolinyl group, a 7-quinazolinyl group, and an 8-quinazolinyl group.
Examples of the group having a phthalazine ring include a 1-phthalazinyl group, a 5-phthalazinyl group, and a 6-phthalazinyl group.
The nitrogen-containing aromatic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring is preferably a group having an imidazole ring, a group having a pyridine ring, or a group having a quinoline ring.

Examples of the nitrogen-containing aromatic heterocyclic group having a nitrogen atom and an oxygen atom as a hetero atom constituting the ring include a group having an oxazole ring and a group having an isoxazole ring.

Examples of the group having an oxazole ring include a 2-oxazolyl group, a 4-oxazolyl group, and a 5-oxazolyl group.
Examples of the group having an isoxazole ring include a 3-isoxazolyl group, a 4-isoxazolyl group, and a 5-isoxazolyl group.
The nitrogen-containing aromatic heterocyclic group having a nitrogen atom and an oxygen atom as hetero atoms constituting the ring is preferably a group having an oxazole ring.

Examples of the nitrogen-containing aromatic heterocyclic group having a nitrogen atom and a sulfur atom as the hetero atoms constituting the ring include a group having a thiazole ring, a group having an isothiazole ring, and the like.

Examples of the group having a thiazole ring include a 2-thiazolyl group, a 4-thiazolyl group, and a 5-thiazolyl group.
Examples of the group having an isothiazole ring include a 3-isothiazolyl group, a 4-isothiazolyl group, and a 5-isothiazolyl group.
The nitrogen-containing aromatic heterocyclic group having a nitrogen atom and a sulfur atom as a hetero atom constituting the ring is preferably a group having a thiazole ring.

The nitrogen-containing heterocyclic group for B is preferably a nitrogen-containing aromatic heterocyclic group, more preferably a nitrogen-containing aromatic heterocyclic group having only a nitrogen atom as a hetero atom constituting the ring, A group having an imidazole ring, a group having a pyridine ring, and a group having a quinoline ring are preferable, and a group having a pyridine ring is particularly preferable.

As the compound represented by the formula (11), as a compound in which R ³¹ is a hydrogen atom,
1-vinylimidazole,
N-methyl-2-vinylimidazole,
N-methyl-4-vinylimidazole,
N-methyl-5-vinylimidazole,
2-vinylpyridine,
3-vinylpyridine,
4-vinylpyridine,
2-vinylquinoline,
3-vinyl quinoline,
4-vinylquinoline can be mentioned.

As the compound represented by the formula (11), as a compound in which R ³¹ is a methyl group,
1-isopropenylimidazole,
N-methyl-2-isopropenylimidazole,
N-methyl-4-isopropenylimidazole,
N-methyl-5-isopropenylimidazole,
2-isopropenyl pyridine,
3-isopropenyl pyridine,
4-isopropenyl pyridine,
2-isopropenyl quinoline,
3-isopropenyl quinoline,
4-Isopropenylquinoline can be mentioned.

As the compound represented by the formula (11), as a compound in which R ³¹ is a vinyl group,
N-methyl-2- (1-methylene-2-propenyl) aziridine,
N-methyl-2- (1-methylene-2-propenyl) pyrrolidine,
N-methyl-3- (1-methylene-2-propenyl) pyrrolidine,
N-methyl-2- (1-methylene-2-propenyl) hexamethyleneimine,
N-methyl-3- (1-methylene-2-propenyl) hexamethyleneimine,
N-methyl-4- (1-methylene-2-propenyl) hexamethyleneimine,
1- (1-methylene-2-propenyl) imidazole,
N-methyl-2- (1-methylene-2-propenyl) imidazole,
N-methyl-4- (1-methylene-2-propenyl) imidazole,
N-methyl-5- (1-methylene-2-propenyl) imidazole,
2- (1-methylene-2-propenyl) pyridine,
3- (1-methylene-2-propenyl) pyridine,
4- (1-methylene-2-propenyl) pyridine,
2- (1-methylene-2-propenyl) quinoline,
3- (1-methylene-2-propenyl) quinoline,
4- (1-methylene-2-propenyl) quinoline can be mentioned.

The compound represented by formula (11) is preferably a compound in which R ³¹ is a hydrogen atom and B is a group having a pyridine ring, and more preferably, R ³¹ is a hydrogen atom, and B is A compound that is a pyridyl group, more preferably 4-vinylpyridine.

R ³³ , R ³⁴ , and R ³⁵ each represent a hydrocarbyl group or a hydrocarbyloxy group.

Examples of the hydrocarbyl group of R ³³ , R ³⁴ , and R ³⁵ 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. The number of carbon atoms of the hydrocarbyl group is preferably 1 to 10, more preferably 1 to 3.

The hydrocarbyl group for R ³³ , R ³⁴ , and R ³⁵ is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably 1 to 3 carbon atoms. And particularly preferably a methyl group or an ethyl group.

Examples of the hydrocarbyloxy group for R ³³ , R ³⁴ , and R ³⁵ include alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group; An aryloxy group such as a phenoxy group can be exemplified. The number of carbon atoms of the hydrocarbyloxy group is preferably 1 to 10, more preferably 1 to 3.

The hydrocarbyloxy group for R ³³ , R ³⁴ , and R ³⁵ is preferably an alkoxy group, more preferably an alkoxy group having 1 to 10 carbon atoms, and still more preferably 1 to 1 carbon atom. 3 is particularly preferably a methoxy group or an ethoxy group.

At least one of R ³³ , R ³⁴ , and R ³⁵ is a hydrocarbyloxy group, and in order to improve fuel economy, preferably at least two of R ³³ , R ³⁴ , and R ³⁵ are hydrocarbyloxy groups, More preferably, three of R ³³ , R ³⁴ , and R ³⁵ are hydrocarbyloxy groups.

R ³⁶ and R ³⁷ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or R ³⁶ and R ³⁷ are bonded to form a nitrogen atom and / or an oxygen atom. which may have hydrocarbylene group, or, R ³⁶ and R ³⁷ form one group represents a group which bonds to a nitrogen atom with a double bond.

In this specification, the hydrocarbyl group having an X atom represents a group having a structure in which a hydrogen atom and / or a carbon atom of the hydrocarbyl group is replaced with an X atom, and the hydrocarbylene group having an X atom is a hydrocarbyl group. This represents a group having a structure in which a hydrogen atom and / or a carbon atom of a len group is replaced with an X atom. For example, examples of the group having a nitrogen atom include a group having a structure in which CH is replaced by N. Examples of the group having an oxygen atom include a group having a structure in which CH ₂ is replaced with O, and a group having a structure in which two hydrogen atoms are replaced with O.

Examples of the hydrocarbyl group for R ³⁶ and R ³⁷ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group; vinyl group, allyl group, Examples thereof include alkenyl groups such as 1-propenyl group and 1-methylethenyl group; alkynyl groups such as ethynyl group and propargyl group; aryl groups such as phenyl group, tolyl group and xylyl group; and aralkyl groups such as benzyl group.

Examples of the hydrocarbyl group having a nitrogen atom of R ³⁶ and R ³⁷ include dialkylaminoalkyl groups such as dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, diethylaminomethyl group, diethylaminoethyl group, and diethylaminopropyl group. Can do.

Examples of the hydrocarbyl group having an oxygen atom of R ³⁶ and R ³⁷ include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, and an ethoxypropyl group; a 2-oxiranyl group, 2 A monooxacycloalkyl group such as an oxetanyl group or 2-tetrahydrofuranyl group; a dioxacycloalkyl group such as a 2-dioxolanyl group; an alkyl group substituted with a monooxacycloalkyl group such as a glycidyl group or a tetrahydrofurfuryl group; A 3,4-epoxycyclohexyl group can be mentioned.

In this specification, the monooxacycloalkyl group represents a group in which one CH ₂ of the cycloalkyl group is replaced with an oxygen atom. The dioxacycloalkyl group represents a group in which _two CH ₂ of the cycloalkyl group are replaced with an oxygen atom.

The number of carbon atoms of the hydrocarbyl group which may have a nitrogen atom and / or an oxygen atom of R ³⁶ and R ³⁷ is preferably 1 to 10, and more preferably 1 to 6.

Examples of the group in which R ³⁶ and R ³⁷ are bonded include a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and a hydrocarbylene group having an oxygen atom. Examples of the hydrocarbylene group include alkylene groups such as trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group. As the hydrocarbylene group having a nitrogen atom, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH—N A group represented by ═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified. Examples of the hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the group to which R ³⁶ and R ³⁷ are bonded is preferably 2 to 20, and more preferably 2 to 12.

Examples of one group in which R ³⁶ and R ³⁷ are bonded to the nitrogen atom with a double bond include an ethylidene group, a propylidene group, a butylidene group, a 1-methylethylidene group, a 1-methylpropylidene group, and 1,3-dimethylbutylidene A hydrocarbylidene group such as a group; 4-N, N-dimethylaminobenzylidene group and the like.

The number of carbon atoms of one group in which R ³⁶ and R ³⁷ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 12.

R ³⁶ and R ³⁷ are preferably a hydrocarbyl group, or a hydrocarbylene group in which R ³⁶ and R ³⁷ are bonded, or R ³⁶ and R ³⁷ are one group, and a nitrogen atom Is a hydrocarbylidene group which is a group bonded by a double bond, more preferably a hydrocarbyl group, and still more preferably an alkyl group. The alkyl group is preferably a methyl group or an ethyl group.

x is a number of 1 to 10, preferably 2 to 4, and more preferably 3.

As the compound represented by the formula (12), as a compound in which R ³⁶ and R ³⁷ are alkyl groups,
[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 a compound represented by Formula (12), as a compound in which R ³⁶ and R ³⁷ are alkoxyalkyl groups,
{3- [bis (methoxymethyl) amino] propyl} trimethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} trimethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} trimethoxysilane,
{3- [bis (ethoxyethyl) amino] propyl} trimethoxysilane,
{3- [bis (methoxymethyl) amino] propyl} triethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} triethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} triethoxysilane,
{3- [bis (alkoxyalkyl) amino] propyl} trialkoxysilanes such as {3- [bis (ethoxyethyl) amino] propyl} triethoxysilane;

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

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

As the compound represented by the formula (12), as a compound in which R ³⁶ and R ³⁷ are oxiranyl groups,
{3- [di (oxiranyl) amino] propyl} trimethoxysilane,
{3- [di (oxiranyl) amino] propyl} triethoxysilane,
{3- [di (oxiranyl) amino] propyl} methyldimethoxysilane,
{3- [di (oxiranyl) amino] propyl} ethyldimethoxysilane,
{3- [di (oxiranyl) amino] propyl} methyldiethoxysilane,
{3- [di (oxiranyl) amino] propyl} ethyldiethoxysilane,
{3- [di (oxiranyl) amino] propyl} dimethylmethoxysilane,
{3- [di (oxiranyl) amino] propyl} diethylmethoxysilane,
{3- [di (oxiranyl) amino] propyl} dimethylethoxysilane,
Examples include {3- [di (oxiranyl) amino] propyl} diethylethoxysilane.

As a compound represented by the formula (12), as a compound in which R ³⁶ and R ³⁷ are tetrahydrofuranyl groups,
{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,
Examples include {3- [di (tetrahydrofuranyl) amino] propyl} diethylethoxysilane.

As a compound represented by Formula (12), as a compound in which R ³⁶ and R ³⁷ are glycidyl groups,
{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,
Examples include {3- [di (glycidyl) amino] propyl} diethylethoxysilane.

As a compound represented by Formula (12), as a compound in which R ³⁶ and R ³⁷ are tetrahydrofurfuryl groups,
{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 {3- [di (tetrahydrofurfuryl) amino] propyl} diethylethoxysilane.

As the compound represented by the formula (12), as a compound in which R ³⁶ and R ³⁷ are bonded,
3- (1-piperidinyl) propyltrimethoxysilane,
3- (1-piperidinyl) propyltriethoxysilane,
3- (1-piperidinyl) propylmethyldimethoxysilane,
3- (1-piperidinyl) propylethyldimethoxysilane,
3- (1-piperidinyl) propylmethyldiethoxysilane,
3- (1-piperidinyl) propylethyldiethoxysilane,
3- (1-hexamethyleneimino) propyltrimethoxysilane,
3- (1-hexamethyleneimino) propyltriethoxysilane,
3- (1-hexamethyleneimino) propylmethyldimethoxysilane,
3- (1-hexamethyleneimino) propylethyldimethoxysilane,
3- (1-hexamethyleneimino) propylmethyldiethoxysilane,
3- (1-hexamethyleneimino) propylethyldiethoxysilane,
3-morpholinopropyltrimethoxysilane,
3-morpholinopropyltriethoxysilane,
3-morpholinopropylmethyldimethoxysilane,
3-morpholinopropylethyldimethoxysilane,
3-morpholinopropylmethyldiethoxysilane,
There may be mentioned 3-morpholinopropylethyldiethoxysilane.

As the compound represented by the formula (12), as a compound in which R ³⁶ and R ³⁷ are one group bonded to a nitrogen atom by a double bond,
N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine,
N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine can be mentioned.

The compound represented by the formula (12) is preferably [3- (dialkylamino) propyl] trialkoxysilane.
More preferably,
[3- (dimethylamino) propyl] trimethoxysilane,
[3- (diethylamino) propyl] trimethoxysilane,
[3- (dimethylamino) propyl] triethoxysilane,
[3- (diethylamino) propyl] triethoxysilane,
More preferably,
[3- (Diethylamino) propyl] trimethoxysilane.

In the conjugated diene polymer (E), the content of the monomer units based on the compound represented by the formula (11) is 0%, where the total amount of the monomer units in the conjugated diene polymer is 100% by mass. 0.01 to 20% by mass. The content is preferably 0.02% by mass or more, more preferably 0.05% by mass or more in order to increase rubber strength. Moreover, in order to improve low fuel consumption, Preferably it is 2 mass% or less, More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less.

In the conjugated diene polymer (E), the total amount of conjugated diene units and monomer units based on the compound represented by the formula (11) is 100 masses of the total amount of monomer units in the conjugated diene polymer. % Is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and still more preferably 100% by mass in order to increase rubber strength.

The Mooney viscosity (ML _{1 + 4} ) of the conjugated diene polymer (E) is preferably 10 or more, more preferably 20 or more, in order to increase rubber strength. Moreover, in order to improve workability, Preferably it is 200 or less, More preferably, it is 150 or less. The Mooney viscosity (ML _{1 + 4} ) is measured at 100 ° C. according to JIS K6300 (1994).

The vinyl bond amount of the conjugated diene polymer (E) is preferably 80 mol% or less, more preferably 70 mol% or less, in order to improve fuel efficiency, with the content of the conjugated diene unit being 100 mol%. It is. Moreover, in order to improve grip property, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more, Most preferably, it is 40 mol% or more. The vinyl bond amount is determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

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

As a suitable manufacturing method of a conjugated diene polymer (E), the manufacturing method which has following process A2 and B2 can be mention | raise | lifted.
(Step A2): Use of a compound represented by the above formula (11) as a monomer component containing a conjugated diene and a compound represented by the above formula (11) with an alkali metal catalyst in a hydrocarbon solvent. The amount is 0.01 to 20% by mass (provided that the total amount of monomer components used is 100% by mass), and is represented by the monomer unit based on the conjugated diene and the above formula (11). A step of obtaining a polymer having an alkali metal derived from an alkali metal catalyst at at least one end of a polymer chain having a monomer unit based on the compound.
(Step B2): A step of reacting the polymer obtained in Step A2 with the compound represented by the above formula (12).

Examples of the alkali metal catalyst used in Step A2 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. An organic lithium compound or an organic sodium compound is preferable, and an organic lithium compound having 2 to 20 carbon atoms or an organic sodium compound having 2 to 20 carbon atoms is more preferable.

The hydrocarbon solvent used in step A2 is a solvent that does not deactivate the organic alkali metal compound catalyst, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Aliphatic hydrocarbons include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-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. One or more of these may be used, and the hydrocarbon solvent may be a mixture of various components such as industrial hexane. Preferably, it is a hydrocarbon having 2 to 12 carbon atoms.

In step A2, a monomer component containing a conjugated diene and a compound represented by the above formula (11) is polymerized with an alkali metal catalyst in a hydrocarbon solvent, and a monomer unit based on the conjugated diene, the above formula A polymer having a monomer unit based on the compound represented by (11) is produced. Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. One or more of these are used. 1,3-butadiene and isoprene are preferred.

The amount of the compound represented by the formula (11) is preferably 0.01% by mass or more in order to increase the rubber strength, with the total amount of the monomer components used in the polymerization being 100% by mass, More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more. In order to improve fuel efficiency, it is preferably 20% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. .

In the polymerization, the total amount of the conjugated diene and the compound represented by the formula (11) is preferably 99.9% in order to increase the rubber strength with the total amount of the monomer used being 100% by mass. % Or more, more preferably 99.95% by mass or more, and still more preferably 100% by mass.

Polymerization in step A2 is an agent for adjusting the vinyl bond amount of the conjugated diene unit, and an agent for adjusting the distribution of the monomer unit based on the conjugated diene unit and the monomer other than the conjugated diene in the conjugated diene polymer chain. (Hereinafter collectively referred to as “regulator”) or the like. Examples of such a regulator 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 ethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, quinoline and the like. Examples of the phosphine compound include trimethylphosphine, triethylphosphine, triphenylphosphine, and the like. One or more of these are used.

The polymerization temperature in the step A2 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 B2, the amount of the compound represented by formula (12) to be reacted with the polymer prepared in step A2 is usually 0.1 to 3 mol per 1 mol of the alkali metal derived from the organic alkali metal catalyst. , Preferably, it is 0.5-2 mol, More preferably, it is 0.7-1.5 mol.

In step B2, the temperature at which the polymer prepared in step A2 is reacted with the compound represented by formula (12) is usually 25 to 100 ° C, preferably 35 to 90 ° C. More preferably, it is 50-80 degreeC. The reaction time is usually 60 seconds to 5 hours, preferably 5 minutes to 1 hour, more preferably 15 minutes to 1 hour.

In the production of the conjugated diene polymers (A) to (E), if necessary, the polymerization of the conjugated diene polymers (A) to (E) can be stopped from the start of the polymerization of the monomer using an alkali metal catalyst. A coupling agent may be added to the hydrocarbon solution. Examples of the coupling agent include compounds represented by the following formula (X).

R ⁹ ML _4-a (X)
(In the formula, R ⁹ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aryl group, M represents a silicon atom or a tin atom, L represents a halogen atom or a hydrocarbyloxy group, and a is a number from 0 to 2. Represents.)

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, in order to improve the processability of the conjugated diene polymer per mol of alkali metal derived from the alkali metal catalyst. It is. Moreover, in order to improve fuel-consumption property, Preferably it is 0.4 mol or less, More preferably, it is 0.3 mol or less.

Examples of a method for recovering the conjugated diene polymer from the hydrocarbon solution of the conjugated diene polymers (A) to (E) include known recovery methods. For example, (i) a method of adding a coagulant to a hydrocarbon solution of conjugated diene polymers (A) to (E), (ii) steam to a hydrocarbon solution of conjugated diene polymers (A) to (E) The method of adding is mentioned. The recovered conjugated diene polymers (A) to (E) may be dried by a known dryer such as a band dryer or an extrusion dryer.

The conjugated diene polymers (A) to (E) can be used as a rubber component, and other rubber components and additives such as silica can be blended to obtain the rubber composition of the present invention. .

The content of the conjugated diene polymers (A) to (E) 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. If the amount is less than 5% by mass, the effect of improving fuel economy tends to be difficult to obtain. Further, the content of the conjugated diene polymers (A) to (E) is preferably 40% by mass or less, and more preferably 30% by mass or less. If it exceeds 40% by mass, the rubber strength tends to decrease and the cost tends to increase.

The rubber component that can be used other than the conjugated diene polymers (A) to (E) is not limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR). ), Acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR) and the like. These rubber components may be used alone or in combination of two or more. Of these, NR and BR are preferable because they exhibit a good balance between low fuel consumption, wear resistance, rubber strength, and wet grip performance.
These rubber components are not particularly limited, and those generally used in the tire industry can be used.

The content of NR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 25% by mass or more, and further preferably 50% by mass or more. If the amount is less than 5% by mass, sufficient fuel economy tends not to be obtained. The NR content is preferably 90% by mass or less, more preferably 70% by mass or less. When it exceeds 90 mass%, workability tends to deteriorate.

The content of BR in 100% by mass of the rubber component is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. When it is less than 1% by mass, sufficient wear resistance tends to be not obtained. The BR content is preferably 40% by mass or less, more preferably 30% by mass or less. When it exceeds 40 mass%, workability tends to deteriorate.

The rubber composition of the present invention uses silica as a reinforcing agent. Examples of the silica include dry silica (anhydrous silicic acid), wet silica (hydrous silicic acid), colloidal silica, precipitated silica, calcium silicate, and aluminum silicate. One or more of these can be used. The BET specific surface area of silica is preferably 50 to 250 m ² / g. The BET specific surface area is measured according to ASTM D1993-03. As a commercial product of silica, the product name Ultrasil VN3-G manufactured by Degussa, the product name VN3, AQ, ER, RS-150 manufactured by Tosoh Silica Co., Ltd., and the product names Zeosil 1115MP, 1165MP manufactured by Rhodia can be used. .

The content of silica is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component. The content is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, in order to improve fuel efficiency. Moreover, in order to improve rubber | gum intensity | strength and workability, Preferably it is 100 mass parts or less, More preferably, it is 40 mass parts or less.

The rubber composition of the present invention may contain additives other than the above-mentioned chemicals. Known additives can be used, such as sulfur vulcanizing agents; thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, guanidine vulcanization accelerators. Vulcanization accelerators such as stearic acid and zinc oxide; organic peroxides such as dicumyl peroxide and ditertiary butyl peroxide; reinforcing agents such as carbon black; calcium carbonate, talc and alumina Examples thereof include fillers such as clay, aluminum hydroxide and mica; silane coupling agents; extension oils; processing aids; anti-aging agents;

Examples of the sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. The sulfur content is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, still more preferably 0.5 parts by mass or more, and preferably 100 parts by mass or more, more preferably 0.5 parts by mass or more. 15 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

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

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

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 5 to 200 m ² / g, more preferably 15 to 120 m ² / g, and the dibutyl phthalate (DBP) absorption amount of carbon black is preferably Is 5 to 300 ml / 100 g, more preferably 80 to 180 ml / 100 g. The nitrogen adsorption specific surface area is measured according to ASTM D4820-93, and the DBP absorption is measured according to ASTM D2414-93. Examples of commercially available products include Tokai Carbon Co., Ltd., trade name SHEET 6, SEAST 7HM, SEAST KH, and Degussa trade name CK3, Special Black 4A.

The content of carbon black is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the rubber component. Further, the content is more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more, in order to increase wear resistance and rubber strength. Moreover, in order to improve low-fuel-consumption property, More preferably, it is 45 mass parts or less, More preferably, it is 40 mass parts or less.

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

The mass ratio of the silica content and the carbon black content used as the reinforcing agent (silica content: carbon black content) is preferably 0.1: 1 to 10: 1. The mass ratio is more preferably 0.5: 1 to 2: 1 in order to improve fuel economy and reinforcement.

As the silane coupling agent, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ- Aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxy Cyril) Pills) tetrasulfide, .gamma.-trimethoxysilylpropyl dimethylthiocarbamoyl tetrasulfide, and the like .gamma.-trimethoxysilylpropyl benzothiazyl tetrasulfide. One or more of these are used. As commercial products, trade names Si69, Si75, etc., manufactured by Degussa Corporation can be used.

The content of the silane coupling agent is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and further preferably 5 to 10 parts by mass with respect to 100 parts by mass of silica.

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

As a method for producing the rubber composition of the present invention, a known method, for example, a method of kneading each component with a known mixer such as a roll or Banbury can be used.

As kneading conditions, when additives other than the vulcanizing agent and the vulcanization accelerator are blended, the kneading temperature is usually 50 to 200 ° C., preferably 80 to 190 ° C., and the kneading time is usually 30 seconds. -30 minutes, preferably 1-30 minutes. When blending a vulcanizing agent and a vulcanization accelerator, the kneading temperature is usually 100 ° C. or lower, preferably room temperature to 80 ° C. A composition containing a vulcanizing agent and a vulcanization accelerator is usually used after being subjected to a 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 provides high fuel economy, wear resistance, rubber strength, and wet grip performance at a high level and in a well-balanced manner.

The rubber composition of the present invention is used for a cap tread of a truck / bus tire (heavy load tire).

The truck / bus tire of the present invention is produced by a conventional method using the rubber composition. That is, a rubber composition containing various additives as necessary is extruded in accordance with the shape of the cap tread at an unvulcanized stage, molded by a normal method on a tire molding machine, Bonding together with the tire member forms 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.

(Polymer production example 1)
The inside of a stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and replaced with dry nitrogen. Industrial hexane (density 680 Kg / m ³ ) 10.2 kg, 1,3-butadiene 608 g, tetrahydrofuran 6.07 ml, ethylene 4.00 ml of glycol diethyl ether was charged into the polymerization reaction vessel. Next, 12.70 mmol of dimethyl-1-piperidinylmethylvinylsilane and 14.59 mmol of n-butyllithium were added as an n-hexane solution to initiate polymerization.
Copolymerization of 1,3-butadiene and dimethyl-1-piperidinylmethylvinylsilane while stirring rate is 130 rpm, polymerization reactor internal temperature is 65 ° C., and monomer is continuously fed into the polymerization reaction vessel. For 3.0 hours. The supply amount of 1,3-butadiene in the entire polymerization was 912 g.
Next, 20 ml of a hexane solution containing 0.77 ml of methanol was added to the obtained polymerization reaction solution, and the polymerization reaction solution was further stirred for 5 minutes.
6. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymerization reaction solution 2 g, 3.6 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymerization reaction solution was allowed to stand at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain polymer 1 (modified BR).

(Polymer production example 2)
The inside of a stainless steel polymerization reactor having an internal volume of 5 liters was washed, dried, and replaced with dry nitrogen. Industrial hexane (density 680 Kg / m ³ ) 2.55 kg, 1,3-butadiene 137 g, tetrahydrofuran 1.52 ml, ethylene 1.12 ml of glycol diethyl ether was charged into the polymerization reaction vessel. Next, 8.70 mmol of dimethyl-1-piperidinylmethylvinylsilane and 3.37 mmol of n-butyllithium were added as an n-hexane solution to initiate polymerization.
Copolymerization of 1,3-butadiene and dimethyl-1-piperidinylmethylvinylsilane while stirring rate is 130 rpm, polymerization reactor internal temperature is 65 ° C., and monomer is continuously fed into the polymerization reaction vessel. For 2.5 hours. The supply amount of 1,3-butadiene in the entire polymerization was 205 g. The polymerization conversion rate was almost 100%.
To the polymerization reaction solution, 10 ml of hexane solution containing 0.20 ml of methanol was added, and the polymerization reaction 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 polymerization reaction solution. 8 g, 0.9 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymerization reaction solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain polymer 2 (modified BR).

(Polymer production example 3)
The inside of the stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and replaced with dry nitrogen. Industrial hexane (density 680 Kg / m ³ ) 10.2 kg, 1,3-butadiene 547 g, tetrahydrofuran 6.07 ml, ethylene 4.00 ml of glycol diethyl ether was charged into the polymerization reaction vessel. Next, 14.46 mmol of n-butyllithium was added as an n-hexane solution to initiate polymerization.
1,3-butadiene was copolymerized 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 reaction vessel. The supply amount of 1,3-butadiene in the entire polymerization was 821 g.
To the polymerization reaction solution, 10 ml of a hexane solution containing 0.75 ml of methanol was added, and the polymerization reaction solution was further stirred for 5 minutes.
7. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymerization reaction solution 0 g, pentaerythrityltetrakis (3-lauryl thiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) 4.0 g was added, and then the polymerization reaction solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain polymer 3 (non-modified BR).

(Polymer production example 4)
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 137 g of 1,3-butadiene, 0.81 g of tert-butoxydiphenylvinylsilane, 1.52 ml of tetrahydrofuran, and 1.18 ml of ethylene glycol diethyl ether were added to the polymerization reactor. It was thrown into. Next, 2.88 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to start the polymerization reaction.

Copolymerization of 1,3-butadiene and tert-butoxydiphenylvinylsilane was carried out for 2 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. It was. The supply amount of 1,3-butadiene was 205 g. In addition, in the total amount of monomers charged / supplied to the polymerization reactor, the charged amount of tert-butoxydiphenylvinylsilane was 0.18% by mass.

10 ml of a hexane solution containing 0.2 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: Sumilizer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer solution was stirred at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 4 (modified BR).

(Polymer Production Example 5)
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 6.1 ml of tetrahydrofuran, and 4.0 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, 12.40 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

The stirring rate was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and the copolymerization reaction of 1,3-butadiene was carried out for 3 hours while continuously supplying the monomer into the polymerization reactor. The supply amount of 1,3-butadiene was 912 g. 20 ml of hexane solution containing 0.8 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.

7. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymer solution 0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) 4.0 g was added, and then the polymer solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain polymer 5 (non-modified BR).

(Polymer Production Example 6)
A stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and substituted with dry nitrogen, and then 1,3-butadiene 1404 g, tetrahydrofuran 328 g, hexane 10.2 kg, n-butyllithium (n-hexane solution 15.0 mmol) Was added and polymerization was carried out at 65 ° C. for 3 hours with stirring. After completion of the polymerization, 7.5 mmol (2.23 g) of triglycidyl isocyanurate was added. After reacting at 65 ° C. for 30 minutes with stirring, 10 ml of methanol was added, and the mixture was further stirred for 5 minutes. Thereafter, the contents of the polymerization reaction vessel are taken out, 10 g of 2,6-di-t-butyl-p-cresol (Sumitomo Chemical Co., Ltd., Sumitizer BHT: the same applies below) is added, and most of the hexane is evaporated. Then, it was dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 6 (modified BR).

(Polymer Production Example 7)
A stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried and replaced with dry nitrogen, and then 1,3-butadiene 1404 g, tetrahydrofuran 328 g, hexane 10.2 kg, n-butyllithium (n-hexane solution 8.5 mmol) Was added and polymerization was carried out at 65 ° C. for 3 hours with stirring. After completion of the polymerization, 0.16 mmol (0.027 g) of silicon tetrachloride was added, and the mixture was reacted at 65 ° C. for 15 minutes with stirring. Further, instead of triglycidyl isocyanurate, 7.65 mmol (1.19 g) of N, N-dimethylaminopropylacrylamide was added, and the mixture was reacted at 65 ° C. for 30 minutes with stirring, and then 10 ml of methanol was added. Stir for another 5 minutes. Thereafter, the contents of the polymerization reaction vessel are taken out, 10 g of 2,6-di-t-butyl-p-cresol (Sumitomo Chemical Co., Ltd., Sumitizer BHT: the same applies below) is added, and most of the hexane is evaporated. Then, it was dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 7 (modified BR).

(Polymer Production Example 8)
The n-butyllithium solution in n-hexane was changed to 8.7 mmol, the silicon tetrachloride was changed to 0.17 mmol (0.029 g), and triglycidyl isocyanurate and N, N-dimethylaminopropylacrylamide were added. Except not having added, it carried out similarly to the polymer manufacture example 7, and obtained the polymer 8 (non-modified BR).

(Polymer production example 9)
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 2.58 g of a mixture of 4-pyrrolidinoethylstyrene and 3-pyrrolidinoethylstyrene, 6.1 ml of tetrahydrofuran, ethylene glycol 4.0 ml of diethyl ether was charged into the polymerization reactor. Next, 15.08 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

While stirring speed was 130 rpm, polymerization reactor internal temperature was 65 ° C. and 1,3-butadiene was continuously fed into the polymerization reactor, 1,3-butadiene, 4-pyrrolidinoethylstyrene, and 3- The copolymerization reaction of pyrrolidinoethylstyrene was performed for 3 hours. The supply amount of 1,3-butadiene was 912 g. The total amount of 4-pyrrolidinoethylstyrene and 3-pyrrolidinoethylstyrene charged in the total amount of monomers charged / supplied to the polymerization reactor was 0.13% by mass.

Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, 12.8 mmol of [3- (diethylamino) propyl] trimethoxysilane was added to the polymer solution, and further stirred for 15 minutes. Next, 20 ml of hexane solution containing 0.8 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.

7. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymer solution 0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) 4.0 g was added, and then the polymer solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 9 (modified BR with modified main chain and terminal).

(Polymer production example 10)
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 7.73 g of a mixture of 4-pyrrolidinoethylstyrene and 3-pyrrolidinoethylstyrene, 6.1 ml of tetrahydrofuran, ethylene glycol 4.0 ml of diethyl ether was charged into the polymerization reactor. Next, 15.38 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to start the polymerization reaction.

While stirring speed was 130 rpm, polymerization reactor internal temperature was 65 ° C. and 1,3-butadiene was continuously fed into the polymerization reactor, 1,3-butadiene, 4-pyrrolidinoethylstyrene, and 3- The copolymerization reaction of pyrrolidinoethylstyrene was performed for 3 hours. The supply amount of 1,3-butadiene was 912 g. The total amount of 4-pyrrolidinoethylstyrene and 3-pyrrolidinoethylstyrene charged in the total amount of monomers charged and supplied to the polymerization reactor was 0.39% by mass.

Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, 12.8 mmol of [3- (diethylamino) propyl] trimethoxysilane was added to the polymer solution, and further stirred for 15 minutes. Next, 20 ml of hexane solution containing 0.8 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.

7. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymer solution 0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) 4.0 g was added, and then the polymer solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 10 (modified BR with modified main chain and terminal).

(Polymer Production Example 11)
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 10.2 kg of hexane (density 680 kg / m ³ ), 547 g of 1,3-butadiene, 6.1 ml of tetrahydrofuran, and 4.7 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, 15.38 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to start the polymerization reaction.

The agitation rate was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene was copolymerized for 3 hours while continuously supplying 1,3-butadiene into the polymerization reactor. The amount of 1,3-butadiene supplied was 821 g.

Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 12.80 mmol of [3- (diethylamino) propyl] trimethoxysilane was added and stirred for 15 minutes. 20 ml of a hexane solution containing 0.8 ml of methanol in the polymer solution was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.

7. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymer solution 0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) 4.0 g was added, and then the polymer solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 11 (modified BR with terminal-modified).

(Polymer Production Example 12)
The inside of the stainless steel polymerization reactor with an internal volume of 5 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 2.55 kg of industrial hexane (density 680 kg / m ³ ), 137 g of 1,3-butadiene, 0.53 g of a mixture of 4-pyrrolidinoethylstyrene and 3-pyrrolidinoethylstyrene, 1.52 ml of tetrahydrofuran, ethylene glycol 1.18 ml of diethyl ether was charged into the polymerization reactor. Next, 3.73 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

While stirring speed was 130 rpm, polymerization reactor internal temperature was 65 ° C. and 1,3-butadiene was continuously fed into the polymerization reactor, 1,3-butadiene, 4-pyrrolidinoethylstyrene, and 3- Copolymerization reaction with pyrrolidinoethylstyrene was carried out for 2 hours. The supply amount of 1,3-butadiene was 205 g. The total amount of 4-pyrrolidinoethylstyrene and 3-pyrrolidinoethylstyrene charged in the polymerization reactor was 0.12% by mass. 10 ml of a hexane solution containing 0.5 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 pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer solution was stirred at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 12 (modified BR with modified main chain).

(Polymer Production Example 13)
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 1.41 g of 4-vinylpyridine, 6.1 ml of tetrahydrofuran, and 4.0 ml of ethylene glycol diethyl ether are placed in the polymerization reactor. I put it in. Next, 18.26 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

While the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene was continuously fed into the polymerization reactor, the copolymerization reaction of 1,3-butadiene and 4-vinylpyridine was conducted. I went for 3 hours. The supply amount of 1,3-butadiene was 912 g. Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of 4-vinylpyridine charged was 0.07% by mass.

Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 13.42 mmol of [3- (diethylamino) propyl] trimethoxysilane was added to the polymer solution, and further stirred for 15 minutes. Next, 20 ml of hexane solution containing 0.8 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.

7. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymer solution 0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) 4.0 g was added, and then the polymer solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 13 (modified BR with modified main chain and terminal).

(Polymer Production Example 14)
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 4.18 g of 4-vinylpyridine, 6.1 ml of tetrahydrofuran, and 4.0 ml of ethylene glycol diethyl ether were placed in the polymerization reactor. I put it in. Next, 22.62 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to start the polymerization reaction.

While the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene was continuously fed into the polymerization reactor, the copolymerization reaction of 1,3-butadiene and 4-vinylpyridine was conducted. I went for 3 hours. The supply amount of 1,3-butadiene was 912 g. Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of 4-vinylpyridine charged was 0.21% by mass.

Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, 13.26 mmol of [3- (diethylamino) propyl] trimethoxysilane was added to the polymer solution, and further stirred for 15 minutes. Next, 20 ml of hexane solution containing 0.8 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.

7. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymer solution 0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) 4.0 g was added, and then the polymer solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 14 (modified BR with modified main chain and terminal).

(Polymer Production Example 15)
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried, and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 547 g of 1,3-butadiene, 6.1 ml of tetrahydrofuran, and 4.7 ml of ethylene glycol diethyl ether were charged into the polymerization reactor. Next, 15.38 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to start the polymerization reaction.

The agitation rate was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene was copolymerized for 3 hours while continuously supplying 1,3-butadiene into the polymerization reactor. The amount of 1,3-butadiene supplied was 821 g.

Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, and 12.80 mmol of [3- (diethylamino) propyl] trimethoxysilane was added and stirred for 15 minutes. 20 ml of a hexane solution containing 0.8 ml of methanol in the polymer solution was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.

7. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymer solution 0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) 4.0 g was added, and then the polymer solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain polymer 15 (modified BR with terminal-modified).

(Polymer Production Example 16)
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 1.41 g of 4-vinylpyridine, 6.1 ml of tetrahydrofuran, and 4.0 ml of ethylene glycol diethyl ether are placed in the polymerization reactor. I put it in. Next, 18.52 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

While the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene was continuously fed into the polymerization reactor, the copolymerization reaction of 1,3-butadiene and 4-vinylpyridine was conducted. I went for 3 hours. The supply amount of 1,3-butadiene was 912 g. Of the total amount of monomers charged / supplied to the polymerization reactor, the amount of 4-vinylpyridine charged was 0.07% by mass.

Next, the obtained polymer solution was stirred at a stirring speed of 130 rpm, 20 ml of a hexane solution containing 0.8 ml of methanol was added to the polymer solution, and the polymer solution was further stirred for 5 minutes.

7. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymer solution 0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) 4.0 g was added, and then the polymer solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 16 (modified BR having a modified main chain).

The following physical property evaluation was performed about the obtained polymers 1-16. The results are shown in Tables 1-5.

(Mooney viscosity (ML _{1 + 4} ))
According to JIS K6300 (1994), the Mooney viscosity of the polymer was measured at 100 ° C.

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

(Molecular weight distribution (Mw / Mn))
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method under the following conditions (1) to (8), and the molecular weight distribution (Mw / Mn) was determined.
(1) Apparatus: HLC-8220 manufactured by Tosoh Corporation
(2) Separation column: HM-H manufactured by Tosoh Corporation (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

Below, various chemical | medical agents used by the Example and the comparative example are demonstrated.
NR: RSS # 3
BR: Ubepol BR150B manufactured by Ube Industries, Ltd.
Polymers 1 to 16: Polymer carbon black synthesized by the above method: Diablack N220 manufactured by Mitsubishi Chemical Corporation (N ₂ SA: 111 m ² / g, DBP absorption: 115 ml / 100 g)
Silica: Ultrasil VN3 manufactured by Degussa (N ₂ SA: 175 m ² / g)
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.
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Stearic acid: Beads manufactured by NOF Corporation Zinc stearate zinc oxide: Zinc flower No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powdered sulfur vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd .: Sumitomo Chemical Co., Ltd. Soxinol CZ

(Examples and Comparative Examples)
In accordance with the formulation shown in Tables 6 to 10, materials other than sulfur and a vulcanization accelerator were kneaded for 5 minutes under a condition of 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 cap tread shape and bonded together with other tire members on a tire molding machine to form an unvulcanized tire, and vulcanized at 150 ° C. for 30 minutes, A test tire (size: 11R22.5) was manufactured.

The following evaluation was performed about the obtained vulcanized rubber composition and the tire for a test. The results are shown in Tables 6-10. In the following evaluation, the reference comparative example in Table 6 is Comparative Example 1, the comparative example in Table 7 is Comparative Example 2, the comparative example in Table 8 is Comparative Example 3, and the comparative example in Table 9 is Comparative Example 5. The reference comparative example in Table 10 was set as Comparative Example 7.

<Evaluation items and test methods>
<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 the reference comparative example being 100. The larger the value, the lower the rolling resistance and the lower the fuel consumption.

<Rubber strength>
A tensile test was performed on the rubber test piece cut out from the tread of the test tire according to JIS K6251, and the elongation at break (break strength) was measured. The measurement results are displayed as an index with the reference comparative example being 100. The larger the index, the better the rubber strength (breaking strength).

<Abrasion resistance>
A test tire is mounted on a domestic 2-D vehicle, the groove depth of the tire tread portion after a mileage of 50,000 km is measured, and the mileage when the tire groove depth decreases by 1 mm is calculated by the following formula: The index was displayed. The higher the index, the better the wear resistance.
(Abrasion resistance index) = (travel distance of each formulation) / (travel distance of reference comparative example) × 100

<Wet grip performance>
The wet grip performance of the test tire was evaluated by the following test.
(1) WET turning performance Place: Sumitomo Rubber Industries, Ltd. Okayama Test Course Method: The lap time when making one round of a course with a radius of 30 m in a wet state was expressed as the reciprocal of the ratio with the reference comparative example. A reference comparative example is set to 100, and a larger value indicates a better result.
(2) WET traction performance Place: Sumitomo Rubber Industries, Ltd. Okayama Test Course Method: The time of a certain section of the course in a wet state was expressed as the reciprocal of the ratio with the reference comparative example. A reference comparative example is set to 100, and a larger value indicates a better result.
(3) WET brake performance Location: Sumitomo Rubber Industries, Ltd. Okayama Test Course Method: The distance from the wet road surface area at a speed of 60 km / hr to braking and stopping is compared to the reference comparative example. Reciprocal of A reference comparative example is set to 100, and a larger value indicates a better result.

As shown in Tables 6 to 10, the examples in which at least one of the conjugated diene polymers (A) to (E) and silica were blended had lower fuel consumption and resistance than the rubber composition of the comparative example. All the performances of wearability, rubber strength and wet grip performance were improved, and these performances were obtained in a highly balanced manner.

Claims (27)

Containing a rubber component and silica,
In 100% by mass of the rubber component, the content of the modified butadiene polymer (A) composed of a structural unit based on 1,3-butadiene and a structural unit based on a compound represented by the following formula (1) is 5% by mass or more , The content of natural rubber is 5 to 90% by mass, the content of butadiene rubber is 1 to 40% by mass ,
A truck / bus tire comprising a cap tread composed of a rubber composition having a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

(Wherein, m represents a number of 1 to 3, R ¹ is a polymerizable carbon - represents a hydrocarbyl group having a carbon double bond, R ² represents a hydrocarbylene group, when R ² is plural, R ² may be the same or different, A represents a substituted amino group, and when there are a plurality of A, a plurality of A may be the same or different, and R ³ represents a hydrocarbyl group, a substituted hydrocarbyl group or a substituted amino group. represents a group, if there are a plurality of R ^3, plural R ³ may be the same or different.) ^2. The track according to claim 1, wherein in the formula (1), m is 1, R ¹ is a group represented by the following formula (2), R ² is an alkylene group, and R ³ is an alkyl group.・ Bus tires.

(In the formula, n represents an integer of 0 to 2, and R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a hydrocarbyl group.) The truck / bus tire according to claim 2, wherein in the formula (2), R ⁴ , R ⁵ and R ⁶ are hydrogen atoms and n is 0. The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the modified butadiene polymer (A) is 1 to 3. Truck and bus tires described in 1. The vinyl bond content of the modified butadiene polymer (A) is 20 mol% or more and 70 mol% or less, where the content of structural units based on 1,3-butadiene is 100 mol%. Truck and bus tires described in 1. The truck / bus tire according to any one of claims 1 to 5, wherein a carbon black content is 10 to 50 parts by mass with respect to 100 parts by mass of the rubber component. Containing a rubber component and silica,
In 100% by mass of the rubber component, the content of the modified butadiene polymer (B) composed of a structural unit based on 1,3-butadiene and a structural unit based on a compound represented by the following formula (4) is 5% by mass or more , The content of natural rubber is 5 to 90% by mass, the content of butadiene rubber is 1 to 40% by mass ,
A truck / bus tire comprising a cap tread composed of a rubber composition having a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

(In the formula, h represents 1 or 2, i represents 1 or 2, h + i is 2 or 3, R ¹¹ represents a hydrocarbyl group having a polymerizable carbon-carbon double bond, and R ¹² represents hydrocarbyl. represents a group, if R ¹² is plural, there R ¹² may be the same or different, R ¹³ represents an aryl group which may have an oxygen-containing substituent, if R ¹³ there are a plurality, A plurality of R ¹³ may be the same or different, and R ¹⁴ represents an alkyl group or a substituted amino group.) In the formula (4), h + i is 3, R ¹¹ is a group represented by the following formula (5), R ¹² is a tertiary alkyl group, and R ¹³ has an alkyl group. The truck / bus tire according to claim 7, which is a good phenyl group.

(In the formula, p is 0 or 1, R ¹⁵ represents a hydrogen atom or a hydrocarbyl group, and T represents a hydrocarbylene group.) The truck / bus tire according to claim 7 or 8 , wherein in the formula (4), R ¹¹ is a vinyl group. The modified butadiene polymer (B) according to claim 7 weight average molecular weight (Mw) and molecular weight distribution represented by the ratio (Mw / Mn) of the number average molecular weight (Mn) of 1.0 to 1.5 of the ~ 9. The truck / bus tire according to any one of 9 . Vinyl bond content of the modified butadiene polymer (B) is 1,3-content of butadiene based structural units as 100 mol%, it claims 7-10 is 70 mol% or less than 20 mol% Truck and bus tires described in 1. The truck / bus tire according to any one of claims 7 to 11, wherein a content of carbon black is 10 to 50 parts by mass with respect to 100 parts by mass of the rubber component. Containing a rubber component and silica,
The rubber component in 100% by mass, in a hydrocarbon solvent, in the coexistence with the Lewis basic compound, 1,3-butadiene monomer over the active butadiene having an alkali metal end obtained by polymerization using an alkali metal catalyst The content of the modified butadiene polymer (C) obtained by reacting the compound represented by the following formula (7) with respect to the polymer is 5% by mass or more , the content of natural rubber is 5 to 90% by mass, and butadiene rubber. Is 1 to 40% by mass ,
A truck / bus tire comprising a cap tread composed of a rubber composition having a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

(Wherein j to l independently represent an integer of 1 to 8) The modified butadiene polymer weight average molecular weight of (C) (Mw) and number average molecular weight (Mn) and the ratio claim 13, wherein (Mw / Mn) in molecular weight distribution represented is 1.0 to 1.5 Truck and bus tires. The truck / bus tire according to claim 13 or 14, wherein the vinyl bond content of the modified butadiene polymer (C) is 10 to 70 mol%, where the content of 1,3-butadiene units is 100 mol%. The truck / bus tire according to any one of claims 13 to 15, wherein a content of carbon black is 10 to 50 parts by mass with respect to 100 parts by mass of the rubber component. Containing a rubber component and silica,
Represented by the following formula (9) to one end of the rubber component in 100% by mass, Ru structural units Tona based on the compound represented by structural units and formula based on 1,3-butadiene (8) butadiene polymer The content of the modified butadiene polymer (D) obtained by reacting the compound is 5% by mass or more , the content of natural rubber is 5 to 90% by mass, and the content of butadiene rubber is 1 to 40% by mass ,
A truck / bus tire comprising a cap tread composed of a rubber composition having a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

(Wherein R ²¹ represents a hydrogen atom or a hydrocarbyl group having 1 to 5 carbon atoms, s is 0 or 1, R ²² represents a hydrocarbylene group, and R ²³ and R ²⁴ are each a hydrocarbyl group. Group, a trihydrocarbylsilyl group, or a hydrocarbylene group in which R ²³ and R ²⁴ are bonded to each other and optionally have a nitrogen atom and / or an oxygen atom, or R ²³ and R ²⁴ are 1 Represents a group which is bonded to a nitrogen atom with a double bond.)

(Wherein t represents an integer of 1 to 10, R ²⁵ , R ²⁶ and R ²⁷ each represents a hydrocarbyl group or a hydrocarbyloxy group, and at least one of R ²⁵ , R ²⁶ and R ²⁷ is a hydrocarbyloxy group. R ²⁸ and R ²⁹ are each a hydrogen atom, a nitrogen atom and / or a hydrocarbyl group optionally having an oxygen atom, or R ²⁸ and R ²⁹ are bonded to form a nitrogen atom and / or (The hydrocarbylene group which may have an oxygen atom, or R ²⁸ and R ²⁹ are one group and represent a group bonded to a nitrogen atom with a double bond.) The truck / bus tire according to claim 17, wherein, in the formula (8), R ²¹ is a hydrogen atom, s is 1, and R ²² is a group represented by the following formula (10).

(In the formula, (CH ₂ ) _u is a substituent on the benzene ring, u represents an integer of 0 to 5, and when u is an integer of 1 to 5, (CH ₂ ) _u is represented by formula (8). To bond with the nitrogen atom.) The truck / bus tire according to claim 17 or 18, wherein, in the formula (9), R ²⁵ , R ²⁶ and R ²⁷ are hydrocarbyloxy groups, and R ²⁸ and R ²⁹ are hydrocarbyl groups. The content of monomer units based on the compound represented by the formula (8) is 0.01 to 20% by mass, where the total amount of monomer units in the modified butadiene polymer (D) is 100% by mass. The truck / bus tire according to any one of claims 17 to 19 . The vinyl bond content of the modified butadiene polymer (D) is 1,3-butadiene content of the monomer units being 100 mole% based on, of claims 17 to 20 is not less than 20 mol% 70 mol% or less The truck / bus tire according to any one of the above. The truck / bus tire according to any one of claims 17 to 21, wherein a content of carbon black is 10 to 50 parts by mass with respect to 100 parts by mass of the rubber component. Containing a rubber component and silica,
Represented by the following formula (12) at one end of the rubber component in 100% by mass, 1,3-butadiene based structural units and formula (11) Ru Tona structural units based on a compound represented by the butadiene polymer The content of the monomer unit obtained by reacting the compound and based on the compound represented by the following formula (11) is 0.01 to 100% by weight based on the total amount of the monomer unit in the butadiene polymer. The content of the modified butadiene polymer (E) being 20% by mass is 5% by mass or more , the content of natural rubber is 5 to 90% by mass, and the content of butadiene rubber is 1 to 40% by mass ,
A truck / bus tire comprising a cap tread composed of a rubber composition having a silica content of 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

(In the formula, R ³¹ represents a hydrogen atom or a hydrocarbyl group, w is 0 or 1, R ³² represents a hydrocarbylene group, and B represents a nitrogen-containing heterocyclic group.)

(Wherein x represents a number of 1 to 10, R ³³ , R ³⁴ and R ³⁵ each represent a hydrocarbyl group or a hydrocarbyloxy group, and at least one of R ³³ , R ³⁴ and R ³⁵ is a hydrocarbyloxy group. R ³⁶ and R ³⁷ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or R ³⁶ and R ³⁷ are bonded to form a nitrogen atom and / or (The hydrocarbylene group which may have an oxygen atom, or R ³⁶ and R ³⁷ are one group and represent a group bonded to a nitrogen atom with a double bond.) The truck / bus tire according to claim 23 , wherein, in the formula (12), R ³³ , R ³⁴ and R ³⁵ are hydrocarbyloxy groups, and R ³⁶ and R ³⁷ are hydrocarbyl groups. The truck / bus tire according to claim 23 or 24 , wherein, in the formula (11), R ³¹ is a hydrogen atom and B is a pyridyl group. The vinyl bond content of the modified butadiene polymer (E) is 1,3-butadiene content of the monomer units being 100 mole% based on, of claims 23-25 is 70 mol% or less than 20 mol% The truck / bus tire according to any one of the above. 27. The truck / bus tire according to claim 23, wherein a content of carbon black is 10 to 50 parts by mass with respect to 100 parts by mass of the rubber component.