JP6334089B2 - Rubber composition for tread and pneumatic tire - Google Patents

Description

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

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

As a method for improving fuel economy, for example, Patent Document 1 proposes a method using a diene rubber (modified rubber) modified with an organosilicon compound containing an amino group and an alkoxy group. However, in recent years, further improvement in fuel economy has been demanded due to an increase in interest in environmental problems. In addition, the performance required for rubber compositions for automobile tires includes wet grip performance and wear resistance, but these performances are generally in contradiction to low fuel consumption. It was difficult to obtain a high dimension and good balance.

JP 2000-344955 A

The object of the present invention is to solve the above problems and provide a rubber composition for a tread that can improve the fuel efficiency, wet grip performance and wear resistance in a well-balanced manner, and a pneumatic tire using the same.

（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 present invention contains a rubber component, silica, and a resin having a softening point of 60 to 120 ° C., and is based on a structural unit based on a conjugated diene and a compound represented by the following formula (1) in 100% by mass of the rubber component The content of the conjugated diene polymer having a unit is 5% by mass or more, the content of the silica with respect to 100 parts by mass of the rubber component is 5 to 150 parts by mass, and the content of the resin is 1 to 30 parts by mass. The present invention relates to a rubber composition for a tread.

(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^２１、Ｒ^２２及びＲ^２３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。） The conjugated diene polymer is a compound in which 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. It is preferable.

(In the formula, n represents an integer of 0 to 2, and R ²¹ , R ²² and R ²³ each independently represents a hydrogen atom or a hydrocarbyl group.)

The conjugated diene polymer is preferably a compound in which R ²¹ , R ²² and R ²³ 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 is preferably 1 to 3.

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

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

According to the present invention, since it is a rubber composition containing a conjugated diene polymer having a specific monomer unit, silica and a resin having a softening point of 60 to 120 ° C., low fuel consumption, wet grip performance And a pneumatic tire with improved wear resistance in a well-balanced manner.

The conjugated diene polymer according to the present invention is a conjugated diene polymer having 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 according to the present invention 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^２１、Ｒ^２２及びＲ^２３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 ²¹ , R ²² and R ²³ each independently represents a hydrogen atom or a hydrocarbyl group.)

Examples of the hydrocarbyl group of R ²¹ , R ²² and R ²³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and a 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 ²¹ , R ²² and R ²³ are hydrogen atoms, n = 0), an allyl group (R ²¹ , R ²² and R ²³ are hydrogen atoms, n = 1) ), 1-propenyl group (R ²¹ is a methyl group, R ²² and R ²³ are hydrogen atoms, n = 0), isopropenyl group (R ²¹ and R ²² are hydrogen atoms, R ²³ is a methyl group, n = 0) A crotyl group (R ²¹ is a methyl group, R ²² and R ²³ are hydrogen atoms, n = 1), and a methallyl group (R ²¹ and R ²² are hydrogen atoms, R ²³ is a methyl group, n = 1).

R ²¹ and R ²² are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

R ²³ is preferably a hydrogen atom or an alkyl group, and 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 ²¹ , R ²² and R ²³ are hydrogen atoms, n = 0), and an allyl group (R ²¹ , R ²² and R ²³ are hydrogen atoms, n = 1). More preferably, it is a vinyl group (R ²¹ , R ²² and R ²³ 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^３１及びＲ^３２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^３１とＲ^３２とが結合した炭素原子数が２〜２０の２価基、又は、Ｒ^３１とＲ^３２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).

(In the formula, R ³¹ and R ³² are each 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 ³¹ and R ³² are bonded, or R ³¹ and R ³² 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 ³¹ and R ³² 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 in the hydrocarbyl group of R ³¹ and R ³² 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 ³¹ and R ³² 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 ³¹ and R ³² 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 ³¹ and R ³² include alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxymethyl group, and ethoxyethyl group; oxacyclo groups such as oxiranyl group and 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 ³¹ and R ³² 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 ³¹ and R ³² include a trialkylsilylalkyl group such as a trimethylsilylmethyl group.

The number of carbon atoms of the hydrocarbyl group having a silicon atom of R ³¹ and R ³² 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 of R ³¹ and R ³² 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 ³¹ and R ³² is preferably 3 to 10, more preferably 3 to 6, and still more preferably 3.

Examples of the divalent group having 2 to 20 carbon atoms to which R ³¹ and R ³² 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 ³¹ and R ³² 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 ³¹ and R ^{32 with} 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 ³¹ and R ^{32 by} a double bond is preferably 2 to 12, more preferably 2 to 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 group, 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 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 dimethyl-1-piperidinylmethylvinylsilane.

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

The content of the constituent unit based on the monomer represented by the formula (1) in the conjugated diene polymer component is preferably 0.001 mmol / g per unit weight of the polymer in order to increase the wear resistance. More than polymer, More preferably, it is 0.002 mmol / g polymer or more, More preferably, it is 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.

The conjugated diene polymer preferably has an aromatic vinyl unit in order to increase the strength. As the content of the aromatic vinyl unit, the total amount of the conjugated diene unit and the aromatic vinyl unit is 100% by mass, preferably 10% by mass or more (the content of the conjugated diene unit is 90% by mass or less), and more Preferably it is 15 mass% or more (content of a conjugated diene unit is 85 mass% or less). In order to improve fuel economy, the content of the aromatic vinyl unit is preferably 50% by mass or less (the content of the conjugated diene unit is 50% by mass or more), more preferably 45% by mass or less (conjugated). The diene unit content is 55% by mass or more).

The vinyl bond content of the conjugated diene polymer is preferably 80 mol% or less, and more preferably 70 mol% or less in order to improve the fuel efficiency by setting the content of the conjugated diene unit to 100 mol%. 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 is preferably 10 or more, more preferably 20 or more, in order to increase the 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 is preferably 1 to 5 and more preferably 1 to 3 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.

[Method for producing conjugated diene polymer]
A preferred method for producing a conjugated diene polymer according to the present invention is a method in which a monomer containing a conjugated diene and a compound represented by formula (1) is polymerized with an alkali metal catalyst in a hydrocarbon solvent. is there. 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. Aromatic vinyl is preferable, and styrene is more preferable.

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. Examples of the tertiary amine 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.

In the production of the conjugated diene polymer, if necessary, a coupling agent may be added to the hydrocarbon solution of the conjugated diene polymer from the start of the polymerization of the monomer by the alkali metal catalyst to the termination of the polymerization. Examples of the coupling agent include compounds represented by the following formula (X).

（式中、Ｒ^１０はアルキル基、アルケニル基、シクロアルケニル基またはアリール基を表し、Ｍはケイ素原子またはスズ原子を表し、Ｌはハロゲン原子またはヒドロカルビルオキシ基を表し、ａは０〜２の整数を表す。）

(Wherein R ¹⁰ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aryl group, M represents a silicon atom or a tin atom, L represents a halogen atom or a hydrocarbyloxy group, and a represents an integer of 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 low-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 polymer include known recovery methods. For example, (i) a method of adding a coagulant to a hydrocarbon solution of a conjugated diene polymer, and (ii) a method of adding steam to a hydrocarbon solution of a conjugated diene polymer. The recovered conjugated diene polymer may be dried by a known dryer such as a band dryer or an extrusion dryer.

The conjugated diene polymer can be used as a rubber component, and the rubber composition of the present invention can be obtained by blending other rubber components and additives such as silica.

The content of the conjugated diene polymer in 100% by mass of the rubber component is 5% by mass or more, preferably 20% by mass or more, more preferably 40% 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 polymer is preferably 90% by mass or less, more preferably 80% by mass or less. When it exceeds 90% by mass, the wear resistance is lowered and the cost tends to be high.

The rubber component that can be used in addition to the conjugated diene polymer 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 preferred because they exhibit a good balance between low fuel consumption, wet grip performance and wear resistance.
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 15% 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 60% by mass or less, more preferably 40% by mass or less. When it exceeds 60 mass%, workability tends to deteriorate.

The content of BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 15% by mass or more. When it is less than 5% by mass, sufficient wear resistance tends to be not obtained. Further, the BR content is preferably 60% by mass or less, more preferably 40% by mass or less. When it exceeds 60% by mass, fuel efficiency 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 30 parts by mass or more, more preferably 50 parts by mass or more, in order to improve fuel efficiency. Moreover, in order to improve abrasion resistance and intensity | strength, Preferably it is 120 mass parts or less, More preferably, it is 100 mass parts or less.

The rubber composition of the present invention contains a resin having a softening point of 60 to 120 ° C. By blending the resin together with the conjugated diene polymer and silica, fuel economy, wear resistance, and wet grip performance can be improved in a well-balanced manner.

The resin is not particularly limited as long as it satisfies the softening point, but from α-methylstyrene and / or aromatic vinyl polymer obtained by polymerizing styrene, coumarone indene resin, indene resin, terpene resin and rosin resin. There are groups such as. Of these, α-methylstyrene resin, coumarone indene resin, terpene resin, rosin resin, and derivatives thereof are preferable because of excellent adhesion when unvulcanized and low fuel consumption. A malon indene resin is more preferred.

The softening point of the resin is 60 ° C. or higher, preferably 75 ° C. or higher. When the temperature is less than 60 ° C., the viscosity of the resin becomes too low, and the kneading property with the rubber component is deteriorated, or a sufficient wet grip performance improving effect cannot be obtained. The softening point of the resin is 120 ° C. or lower, preferably 100 ° C. or lower. When the temperature exceeds 120 ° C., the loss elastic modulus in the high temperature region increases significantly, energy loss increases, and fuel efficiency tends to deteriorate.
In this specification, the softening point is a temperature at which a sphere descends when a softening point defined in JIS K6220-1: 2001 is measured with a ring and ball softening point measuring apparatus.

Content of the said resin is 1 mass part or more with respect to 100 mass parts of rubber components, Preferably it is 3 mass parts or more, More preferably, it is 5 mass parts or more. If it is less than 1 part by mass, the wet grip performance may not be sufficiently improved. The content of the resin is 30 parts by mass or less, preferably 15 parts by mass or less. When it exceeds 30 mass parts, there exists a tendency for low-fuel-consumption property and abrasion resistance to deteriorate.

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 content of sulfur is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. It is.

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, and the dibutyl phthalate (DBP) absorption amount of carbon black is preferably 5 to 300 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. As a commercial item, Mitsubishi Chemical Corporation trade name Dia Black N339, Tokai Carbon Co., Ltd. trade name Seast 6, Seast 7HM, Seast KH, Degussa Corporation trade name CK3, Special Black 4A, etc. can be used.

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 3 parts by mass or more, and still more preferably 4 parts by mass or more, in order to increase wear resistance and strength. Moreover, in order to improve low fuel consumption, More preferably, it is 30 mass parts or less, More preferably, it is 10 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 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 2: 1 to 50: 1. The mass ratio is more preferably 5: 1 to 20: 1 in order to increase fuel efficiency and enhance reinforcement.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 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 vulcanization treatment such as press vulcanization. The vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.

The rubber composition of the present invention has a high level of good balance between low fuel consumption, wet grip performance and wear resistance.

The rubber composition of the present invention is used for tire treads (cap treads).

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, a rubber composition containing various additives as necessary is extruded in accordance with the shape of the tread of the tire at an unvulcanized stage, molded by a normal method on a tire molding machine, etc. The tire members are bonded together to form an unvulcanized tire. This unvulcanized tire can be heated and pressurized in a vulcanizer to produce the pneumatic tire of the present invention.

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

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

(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, and 10.2 kg of industrial hexane (density 680 Kg / m ³ ), 608 g of 1,3-butadiene, 192 g of styrene, tetrahydrofuran 6. 07 ml and ethylene glycol diethyl ether 4.00 ml were 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.
While stirring speed was 130 rpm, polymerization reactor internal temperature was 65 ° C., and monomers were continuously fed into the polymerization reaction vessel, 1,3-butadiene, styrene, and dimethyl-1-piperidinylmethylvinylsilane Copolymerization was carried out for 3.0 hours. The amount of 1,3-butadiene supplied during the entire polymerization was 912 g, and the amount of styrene supplied was 288 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 a polymer 1.

(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, 2.55 kg of industrial hexane (density 680 Kg / m ³ ), 137 g of 1,3-butadiene, 43 g of styrene, tetrahydrofuran 1. 52 ml and 1.12 ml of ethylene glycol diethyl ether were 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.
While stirring speed was 130 rpm, polymerization reactor internal temperature was 65 ° C., and monomers were continuously fed into the polymerization reaction vessel, 1,3-butadiene, styrene, and dimethyl-1-piperidinylmethylvinylsilane Copolymerization was carried out for 2.5 hours. The supply amount of 1,3-butadiene in the entire polymerization was 205 g, and the supply amount of styrene was 65 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 a polymer 2.

(Polymer Production Example 3) (Comparative Example)
The inside of the stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried and replaced with dry nitrogen, and 10.2 kg of industrial hexane (density 680 Kg / m ³ ), 547 g of 1,3-butadiene, 173 g of styrene, tetrahydrofuran 6. 07 ml and ethylene glycol diethyl ether 4.00 ml were charged into the polymerization reaction vessel. Next, 14.46 mmol of n-butyllithium was added as an n-hexane solution to initiate polymerization.
The stirring rate was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene and styrene were copolymerized for 3 hours while continuously supplying the monomer into the polymerization reaction vessel. The supply amount of 1,3-butadiene in the total polymerization was 821 g, and the supply amount of styrene was 259 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 a polymer 3.

The following physical property evaluation was performed about the obtained polymers 1-3. The results are shown in Table 1.

(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 in the polymer was determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

(Styrene unit content (unit: mass%))
According to JIS K6383 (1995), the content of styrene units in the polymer was determined from the refractive index.

(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.
Natural rubber (NR): RSS # 3
Butadiene rubber (BR): Ubepol BR150B manufactured by Ube Industries, Ltd.
Polymers 1-3: Polymer carbon black obtained in Production Examples 1 to 3 above: Diablack N220 (N ₂ SA: 111 m ² / g, DBP absorption: 115 ml / 100 g) manufactured by Mitsubishi Chemical Corporation
Silica: Ultrasil VN3 manufactured by Degussa (N ₂ SA: 175 m ² / g)
Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa
Resin 1: NOVARES C90 (coumarone indene resin, softening point: 90 ° C.) manufactured by Tortcars Chemical Co.
Resin 2: SYLVARES SA85 (α-methylstyrene resin, softening point: 85 ° C.) manufactured by Arizona Chemical
Resin 3: NOVARES C30 (Coumaron indene resin, softening point: 30 ° C.) manufactured by Tortoise Chemicals
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Anti-aging agent: Antigen 3C manufactured by Sumitomo Chemical Co., Ltd.
Stearic acid: Beads manufactured by NOF Corporation Zinc stearate Zinc oxide: Zinc flower No. 1 manufactured by Mitsui Kinzoku Mining Co., Ltd. Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. 1: Soxinol CZ manufactured by Sumitomo Chemical Co., Ltd.
Vulcanization accelerator 2: Soxinol D manufactured by Sumitomo Chemical Co., Ltd.

<Examples and Comparative Examples>
According to the blending content shown in Table 2, materials other than sulfur and vulcanization accelerator were kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer manufactured by Kobe Steel Co., Ltd. Obtained. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes under the condition of 80 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized with a 0.5 mm thick mold at 170 ° C. for 20 minutes to obtain a vulcanized rubber composition.
Further, the obtained unvulcanized rubber composition is molded into a tread shape and bonded together with other tire members on a tire molding machine to form an unvulcanized tire, which is vulcanized at 170 ° C. for 12 minutes, and tested. Tires (size: 195 / 65R15) were manufactured.

The following evaluation was performed about the obtained vulcanized rubber composition and the tire for a test. The results are shown in Table 2.

(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 molded body and subjected to the test. The measurement is performed by measuring the loss tangent (tan δ (70 ° C.)) of the test piece at a temperature of 70 ° C. under the conditions of a strain of 1% and a frequency of 10 Hz using a viscoelasticity measuring device (manufactured by Ueshima Seisakusho Co., Ltd.). It was displayed as an index when Example 1 was taken as 100. The larger the index, the better the fuel economy.

(Rolling resistance)
Using a rolling resistance tester, the rolling resistance when a test tire is run at a rim (15 × 6JJ), internal pressure (230 kPa), load (3.43 kN), speed (80 km / h) is measured and compared. It was displayed as an index when Example 1 was taken as 100. A larger index is better (low fuel consumption).

(Wet grip performance)
Each test tire was mounted on all wheels of a vehicle (domestic FF2000cc), and a braking distance from an initial speed of 100 km / h was determined on a wet asphalt road surface. The result is expressed as an index. The larger the number, the better the wet skid performance (wet grip performance). The index was calculated by the following formula.
Wet skid performance = (braking distance of comparative example 1) / (braking distance of each formulation) × 100

(Abrasion resistance)
Using a LAT tester (Laboratory Abrasion and Skid Tester), the volume loss of each vulcanized rubber composition was measured under the conditions of a load of 50 N, a speed of 20 km / h, and a slip angle of 5 °. The numerical value (LAT index) in Table 2 is a relative value when the volume loss amount of Comparative Example 1 is 100. The larger the value, the better the wear resistance.

From the evaluation results of Table 2, by using a specific modified conjugated diene polymer in the present invention and a resin having a specific softening point, the fuel efficiency, wet grip performance, and wear resistance are improved synergistically, These performances can be improved in a well-balanced manner at a high level.

Claims (7)

Containing a rubber component, silica and a resin having a softening point of 60 to 120 ° C .;
In 100% by mass of the rubber component, the content of a conjugated diene polymer having a structural unit based on a conjugated diene and a structural unit based on a compound represented by the following formula (1) is 5% by mass or more.
The silica content is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component, and the resin content is 1 to 30 parts by mass.
A rubber composition for a tread, wherein the resin is at least one selected from the group consisting of α-methylstyrene and / or an aromatic vinyl polymer obtained by polymerizing styrene, coumarone indene resin, indene resin, terpene resin and rosin resin. .

(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.) In the compound represented by 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. The rubber composition for a tread according to claim 1, wherein the rubber composition is a compound.

(In the formula, n represents an integer of 0 to 2, and R ²¹ , R ²² and R ²³ each independently represents a hydrogen atom or a hydrocarbyl group.) A group represented by the formula (2) ^is, R ^{21, R 22,} and ^{R 23} is a hydrogen atom, a tread rubber composition according to claim 2 n is a group represented by 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 is 1 to 3. Rubber composition for treads. The rubber for treads according to any one of claims 1 to 4, wherein the vinyl bond content of the conjugated diene polymer is 20 mol% or more and 70 mol% or less, with the content of structural units based on diene being 100 mol%. Composition. The rubber composition for a tread according to any one of claims 1 to 5, wherein, in 100% by mass of the rubber component, the content of natural rubber is 5 to 60% by mass and the content of butadiene rubber is 5 to 60% by mass. The pneumatic tire produced using the rubber composition for treads in any one of Claims 1-6.