JP2014105321A - Rubber composition for base tread and pneumatic tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition for a base tread capable of improving fuel consumption property and fracture strength resistance in a good balance and to provide a tire.SOLUTION: The invention relates to a rubber composition for a base tread having the content of a conjugated diene-based polymer obtained by reacting a compound represented by the formula (II) to a terminal of a conjugated diene-based polymer having a constitutional unit based on a compound represented by the formula (I) (the content is 0.01 to 20 mass%) of 5 mass% or more and the content of silica of 5 to 150 pts.mass based on 100 pts.mass of a rubber component.

Description

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

Conventionally, a method of blending silica as a filler is known as a technique for reducing rolling resistance of a tire (reducing fuel consumption of a vehicle). For example, rolling resistance can be reduced by blending silica in a tread. At the same time, the WET traction performance can be improved at the same time. Patent Documents 1 to 3 disclose a method of improving fuel efficiency by blending two types of silica having different nitrogen adsorption specific surface areas and particle diameters into a tread. However, there is a limit to the improvement in fuel efficiency when only the tread is improved, and the base tread is also required to have excellent low heat generation.

Unlike the tread, carbon black having a large particle size has been used for the base tread in order to improve fuel efficiency. Therefore, even if part or all of the carbon black is replaced with silica, the effect of reducing rolling resistance is not so great. Moreover, there is also a problem that the fracture strength and workability are reduced by the replacement. As another technique capable of reducing the rolling resistance, a method of reducing the content of the filler is also known, but this method also has a problem that the fracture resistance is lowered. Therefore, there is a demand for a method for improving fuel economy, fracture resistance and workability in a well-balanced manner.

JP 2006-233177 A JP 2008-50570 A JP 2008-101127 A

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

（式中、Ｒ^１１は水素原子又はヒドロカルビル基を表し、ｍは０又は１であり、Ｒ^１２はヒドロカルビレン基を表し、Ｔは含窒素複素環基を表す。）

（式中、ｎは１〜１０の数を表し、Ｒ^２１、Ｒ^２２及びＲ^２３は、それぞれ、ヒドロカルビル基又はヒドロカルビルオキシ基を表し、Ｒ^２１、Ｒ^２２及びＲ^２３の少なくとも１つがヒドロカルビルオキシ基であり、Ｒ^２４及びＲ^２５は、それぞれ、水素原子、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビル基、あるいは、Ｒ^２４とＲ^２５とが結合して、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビレン基、又は、Ｒ^２４とＲ^２５は１つの基であって、窒素原子に二重結合で結合する基を表す。） The present invention includes a rubber component and silica, and one end 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 (I) in 100% by mass of the rubber component. Obtained by reacting the compound represented by the following formula (II) with the monomer unit based on the compound represented by the following formula (I), the monomer unit in the conjugated diene polymer The content of the conjugated diene polymer that is 0.01 to 20% by mass is 5% by mass or more, and the content of the silica is 5 to 150% by mass with respect to 100 parts by mass of the rubber component. It is related with the rubber composition for base treads which is a part.

(In the formula, R ¹¹ represents a hydrogen atom or a hydrocarbyl group, m is 0 or 1, R ¹² represents a hydrocarbylene group, and T represents a nitrogen-containing heterocyclic group.)

(In the formula, n represents a number of 1 to 10, R ²¹ , R ²² and R ²³ each represent a hydrocarbyl group or a hydrocarbyloxy group, and at least one of R ²¹ , R ²² and R ²³ is a hydrocarbyloxy group. R ²⁴ and R ²⁵ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or R ²⁴ and R ²⁵ are bonded to form a nitrogen atom and / or (The hydrocarbylene group which may have an oxygen atom, or R ²⁴ and R ²⁵ are one group and represent a group bonded to a nitrogen atom with a double bond.)

In the formula (II), R ²¹ , R ²² and R ²³ are preferably hydrocarbyloxy groups, and R ²⁴ and R ²⁵ are preferably hydrocarbyl groups.

In formula (I), R ¹¹ is preferably a hydrogen atom, and T is preferably a pyridyl group.

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

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

According to the present invention, since it is a rubber composition in which a conjugated diene polymer having a specific monomer unit and a terminal is modified with a specific compound and silica, the fuel efficiency and resistance A pneumatic tire having improved fracture strength and workability in a well-balanced manner can be provided.

（式中、Ｒ^１１は水素原子又はヒドロカルビル基を表し、ｍは０又は１であり、Ｒ^１２はヒドロカルビレン基を表し、Ｔは含窒素複素環基を表す。）

（式中、ｎは１〜１０の数を表し、Ｒ^２１、Ｒ^２２及びＲ^２３は、それぞれ、ヒドロカルビル基又はヒドロカルビルオキシ基を表し、Ｒ^２１、Ｒ^２２及びＲ^２３の少なくとも１つがヒドロカルビルオキシ基であり、Ｒ^２４及びＲ^２５は、それぞれ、水素原子、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビル基、あるいは、Ｒ^２４とＲ^２５とが結合して、窒素原子及び／又は酸素原子を有していてもよいヒドロカルビレン基、又は、Ｒ^２４とＲ^２５は１つの基であって、窒素原子に二重結合で結合する基を表す。） The conjugated diene polymer according to the present invention includes a monomer unit based on a conjugated diene and a monomer unit based on a compound represented by the following formula (I) at one end of the following formula ( It is a conjugated diene polymer obtained by reacting the compound represented by II).

(In the formula, R ¹¹ represents a hydrogen atom or a hydrocarbyl group, m is 0 or 1, R ¹² represents a hydrocarbylene group, and T represents a nitrogen-containing heterocyclic group.)

(In the formula, n represents a number of 1 to 10, R ²¹ , R ²² and R ²³ each represent a hydrocarbyl group or a hydrocarbyloxy group, and at least one of R ²¹ , R ²² and R ²³ is a hydrocarbyloxy group. R ²⁴ and R ²⁵ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or R ²⁴ and R ²⁵ are bonded to form a nitrogen atom and / or (The hydrocarbylene group which may have an oxygen atom, or R ²⁴ and R ²⁵ are one group and represent a group bonded to a nitrogen atom with a double bond.)

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

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

R ¹¹ represents a hydrogen atom or a hydrocarbyl group.

Examples of the hydrocarbyl group for R ¹¹ include an alkyl group and an alkenyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group is preferable. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and a 1-methylethenyl group, and a vinyl group is preferable.

R ¹¹ is preferably a hydrogen atom, a methyl group, or a vinyl group.

Examples of the hydrocarbylene group for R ¹² include an alkylene group, an arylene group, and a group in which an arylene group and an alkylene group are bonded.

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

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

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

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

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

（式中、ｒは１〜５の整数を表す。）

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

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

Examples of the nitrogen-containing heterocyclic group represented by T include a nitrogen-containing alicyclic heterocyclic group and a nitrogen-containing aromatic heterocyclic group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

R ²¹ , R ²² , and R ²³ each represent a hydrocarbyl group or a hydrocarbyloxy group.

Examples of the hydrocarbyl group of R ²¹ , R ²² , and R ²³ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. be able to. The number of carbon atoms of the hydrocarbyl group is preferably 1 to 10, more preferably 1 to 3.

The hydrocarbyl group of R ²¹ , R ²² , and R ²³ is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably 1 to 3 carbon atoms. And particularly preferably a methyl group or an ethyl group.

Examples of the hydrocarbyloxy group for R ²¹ , R ²² , and R ²³ include alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group; An aryloxy group such as a phenoxy group can be exemplified. The number of carbon atoms of the hydrocarbyloxy group is preferably 1 to 10, more preferably 1 to 3.

The hydrocarbyloxy group for R ²¹ , R ²² , and R ²³ is preferably an alkoxy group, more preferably an alkoxy group having 1 to 10 carbon atoms, and still more preferably 1 to 1 carbon atom. 3 is particularly preferably a methoxy group or an ethoxy group.

At least one of R ²¹ , R ²² , and R ²³ is a hydrocarbyloxy group, and in order to improve fuel efficiency, preferably at least two of R ²¹ , R ²² , and R ²³ are hydrocarbyloxy groups, More preferably, three of R ²¹ , R ²² , and R ²³ are hydrocarbyloxy groups.

R ²⁴ and R ²⁵ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or R ²⁴ and R ²⁵ are bonded to form a nitrogen atom and / or an oxygen atom. which may have hydrocarbylene group, or, R ²⁴ and R ²⁵ form one group represents a group which bonds to a nitrogen atom with a double bond.

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

Examples of the hydrocarbyl group of R ²⁴ and R ²⁵ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group; vinyl group, allyl group, Examples thereof include alkenyl groups such as 1-propenyl group and 1-methylethenyl group; alkynyl groups such as ethynyl group and propargyl group; aryl groups such as phenyl group, tolyl group and xylyl group; and aralkyl groups such as benzyl group.

Examples of the hydrocarbyl group having a nitrogen atom of R ²⁴ and R ²⁵ include dialkylaminoalkyl groups such as a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a diethylaminomethyl group, a diethylaminoethyl group, and a diethylaminopropyl group. Can do.

Examples of the hydrocarbyl group having an oxygen atom of R ²⁴ and R ²⁵ include alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxymethyl group, ethoxyethyl group, and ethoxypropyl group; 2-oxiranyl group, 2 A monooxacycloalkyl group such as an oxetanyl group or 2-tetrahydrofuranyl group; a dioxacycloalkyl group such as a 2-dioxolanyl group; an alkyl group substituted with a monooxacycloalkyl group such as a glycidyl group or a tetrahydrofurfuryl group; A 3,4-epoxycyclohexyl group can be mentioned.

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

The number of carbon atoms of the hydrocarbyl group which may have a nitrogen atom and / or an oxygen atom of R ²⁴ and R ²⁵ is preferably 1 to 10, and more preferably 1 to 6.

Examples of the group in which R ²⁴ and R ²⁵ are bonded include a hydrocarbylene group, a hydrocarbylene group having a nitrogen atom, and a hydrocarbylene group having an oxygen atom. Examples of the hydrocarbylene group include alkylene groups such as trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group. As the hydrocarbylene group having a nitrogen atom, a group represented by —CH ₂ CH ₂ —NH—CH ₂ —, a group represented by —CH ₂ CH ₂ —N═CH—, —CH═CH—N A group represented by ═CH— and a group represented by —CH ₂ CH ₂ —NH—CH ₂ CH ₂ — can be exemplified. Examples of the hydrocarbylene group having an oxygen atom include a group represented by —CH ₂ CH ₂ —O—CH ₂ CH ₂ —.

The number of carbon atoms of the group to which R ²⁴ and R ²⁵ are bonded is preferably 2 to 20, and more preferably 2 to 12.

Examples of one group in which R ²⁴ and R ²⁵ are bonded to the nitrogen atom with a double bond include ethylidene group, propylidene group, butylidene group, 1-methylethylidene group, 1-methylpropylidene group, 1,3-dimethylbutylidene A hydrocarbylidene group such as a group; 4-N, N-dimethylaminobenzylidene group and the like.

The number of carbon atoms of one group in which R ²⁴ and R ²⁵ are bonded to the nitrogen atom with a double bond is preferably 2 to 20, and more preferably 2 to 12.

R ²⁴ and R ²⁵ are preferably a hydrocarbyl group, or a hydrocarbylene group in which R ²⁴ and R ²⁵ are bonded, or R ²⁴ and R ²⁵ are one group, and a nitrogen atom Is a hydrocarbylidene group which is a group bonded by a double bond, more preferably a hydrocarbyl group, and still more preferably an alkyl group. The alkyl group is preferably a methyl group or an ethyl group.

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

As a compound represented by the formula (II), as a compound in which R ²⁴ and R ²⁵ are alkyl groups,
[3- (dimethylamino) propyl] trimethoxysilane,
[3- (diethylamino) propyl] trimethoxysilane,
[3- (ethylmethylamino) propyl] trimethoxysilane,
[3- (dimethylamino) propyl] triethoxysilane,
[3- (diethylamino) propyl] triethoxysilane,
[3- (dialkylamino) propyl] trialkoxysilanes such as [3- (ethylmethylamino) propyl] triethoxysilane;

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

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

Examples of the compound represented by the formula (II) include compounds in which R ²⁴ and R ²⁵ are alkoxyalkyl groups.
{3- [bis (methoxymethyl) amino] propyl} trimethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} trimethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} trimethoxysilane,
{3- [bis (ethoxyethyl) amino] propyl} trimethoxysilane,
{3- [bis (methoxymethyl) amino] propyl} triethoxysilane,
{3- [bis (ethoxymethyl) amino] propyl} triethoxysilane,
{3- [bis (methoxyethyl) amino] propyl} triethoxysilane,
{3- [bis (alkoxyalkyl) amino] propyl} trialkoxysilanes such as {3- [bis (ethoxyethyl) amino] propyl} triethoxysilane;

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

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

As a compound represented by the formula (II), as a compound in which R ²⁴ and R ²⁵ are oxiranyl groups,
{3- [di (oxiranyl) amino] propyl} trimethoxysilane,
{3- [di (oxiranyl) amino] propyl} triethoxysilane,
{3- [di (oxiranyl) amino] propyl} methyldimethoxysilane,
{3- [di (oxiranyl) amino] propyl} ethyldimethoxysilane,
{3- [di (oxiranyl) amino] propyl} methyldiethoxysilane,
{3- [di (oxiranyl) amino] propyl} ethyldiethoxysilane,
{3- [di (oxiranyl) amino] propyl} dimethylmethoxysilane,
{3- [di (oxiranyl) amino] propyl} diethylmethoxysilane,
{3- [di (oxiranyl) amino] propyl} dimethylethoxysilane,
Examples include {3- [di (oxiranyl) amino] propyl} diethylethoxysilane.

Examples of the compound represented by the formula (II) include compounds in which R ²⁴ and R ²⁵ are tetrahydrofuranyl groups.
{3- [di (tetrahydrofuranyl) amino] propyl} trimethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} triethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} methyldimethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} ethyldimethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} methyldiethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} ethyldiethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} dimethylmethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} diethylmethoxysilane,
{3- [di (tetrahydrofuranyl) amino] propyl} dimethylethoxysilane,
Examples include {3- [di (tetrahydrofuranyl) amino] propyl} diethylethoxysilane.

As a compound represented by the formula (II), as a compound in which R ²⁴ and R ²⁵ are glycidyl groups,
{3- [di (glycidyl) amino] propyl} trimethoxysilane,
{3- [di (glycidyl) amino] propyl} triethoxysilane,
{3- [di (glycidyl) amino] propyl} methyldimethoxysilane,
{3- [di (glycidyl) amino] propyl} ethyldimethoxysilane,
{3- [di (glycidyl) amino] propyl} methyldiethoxysilane,
{3- [di (glycidyl) amino] propyl} ethyldiethoxysilane,
{3- [di (glycidyl) amino] propyl} dimethylmethoxysilane,
{3- [di (glycidyl) amino] propyl} diethylmethoxysilane,
{3- [di (glycidyl) amino] propyl} dimethylethoxysilane,
Examples include {3- [di (glycidyl) amino] propyl} diethylethoxysilane.

Examples of the compound represented by the formula (II) include compounds in which R ²⁴ and R ²⁵ are tetrahydrofurfuryl groups.
{3- [di (tetrahydrofurfuryl) amino] propyl} trimethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} triethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} methyldimethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} ethyldimethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} methyldiethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} ethyldiethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} dimethylmethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} diethylmethoxysilane,
{3- [di (tetrahydrofurfuryl) amino] propyl} dimethylethoxysilane,
Examples include {3- [di (tetrahydrofurfuryl) amino] propyl} diethylethoxysilane.

As the compound represented by the formula (II), as a compound in which R ²⁴ and R ²⁵ are bonded,
3- (1-piperidinyl) propyltrimethoxysilane,
3- (1-piperidinyl) propyltriethoxysilane,
3- (1-piperidinyl) propylmethyldimethoxysilane,
3- (1-piperidinyl) propylethyldimethoxysilane,
3- (1-piperidinyl) propylmethyldiethoxysilane,
3- (1-piperidinyl) propylethyldiethoxysilane,
3- (1-hexamethyleneimino) propyltrimethoxysilane,
3- (1-hexamethyleneimino) propyltriethoxysilane,
3- (1-hexamethyleneimino) propylmethyldimethoxysilane,
3- (1-hexamethyleneimino) propylethyldimethoxysilane,
3- (1-hexamethyleneimino) propylmethyldiethoxysilane,
3- (1-hexamethyleneimino) propylethyldiethoxysilane,
3-morpholinopropyltrimethoxysilane,
3-morpholinopropyltriethoxysilane,
3-morpholinopropylmethyldimethoxysilane,
3-morpholinopropylethyldimethoxysilane,
3-morpholinopropylmethyldiethoxysilane,
There may be mentioned 3-morpholinopropylethyldiethoxysilane.

As the compound represented by the formula (II), as a compound in which R ²⁴ and R ²⁵ are one group bonded to a nitrogen atom by a double bond,
N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine,
N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine can be mentioned.

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

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

The conjugated diene polymer according to the present invention preferably has monomer units (vinyl aromatic hydrocarbon units) based on vinyl aromatic hydrocarbons in order to increase strength. Examples of the vinyl aromatic hydrocarbon include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene. Styrene is preferable.

The content of the vinyl aromatic hydrocarbon unit is 0% by mass or more (the content of the conjugated diene unit is 100% by mass or less), where the total amount of the conjugated diene unit and the vinyl aromatic hydrocarbon unit is 100% by mass. In order to increase the strength, it is preferably 10% by mass or more (the content of the conjugated diene unit is 90% by mass or less), more preferably 15% by mass or more (the content of the conjugated diene unit is 85% by mass or less). is there. In order to improve fuel economy, the content of vinyl aromatic hydrocarbon units is preferably 50% by mass or less (the content of conjugated diene units is 50% by mass or more), more preferably 45% by mass or less. (The content of the conjugated diene unit is 55% by mass or more).

The total amount of the monomer unit and the vinyl aromatic hydrocarbon unit based on the conjugated diene unit and the compound represented by the formula (I) is 100% by mass based on the total amount of the monomer unit in the conjugated diene polymer. In order to improve the wear resistance, the content is preferably 99.9% by mass or more, more preferably 99.95% by mass or more, and still more preferably 100% by mass.

The Mooney viscosity (ML _{1 + 4} ) of the conjugated diene polymer according to the present invention 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 vinyl bond content of the conjugated diene polymer according to the present invention is preferably 80 mol% or less, more preferably 70 mol%, in order to improve fuel efficiency, with the content of the conjugated diene unit being 100 mol%. It is as follows. Moreover, in order to improve grip property, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more, Most preferably, it is 40 mol% or more. The vinyl bond amount is determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

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

As a suitable production method of the conjugated diene polymer according to the present invention, a production method having the following steps A and B can be mentioned.
(Step A): Use of a compound represented by the above formula (I) as a monomer component containing a conjugated diene and a compound represented by the above formula (I) with an alkali metal catalyst in a hydrocarbon solvent. The amount is 0.01 to 20% by mass (provided that the total amount of monomer components used is 100% by mass), and is represented by the monomer unit based on the conjugated diene and the above formula (I). A step of obtaining a polymer having an alkali metal derived from an alkali metal catalyst at at least one end of a polymer chain having a monomer unit based on the compound.
(Step B): A step of reacting the polymer obtained in Step A with the compound represented by the above formula (II).

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

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

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

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

In Step A, polymerization may be carried out by combining a vinyl aromatic hydrocarbon with a conjugated diene and a compound represented by the formula (I) as a monomer. Examples of the vinyl aromatic hydrocarbon include styrene, α -Methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and the like can be mentioned. Styrene is preferable.

The amount of vinyl aromatic hydrocarbon used is 0% by mass or more (the amount of conjugated diene used is 100% by mass or less), where the total amount of conjugated diene and vinyl aromatic hydrocarbon is 100% by mass. In order to increase it, it is preferably 10% by mass or more (the amount of conjugated diene used is 90% by mass or less), more preferably 15% by mass or more (the amount of conjugated diene used is 85% by mass or less). In order to improve fuel efficiency, the amount of vinyl aromatic hydrocarbon used is preferably 50% by mass or less (the amount of conjugated diene used is 50% by mass or more), more preferably 45% by mass or less (conjugated). The amount of diene used is 55% by mass or more).

In the polymerization, the total amount of the conjugated diene, the compound represented by the formula (I), and the vinyl aromatic hydrocarbon is set to 100% by mass to increase the wear resistance. , Preferably it is 99.9 mass% or more, More preferably, it is 99.95 mass% or more, More preferably, it is 100 mass%.

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

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

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

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

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

R ³¹ _a ML _4-a (III)
(In the formula, R ³¹ 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 a number of 0 to 2. Represents.)

As the coupling agent represented by the formula (III), 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, per 1 mol of alkali metal derived from the alkali metal catalyst in order to improve the processability of the conjugated diene polymer. 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.

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

The conjugated diene polymer according to the present invention can be used as a conjugated diene polymer composition by blending other polymer components and additives.

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 preferable, and NR is more preferable because low fuel consumption, fracture strength, and processability are exhibited in a well-balanced manner. These rubber components are not particularly limited, and those generally used in the tire industry can be used.

The content of NR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 25% by mass or more, and further preferably 45% by mass or more. If the amount is less than 5% by mass, sufficient fuel economy tends not to be obtained. The NR content is preferably 90% by mass or less, more preferably 70% by mass or less. When it exceeds 90 mass%, workability tends to deteriorate.

The 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, use a product name Ultrasil VN3-G manufactured by Degussa, a product name VN3, AQ, ER, RS-150 manufactured by Tosoh Silica Co., Ltd., a product name Zeosil 1115MP, 1165MP manufactured by Rhodia Can do.

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 15 parts by mass or more, more preferably 25 parts by mass or more, in order to improve fuel efficiency. Moreover, in order to improve fracture strength and workability, Preferably it is 100 mass parts or less, More preferably, it is 50 mass parts or less.

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

Examples of the sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. The 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 20 parts by mass or more, and still more preferably 30 parts by mass or more, in order to increase the fracture resistance. Moreover, in order to improve low fuel consumption, More preferably, it is 45 mass parts or less, More preferably, it is 40 mass parts or less.

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

The mass ratio of the silica content and the carbon black content used as the reinforcing agent (silica content: carbon black content) is preferably 0.1: 1 to 10: 1. The mass ratio is more preferably 0.5: 1 to 2: 1 in order to enhance 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 balance between low fuel consumption, fracture resistance and processability.

The rubber composition of the present invention is used for a tire tread.

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, a rubber composition blended with various additives as necessary is extruded according to the shape of the base tread of the tire at an unvulcanized stage, and molded by a normal method on a tire molding machine, Bonding together with other tire members forms 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>
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 1.41 g of 4-vinylpyridine, 6.1 ml of tetrahydrofuran, and 4.0 ml of ethylene glycol diethyl ether are placed in the polymerization reactor. I put it in. Next, 18.26 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to initiate the polymerization reaction.

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

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

7. 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) in the polymer solution 0 g, pentaerythrityltetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D) 4.0 g was added, and then the polymer solution was added at room temperature for 24 hours. Evaporated and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer 1.

<Polymer Production Example 2>
A stainless polymerization reactor with an internal volume of 20 liters equipped with a stirrer was washed, dried and replaced with dry nitrogen. Next, 10.2 kg of industrial hexane (density 680 kg / m ³ ), 608 g of 1,3-butadiene, 4.18 g of 4-vinylpyridine, 6.1 ml of tetrahydrofuran, and 4.0 ml of ethylene glycol diethyl ether were placed in the polymerization reactor. I put it in. Next, 22.62 mmol of n-butyllithium was charged into the polymerization reactor as an n-hexane solution to start the polymerization reaction.

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

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

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

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

While the stirring speed was 130 rpm, the temperature in the polymerization reactor was 65 ° C., and 1,3-butadiene was continuously fed into the polymerization reactor, the copolymerization reaction with 1,3-butadiene was carried out for 3 hours. The amount of 1,3-butadiene supplied was 821 g.

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

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

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

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

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

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

The obtained polymers 1 to 4 were analyzed by the following method. 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.

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

(Molecular weight distribution (Mw / Mn))
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method under the following conditions (i) to (viii), and the molecular weight distribution (Mw / Mn) was determined.
(I) Apparatus: HLC-8220 manufactured by Tosoh Corporation
(Ii) Separation column: HM-H manufactured by Tosoh Corporation (two in series)
(Iii) Measurement temperature: 40 ° C
(Iv) Carrier: Tetrahydrofuran (v) Flow rate: 0.6 mL / min (vi) Injection volume: 5 μL
(Vii) Detector: differential refraction (viii) 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 to 4: Polymer carbon black obtained in Production Examples 1 to 4 above: Diablack N220 manufactured by Mitsubishi Chemical Corporation (N ₂ SA: 111 m ² / g, DBP absorption: 115 ml / 100 g)
Silica: Ultrasil VN3 manufactured by Degussa (N ₂ SA: 175 m ² / g)
Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa
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 .: Soxinol CZ 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.

The following evaluation was performed about the obtained unvulcanized rubber composition and vulcanized rubber composition. The results are shown in Table 2.

(Mooney viscosity)
According to JIS K6300: 1994, the Mooney viscosity of the unvulcanized rubber composition was measured at 100 ° C., and the reciprocal number was expressed as an index when Comparative Example 1 was set to 100. The larger the index, the smaller the Mooney viscosity and the better the workability.

(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 was performed by measuring the loss tangent (tan δ (70 ° C.)) of the test piece at a temperature of 70 ° C. under a condition of 1% strain and a frequency of 10 Hz using a viscoelasticity measuring apparatus (manufactured by Ueshima Seisakusho Co., Ltd.). Displayed as an index when Comparative Example 1 is taken as 100. A larger index is better (low fuel consumption).

(Destructive strength)
The vulcanized rubber composition was subjected to a tensile test using a No. 3 dumbbell according to JIS K6251, and the breaking strength (TB) was measured as the elongation at break EB (%). The numerical value of TB × EB / 2 was used as the fracture resistance, and the index was expressed as an index with the fracture resistance of Comparative Example 1 as 100. The larger the index, the better the fracture strength.

As shown in Table 2, the examples in which specific modified conjugated diene polymers (Polymers 1 and 2) and silica were blended had lower fuel consumption and higher fracture resistance than the rubber compositions of Comparative Examples. In addition, the processability improved synergistically, and these performances were obtained at a high level and in a well-balanced manner.

Claims (5)

Containing a rubber component and silica,
In 100% by mass of the rubber component, a compound represented by the following formula (II) is attached to one end of a conjugated diene polymer having a structural unit based on a conjugated diene and a structural unit based on the compound represented by the following formula (I). The content of the monomer units obtained by the reaction and based on the compound represented by the following formula (I) is 0.01 to 100% by weight based on the total amount of the monomer units in the conjugated diene polymer. The content of the conjugated diene polymer that is 20% by mass is 5% by mass or more,
A rubber composition for a base tread, wherein the silica content is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component.

(In the formula, R ¹¹ represents a hydrogen atom or a hydrocarbyl group, m is 0 or 1, R ¹² represents a hydrocarbylene group, and T represents a nitrogen-containing heterocyclic group.)

(In the formula, n represents a number of 1 to 10, R ²¹ , R ²² and R ²³ each represent a hydrocarbyl group or a hydrocarbyloxy group, and at least one of R ²¹ , R ²² and R ²³ is a hydrocarbyloxy group. R ²⁴ and R ²⁵ are each a hydrocarbyl group optionally having a hydrogen atom, a nitrogen atom and / or an oxygen atom, or R ²⁴ and R ²⁵ are bonded to form a nitrogen atom and / or (The hydrocarbylene group which may have an oxygen atom, or R ²⁴ and R ²⁵ are one group and represent a group bonded to a nitrogen atom with a double bond.) The rubber composition for base treads according to claim 1, wherein, in the formula (II), R ²¹ , R ²² and R ²³ are hydrocarbyloxy groups, and R ²⁴ and R ²⁵ are hydrocarbyl groups. The rubber composition for base treads according to claim 1, wherein R ^{11 in the} formula (I) is a hydrogen atom, and T is a pyridyl group. The vinyl bond content of the conjugated diene polymer is 20 mol% or more and 70 mol% or less, where the content of monomer units based on the conjugated diene is 100 mol%. Rubber composition for base tread. The pneumatic tire produced using the rubber composition in any one of Claims 1-4.