KR20200001996A - Method for producing modified conjugated diene polymer composition - Google Patents

Abstract

Provided is a method of preparing a modified conjugated diene-based polymer mixture which has excellent low hysteresis loss and has an excellent balance in wear resistance and processability when using the modified conjugated diene-based polymer mixture as a vulcanizate comprising a silica-based filler. The method comprises: continuously polymerizing a modified conjugated diene-based polymer (A) having a weight average molecular weight (Mw) of 70×10^4 to 300×10^4 measured by gel permeation chromatography (GPC) and a modified conjugated diene-based polymer (B) having a Mw of not less than 10×10^4 to less than 70×10^4 measured by GPC by using one or more reactors for each of the polymers; solution-mixing a polymer solution comprising the modified conjugated diene-based polymer (A) with a polymer solution comprising the modified conjugated diene-based polymer (B); and performing a process of removing a solvent from the mixture to obtain the modified conjugated diene-based polymer mixture (C), wherein the modified conjugated diene-based polymer mixture (C) has a molecular weight distribution (Mw/Mn) of 1.8 to 4.5.

Description

Method for producing a modified conjugated diene-based polymer mixture {METHOD FOR PRODUCING MODIFIED CONJUGATED DIENE POLYMER COMPOSITION}

The present invention relates to a process for preparing the modified conjugated diene-based polymer mixture.

In recent years, consideration for the environment has become a social request, and the demand for fuel economy saving is increasing for automobiles. At the same time, high safety is also required.

Specifically, from the viewpoint of fuel economy saving, a material for tires having a low resistance to the road surface is required when driving a vehicle, and particularly a material having a low rolling resistance, namely low hysteresis loss, in a tire tread directly contacting the road surface. There is a demand for materials having properties.

From the standpoint of high safety, a material that is excellent in wet skid resistance and has practically sufficient fracture characteristics is desired.

Conventionally, as a reinforcing filler used in a tire tread portion, carbon black has been used a lot, but in recent years, silica tends to be used a lot from the viewpoint of excellent low hysteresis loss and wet skid resistance.

By introducing a functional group having affinity with silica in the rubber molecule, it is thought that the mobility of the rubber molecule is suppressed and excellent low hysteresis loss and wet skid resistance are expressed. According to this idea, the technique of introducing the functional group which has affinity with a silica in a rubber molecule is proposed.

For example, in patent document 1, the modified diene type polymer obtained using the polymerization initiator which has an amino group is proposed. Moreover, in patent document 2, the rubber composition containing two types of modified conjugated diene type polymers different from each other is proposed.

Japanese Patent Publication No. 2015-131955 Japanese Patent Publication No. 2016-17097

However, in recent years, further improvement of low hysteresis loss property is calculated | required and the method of efficiently manufacturing the modified conjugated diene type polymer composition excellent in the balance of abrasion resistance and workability is calculated | required.

Accordingly, the present invention provides a method for efficiently producing a modified conjugated diene-based polymer mixture having excellent low hysteresis loss property and excellent balance of wear resistance and workability when used as a vulcanizate containing a silica-based inorganic filler. The purpose.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors mixed with the modified conjugated diene type polymer (A) and (B) from which a weight average molecular weight (Mw) differs, and it is made into the vulcanizate containing a silica type inorganic filler. In one case, a modified conjugated diene-based polymer mixture having excellent low hysteresis loss property and excellent balance of wear resistance and processability can be prepared, and two different types of modified conjugated diene-based polymers are mixed in a solution state after polymerization. By removing the solvent, it was found that a modified conjugated diene-based polymer mixture having excellent low hysteresis loss property when used as a vulcanized product and having excellent balance of wear resistance and workability can be efficiently produced in one finishing process. The present invention has been completed.

That is, this invention is as follows.

〔One〕

A modified conjugated diene polymer (A) having a weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of 70 × 10 ⁴ or more and 300 × 10 ⁴ or less,

The modified conjugated diene polymer (B) having a Mw of 10 × 10 ⁴ or more and less than 70 × 10 ⁴ measured by GPC is continuously polymerized using one or more reactors, respectively.

Solution-mixing the polymer solution containing the said modified conjugated diene type polymer (A), and the polymer solution containing the said modified conjugated diene type polymer (B),

Thereafter, the solvent is removed to obtain a modified conjugated diene polymer mixture (C).

Method of producing a modified conjugated diene-based polymer mixture,

The molecular weight distribution (Mw / Mn) of the said modified conjugated diene type polymer mixture (C) is 1.8 or more and 4.5 or less, The manufacturing method of the modified conjugated diene type polymer mixture.

〔2〕

The mixed mass ratio ((A) / (B)) of the modified conjugated diene-based polymer (A) and the modified conjugated diene-based polymer (B) in the modified conjugated diene-based polymer mixture (C) is 90/10 to The manufacturing method of the modified conjugated diene type polymer mixture as described in said [1] adjusted to 40/60.

[3]

The manufacturing method of the modified conjugated diene type polymer mixture as described in said [1] or [2] whose Mw of the said modified conjugated diene type polymer (A) is 100 * 10 <^4> or more and 300 * 10 <^4> or less.

〔4〕

The modification as described in any one of said [1] to [3] whose difference ((DELTA) Mw) of the weight average molecular weight of the said modified conjugated diene type polymer (A) and the said modified conjugated diene type polymer (B) is 50x10 <^4> or more. Process for the preparation of conjugated diene polymer mixtures.

[5]

The modified conjugated diene-based polymer mixture according to any one of the above [1] to [4], wherein the modification ratio of the modified conjugated diene-based polymer mixture (C) to the total amount of the conjugated diene-based polymer is adjusted to 50% by mass or more. Method of preparation.

[6]

Any one of said [1] to [5] whose shrinkage factor (g ') by 3D-GPC of the modified conjugated diene polymer (A) and / or the modified conjugated diene polymer (B) is 0.70 or more and 1.0 or less. The manufacturing method of the modified conjugated diene type polymer mixture of description.

[7]

Any one of said [1] to [5] whose shrinkage factor (g ') by 3D-GPC of the said modified conjugated diene type polymer (A) and / or the said modified conjugated diene type polymer (B) is 0.30 or more and less than 0.70. The manufacturing method of the modified conjugated diene type polymer mixture of description.

〔8〕

The said modified conjugated diene type polymer (A) and / or the said modified conjugated diene type polymer (B) has a functional group represented by following General formula (1) in the superposition | polymerization start terminal, in any one of said [1]-[7]. The manufacturing method of the modified conjugated diene type polymer mixture of one.

(In General Formula (1), R ¹ and R ² may be any one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Here, R <^1> and R <^2> may combine and form the cyclic structure with adjacent nitrogen atom, and in that case, R <^1> and R <^2> is a hydrocarbon group of 4-12 carbon atoms in total. R ¹ and R ² may have an unsaturated bond or may have a branched structure.)

[9]

The modified conjugated diene-based polymer (A) and / or the modified conjugated diene-based polymer (B) has a functional group represented by the general formula (1) at the end of polymerization, and is also represented by the general formula (1). The manufacturing method of the modified conjugated diene polymer mixture as described in said [8] which has a functional group containing an alkoxysilyl group and an amine in the terminal different from the said polymerization start terminal which has a functional group.

[10]

The modified conjugated diene-based polymer (B) has a modification ratio of 50% by mass or more with respect to the total amount of the conjugated diene-based polymer, and a peak having a minimum molecular weight when there are a plurality of peak tops in the molecular weight curve or the peak tops. The modification rate of the component of the molecular weight which is 1/2 of the molecular weight of a saw is 1/2 or more of the modification ratio with respect to the total amount of the said modified conjugated diene type polymer, and is content of nitrogen contained in the said modified conjugated diene type polymer (B) The manufacturing method of the modified conjugated diene type polymer mixture in any one of said [1]-[7] which is 3 mass ppm or more and 70 mass ppm or less.

According to the present invention, a modified conjugated diene capable of efficiently producing a modified conjugated diene-based polymer mixture having excellent low hysteresis loss and excellent balance of wear resistance and processability when used as a vulcanizate containing a silica filler. It is possible to provide a process for producing a system polymer mixture.

EMBODIMENT OF THE INVENTION Hereinafter, the concrete content (henceforth "this embodiment") for implementing this invention is demonstrated in detail.

In addition, the following this embodiment is an illustration for demonstrating this invention, This invention is not limited to the following embodiment, It can variously deform and implement within the range of the summary.

[Method for producing modified conjugated diene polymer mixture]

The manufacturing method of the modified conjugated diene polymer mixture of this embodiment,

A modified conjugated diene polymer (A) having a weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of 70 × 10 ⁴ or more and 300 × 10 ⁴ or less,

The modified conjugated diene polymer (B) having a Mw of 10 × 10 ⁴ or more and less than 70 × 10 ⁴ measured by GPC is continuously polymerized using one or more reactors, respectively.

Solution-mixing the polymer solution containing the said modified conjugated diene type polymer (A), and the polymer solution containing the said modified conjugated diene type polymer (B),

Thereafter, the solvent is removed to obtain a modified conjugated diene polymer mixture (C).

The molecular weight distribution (Mw / Mn) of the said modified conjugated diene type polymer mixture (C) shall be 1.8 or more and 4.5 or less.

(Modified conjugated diene polymer (A) and Modified conjugated diene polymer (B))

The modified conjugated diene polymer (A) has a weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of 70 × 10 ⁴ or more and 300 × 10 ⁴ or less, and the modified conjugated diene polymer (B) is measured by GPC. Mw to be made is 10x10 <^4> or more and 70x10 <^4> or less.

In the method for producing the modified conjugated diene-based polymer mixture of the present embodiment, the two kinds of modified conjugated diene-based polymers (A) and (B) are successively polymerized using one or more reactors, respectively to obtain a polymer solution. .

(Manufacturing method of modified conjugated diene polymer (A) and modified conjugated diene polymer (B))

<Polymerization process>

In the polymerization process of a modified conjugated diene polymer (A), (B), at least a conjugated diene compound is polymerized using an organolithium compound as a polymerization initiator, and a conjugated diene polymer is obtained.

As for the polymerization process, superposition | polymerization by the growth reaction by a living anion polymerization reaction is preferable, and by this, the conjugated diene type polymer which has an active terminal can be obtained, and there exists a tendency which can obtain the modified conjugated diene type polymer of high modification rate. .

In the polymerization step, at least the conjugated diene compound is polymerized, and if necessary, the conjugated diene compound and the aromatic vinyl compound are copolymerized to obtain a conjugated diene copolymer.

Although it will not specifically limit, if it is a monomer which can superpose | polymerize as a conjugated diene compound, The conjugated diene compound containing 4-12 carbon atoms per molecule is preferable, More preferably, the conjugated diene compound containing 4-8 carbon atoms to be.

Examples of such conjugated diene compounds include, but are not limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1, 3-pentadiene, 1,3-hexadiene, and 1,3-heptadiene are mentioned.

Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability. These may be used individually by 1 type and may use 2 or more types together.

Although it will not specifically limit, if it is a monomer copolymerizable with a conjugated diene compound as an aromatic vinyl compound, A monovinyl aromatic compound is preferable.

Examples of the monovinyl aromatic compound include, but are not limited to, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene. Among these, styrene is preferable from the viewpoint of industrial availability. These may be used individually by 1 type and may use 2 or more types together.

The conjugated diene polymer obtained in the polymerization step may be a random copolymer or a block copolymer.

In order to make a conjugated diene type polymer into a rubbery polymer, it is preferable to use 40 mass% or more of conjugated diene compounds with respect to the whole monomer of a conjugated diene type polymer, and it is more preferable to use 55 mass% or more.

Although it is not limited to the following as a random copolymer, For example, the random copolymer which consists of 2 or more types of conjugated diene compounds, such as butadiene-isoprene random copolymer, butadiene-styrene random copolymer, isoprene-styrene random copolymer, The random copolymer which consists of a conjugated diene compound and an aromatic vinyl compound of butadiene-isoprene-styrene random copolymer is mentioned.

The composition distribution of each monomer in the copolymer chain is not particularly limited, and examples thereof include a completely random copolymer close to a statistically random composition and a taper (gradient) random copolymer in which the composition is distributed in a tapered form. The bonding style of conjugated diene, that is, compositions such as 1,4-bonds and 1,2-bonds may be uniform or may be distributed.

As a block copolymer, although it is not limited to the following, For example, the 2 type block copolymer (diblock) which consists of two blocks, the 3 type block copolymer (triblock) which consists of three, and the 4 type block which consists of four And copolymers (tetra blocks). As a polymer which comprises one block, the polymer which consists of one type of monomer, or the copolymer which consists of 2 or more types of monomers may be sufficient. For example, the polymer block consisting of 1,3-butadiene is represented by "B", the copolymer of 1,3-butadiene and isoprene is represented by "B / I", and the copolymer of 1,3-butadiene and styrene is shown. When represented by "B / S" and the polymer block which consists of styrene is represented by "S", BB / I2 type block copolymer, BB / S2 type block copolymer, S-B2 type block copolymer, BB / S-S3 type Block copolymers, SB-S3 type block copolymers, SBS-B4 type block copolymers, and the like.

In the above formula, the boundary of each block does not necessarily need to be clearly distinguished. In addition, when one polymer block is a copolymer which consists of two types of monomers A and B, A and B in a block may be distributed uniformly or may be distributed in taper shape.

<Polymerization initiator>

An organolithium compound can be used as a polymerization initiator in a polymerization process.

Although not limited to the following as an organolithium compound, For example, the organolithium compound of a low molecular weight compound and a solubilized oligomer is mentioned.

Moreover, as an organolithium compound, the compound which has a carbon-lithium bond, the compound which has a nitrogen-lithium bond, and the compound which has a tin-lithium bond are mentioned, for example in the bond mode of the organic group and this lithium. .

It is preferable to determine the usage-amount of a polymerization initiator according to the molecular weight of the target conjugated diene type polymer or a modified conjugated diene type polymer. The amount of monomers such as conjugated diene compound to the amount of polymerization initiator used is related to the degree of polymerization. That is, there exists a tendency which relates to a number average molecular weight and / or a weight average molecular weight. Therefore, what is necessary is just to adjust in the direction which reduces a polymerization initiator in order to increase molecular weight, and to adjust in the direction which increases the amount of polymerization initiators in order to reduce molecular weight.

The organolithium compound as the polymerization initiator is preferably an alkyllithium compound from the viewpoint of industrial availability and ease of control of the polymerization reaction. In this case, the conjugated diene type polymer which has an alkyl group in the superposition | polymerization start terminal is obtained.

Examples of the alkyllithium compound include, but are not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, and stilbenlithium. . As the alkyllithium compound, n-butyllithium and sec-butyllithium are preferable from the viewpoint of industrial availability and ease of control of the polymerization reaction.

The compound having a nitrogen-lithium bond as a polymerization initiator (hereinafter sometimes referred to as a lithium amide compound) is preferably used in one method of introducing a nitrogen atom into the conjugated diene polymer, preferably a substituted amino group. It is an alkyl lithium compound or dialkyl amino lithium compound which has a.

In this case, the conjugated diene type polymer which has a nitrogen atom containing the amino group which has an amino group which has a functional group represented by following General formula (1), and a modified conjugated diene type polymer (A), (B) at the polymerization start terminal, Obtained.

By introducing a nitrogen atom into the conjugated diene polymer, there is a tendency for low hysteresis loss and wet skid resistance to be improved.

(In General Formula (1), R ¹ and R ² may be any one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Here, R <^1> and R <^2> may combine and form the cyclic structure with adjacent nitrogen atom, and in that case, R <^1> and R <^2> is a hydrocarbon group of 4-12 carbon atoms in total. R <^1> and R <^2> may have an unsaturated bond and may have a branched structure.).

The alkyllithium compound or dialkylaminolithium compound having the substituted amino group is, for example, a compound represented by the following General Formula (2).

(In said general formula (2), R <^1> and R <^2> is any selected from the group which consists of a C1-C12 alkyl group, a C3-C14 cycloalkyl group, and a C6-C20 aryl group, and may be same or different. Here, R <^1> and R <^2> may combine and form the cyclic structure with the adjacent nitrogen atom, and R <^1> and R <^2> in that case is a hydrocarbon group of 4-12 total carbons. ¹ and R ² may have an unsaturated bond or may have a branched structure.).

As a compound represented by said Formula (2), for example, 1-rithiopyrrolidine, 1-rithiopiperidine, 1-rithioacycloheptane, 1-rithioacyclooctane, 1-rithioaza Cycloundecane, lithium diethylamide, lithium dibutylamide, lithium dihexylamide, 6-rithio-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, lithium ethylbutylamide, lithium ethyl Hexylamide, lithium butylhexylamide, lithium methylphenylamide, lithium benzylmethylamide, 1-rithio-1,2,3,4-tetrahydropyridine and the like.

In addition, the compound represented by the said Formula (2) is not limited to these, If the said conditions are satisfied, these analogues are included.

From the viewpoint of reducing the hysteresis loss of the resin composition using the modified conjugated diene-based polymer mixture obtained by the present embodiment, as the compound represented by the formula (2), 1-rithiopyrrolidine, 1-rithiopiperidine, 1 -Rithioazacycloheptane, lithium dibutylamide, 6-rithio-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1-rithio-1,2,3,4-tetra Hydropyridine and the like are preferred.

More preferably, they are 1-rithiopyrrolidine, 1-rithiopiperidine, and 1-rithioaza cycloheptane, More preferably, they are 1-rithiopiperidine and 1-rithioazacycloheptane.

The said lithium amide compound can be synthesize | combined by a well-known method. For example, it is obtained by making secondary amine and an organolithium compound react in a hydrocarbon solvent.

Examples of the hydrocarbon solvent include, but are not limited to, hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specifically, Aliphatic hydrocarbons, such as butane, a pentane, hexane, heptane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; And hydrocarbons containing aromatic hydrocarbons such as benzene, toluene and xylene and mixtures thereof.

Although it is not limited to the following as said secondary amine, For example, the compound represented by following General formula (3) is mentioned.

In said Formula (3), R <^1> and R <^2> is any selected from the group which consists of a C1-C12 alkyl group, a C3-C14 cycloalkyl group, and a C6-C20 aryl group, and may be same or different. do. R ¹ and R ² may be bonded to each other to form a cyclic structure with an adjacent nitrogen atom, in which case R ¹ and R ² are hydrocarbon groups having 4 to 12 carbon atoms in total. R <^1> and R <^2> may have an unsaturated bond and may have a branched structure.

As a compound represented by said Formula (3), For example, pyrrolidine, a piperidine, azacycloheptane, azacyclooctane, azacyclo undecane, diethylamine, dibutylamine, dihexylamine, 1, 3,3-trimethyl-6-azabicyclo [3.2.1] octane, ethylbutylamine, ethylhexylamine, butylhexylamine, methylphenylamine, benzylmethylamine, 1,2,3,4-tetrahydropyridine and the like. Can be.

The compound represented by the said Formula (3) is not limited to these, If the said conditions are satisfied, these analogues are included.

From the viewpoint of reducing the hysteresis loss of the modified conjugated diene-based polymer mixture obtained by the present embodiment, as the compound represented by the formula (3), pyrrolidine, piperidine, azacycloheptane, dibutylamine, 1,3 Preference is given to, 3-trimethyl-6-azabicyclo [3.2.1] octane, 1,2,3,4-tetrahydropyridine. More preferably, they are pyrrolidine, piperidine, and azacycloheptane. More preferred are piperidine and azacycloheptane.

The organolithium compound which has these substituted amino groups can also be used as the organic monolithium compound of the oligomer which solubilized the monomer which can superpose | polymerize, for example, monomers, such as 1, 3- butadiene, isoprene, and styrene.

The organolithium compound is preferably an alkyllithium compound from the viewpoint of industrial availability and ease of control of the polymerization reaction. In this case, the conjugated diene type polymer which has an alkyl group in the superposition | polymerization start terminal is obtained.

Although it is not limited to the following as an alkyl lithium compound, For example, n-butyllithium, sec-butyllithium, tert- butyllithium, n-hexyl lithium, benzyl lithium, phenyl lithium, and stilben lithium are mentioned. have.

As said alkyllithium compound, n-butyllithium and sec-butyllithium are preferable from a viewpoint of the industrial availability and the control of a polymerization reaction.

These organolithium compounds may be used individually by 1 type, and may use 2 or more types together.

Moreover, you may use together with another organometallic compound. As this organometallic compound, an alkaline-earth metal compound, another alkali metal compound, other organometallic compound is mentioned, for example. Although it is not limited to the following as an alkaline earth metal compound, For example, an organic magnesium compound, an organic calcium compound, and an organic strontium compound are mentioned. Furthermore, the compound of the alkoxide, sulfonate, carbonate, and amide of an alkaline earth metal is also mentioned. As an organic magnesium compound, dibutyl magnesium and ethyl butyl magnesium are mentioned, for example. As another organometallic compound, an organoaluminum compound is mentioned, for example.

As a polymerization reaction mode in a polymerization process, it is preferable to carry out by a continuous polymerization reaction mode.

In the continuous mode, the polymerization can be carried out using one or two or more connected reactors.

As the continuous reactor, for example, a tubular or tubular one with a stirrer is used. In the continuous mode, preferably, the monomer, the inert solvent, and the polymerization initiator are continuously fed to the reactor to obtain a polymer solution containing the polymer in the reactor, and the polymer solution is continuously discharged.

It is preferable to superpose | polymerize a superposition | polymerization process in an inert solvent. As an inert solvent, hydrocarbon type solvents, such as a saturated hydrocarbon and an aromatic hydrocarbon, are mentioned, for example. Examples of the specific hydrocarbon solvent include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane and heptane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; And hydrocarbons including aromatic hydrocarbons such as benzene, toluene and xylene and mixtures thereof.

Before providing to the polymerization reaction, by treating the allenes and acetylenes as impurities with an organometallic compound, a conjugated diene polymer having a high concentration of active terminal tends to be obtained, and a modified conjugated diene polymer having a high modification rate (A And (B) are preferred because they tend to be obtained.

In a polymerization process, you may add a polar compound. By adding a polar compound, an aromatic vinyl compound can be randomly copolymerized with a conjugated diene compound, and it tends to be used also as a vinylating agent for controlling the microstructure of a conjugated diene part. Moreover, there exists a tendency which is effective also in acceleration of a polymerization reaction.

Examples of the polar compound include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, Ethers such as dimethoxybenzene and 2,2-bis (2-oxolanyl) propane; Tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine and quinuclidin; Alkali metal alkoxide compounds such as potassium-tert-amylate, potassium-tert-butyrate, sodium-tert-butyrate, and sodium amylate; Phosphine compounds, such as a triphenyl phosphine, etc. are mentioned.

These polar compounds may be used individually by 1 type, and may use 2 or more types together.

Although the usage-amount of a polar compound is not specifically limited and can be selected according to the objective etc., It is preferable that they are 0.01 mol or more and 100 mol or less with respect to 1 mol of polymerization initiators. Such a polar compound (vinylating agent) can be suitably used as a regulator of the microstructure of the conjugated diene part of the polymer obtained according to a desired amount of vinyl bonds.

Many polar compounds have an effective randomization effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and tend to be used as an agent for adjusting the distribution of the aromatic vinyl compound and the amount of styrene blocks.

As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, for example, the copolymerization reaction is initiated with the entire amount of styrene and a part of 1,3-butadiene, as described in JP-A-59-140211. You may use the method of intermittently adding the remaining 1,3-butadiene in the middle of a copolymerization reaction.

The modified conjugated diene-based polymer (B) constituting the modified conjugated diene-based polymer mixture obtained in the present embodiment has a molecular weight of a peak top having a minimum molecular weight when there are a plurality of peak tops in the GPC curve or the peak tops. It is preferable that the modification rate of the component of the molecular weight which is 1/2 of ie, low molecular weight component is 1/2 or more of the modification rate with respect to the total amount of a conjugated diene type polymer.

It is considered that the low molecular weight component contributes to the processability of the polymer in the polymer as a whole. The modified conjugated diene polymer (B) has a lower molecular weight than the modified conjugated diene polymer (A), and the modified conjugated diene polymer When the modification rate of the low molecular weight component of (B) is in the said range, it exists in the tendency for the workability at the time of making it vulcanized.

In order to obtain such a modified conjugated diene polymer, it is effective to obtain a conjugated diene polymer by a polymerization method in which the growth reaction is stopped or the chain transfer is very small.

Therefore, the ultra high purity of the monomer and solvent which are introduce | transduced into a polymerization reactor require the level more than before.

Therefore, it is preferable that the total amount of impurities is 30 ppm or less in the monomer component to be used, It is preferable that content concentrations (mass) of impurities, such as allenes, acetylene, primary, and secondary amine, are 20 ppm or less, and, as for 10 ppm or less, As for acetylene, it is more preferable that it is 20 ppm or less, It is more preferable that it is 10 ppm or less, It is preferable that primary and secondary amines are 4 ppm or less as a total nitrogen content, It is more preferable that it is 2 ppm or less.

Examples of the allenes include, but are not limited to, propadiene and 1,2-butadiene. Examples of the acetylenes include, but are not limited to, ethyl acetylene and vinyl acetylene. Although it is not limited to the following as a primary and secondary amine, For example, methylamine and dimethylamine are mentioned.

Thus, by performing ultra high purity of a monomer and a solvent, also in the modified conjugated diene type polymer with a comparatively low nitrogen content of 3 mass ppm or more and 70 mass ppm or less, the modification rate of a low molecular weight component is made into the conjugated diene type polymer as mentioned later. The denaturation rate with respect to the total amount of can be made 1/2 or more.

Ultra-high purity of a monomer and a solvent can be achieved by fully refine | purifying both the monomer and solvent used for superposition | polymerization.

In the purification of butadiene as a monomer, it is important not only to remove the polymerization inhibitor, but also to remove dimethylamine, N-methyl-γ-aminobutyric acid and the like which may adversely affect anionic polymerization. As a method of removing these, for example, 1,3-butadiene containing a polymerization inhibitor is washed with low oxygen water having an oxygen concentration of less than 2 mg / L as washing water, and then in 1,3-butadiene The method of removing a polymerization inhibitor is mentioned.

In the purification of styrene which is a monomer, it is important to remove phenyl acetylene etc. which may adversely affect anionic polymerization. As a method of removing phenylacetylenes, the method of performing a hydrogenation reaction using a palladium carrying alumina catalyst is mentioned, for example.

In the purification of normal hexane which is a polymerization solvent, it is important to remove water which may adversely affect anionic polymerization. As a method of removing this, the method of using (gamma) -alumina, synthetic zeolite, etc. is mentioned, for example. Among these, the method of using a synthetic zeolite is preferable, It is preferable that a pore diameter is large as a synthetic zeolite, It is more preferable that a pore diameter is 0.35 nm or more, It is still more preferable that it is 0.42 nm or more.

As a polymerization method with very few stops or chain transfers of the growth reaction, a method of controlling the polymerization temperature and controlling the monomer conversion rate is effective.

The lower the polymerization temperature is preferable from the viewpoint of stopping the growth reaction or the chain movement, but from the viewpoint of productivity, the polymerization temperature is preferably a temperature at which the living anion polymerization sufficiently proceeds, and specifically, it is preferably 0 ° C. or more. It is preferable that it is 80 degrees C or less. More preferably, they are 50 degreeC or more and 75 degrees C or less. Moreover, it is preferable to make the conversion rate of the whole monomer react with a modifier at less than 99 mass%. By adding a denaturant in the stage where the monomer remains in the polymerizer and reacting the polymer chain with the denaturant during growth while the monomer is not consumed, a polymer having no terminal end modified or producing other side reactions occurs. It can be suppressed. More preferably, the conversion rate is less than 98 mass%.

Conjugated diene polymer or modified conjugated diene polymer (A) and (B) obtained in the polymerization step of the modified conjugated diene polymer (A) and (B) constituting the modified conjugated diene polymer mixture obtained by the present embodiment. Although the amount of conjugated diene in particular is not specifically limited, It is preferable that they are 40 mass% or more and 100 mass% or less, and it is more preferable that they are 55 mass% or more and 80 mass% or less. The amount of the bonded aromatic vinyl in the conjugated diene polymer or the modified conjugated diene polymer (A) and (B) is not particularly limited, but is preferably 0% by mass to 60% by mass, and is preferably 20% by mass to 45% by mass. It is more preferable that it is% or less.

If the amount of conjugated diene and the amount of aromatic aromatic vinyl are within the above ranges, there is a tendency that the balance between low hysteresis loss and wet skid resistance, abrasion resistance, and fracture characteristics when used as a vulcanized product are more excellent. Here, the amount of bound aromatic vinyl can be measured by ultraviolet absorption of a phenyl group, and the amount of bound conjugated diene can also be obtained from this. Specifically, it can measure according to the method as described in the Example mentioned later.

In the conjugated diene polymer or the modified conjugated diene polymer, the amount of vinyl bonds in the conjugated diene bonding unit is not particularly limited, but is preferably 10 mol% or more and 75 mol% or less, and preferably 20 mol% or more and 65 mol% or less. More preferred. If the amount of vinyl bonds is within the above range, there is a tendency that the balance between low hysteresis loss and wet skid resistance, wear resistance, and breaking strength when the vulcanizate is more excellent. Here, in the case where the modified diene polymer is a copolymer of butadiene and styrene, the amount of vinyl bonds in the butadiene bonding unit (1,2-bonding) by Hampton's method (RRHampton, Analytical Chemistry, 21, 923 (1949)) Quantity) can be obtained. Specifically, it can measure by the method as described in the Example mentioned later.

Regarding the microstructures of the modified conjugated diene-based polymers (A) and (B), the amount of each bond in the modified conjugated diene-based polymers (A) and (B) is in the above range, and the modified conjugated diene-based polymer (A) and When the glass transition temperature of (B) exists in the range of -45 degreeC or more and -15 degrees C or less, there exists a tendency which can obtain the vulcanized material which is more excellent in the balance of low hysteresis loss | weakness and wet skid resistance. For the glass transition temperature, the DSC curve is recorded while the temperature is raised in a predetermined temperature range according to ISO 22768: 2006, and the peak top of the DSC differential curve is referred to as the glass transition temperature.

When the modified conjugated diene-based polymers (A) and (B) are conjugated diene-aromatic vinyl copolymers, it is preferable that the number of blocks in which the aromatic vinyl units are chained by 30 or more is small or absent. More specifically, when the copolymer is a butadiene-styrene copolymer, the copolymer is decomposed by Kolthoff's method (IMKOLTHOFF, et al., J. Polym. Sci. 1,429 (1946)) and dissolved in methanol. In the well-known method of analyzing the amount of insoluble polystyrene, the block in which the aromatic vinyl unit chains 30 or more is preferably 5.0 mass% or less, more preferably 3.0 mass% or less with respect to the total amount of the copolymer.

When the conjugated diene polymer before the modification of the modified conjugated diene polymer (A) and (B) is a conjugated diene-aromatic vinyl copolymer, it is preferable that a large proportion of aromatic vinyl units exist alone. Specifically, in the case where the copolymer is a butadiene-styrene copolymer, the copolymer is decomposed by ozone decomposition known as Tanaka et al. (Polymer, 22, 1721 (1981)), and styrene chains by GPC. When analyzing distribution, it is preferable that the amount of isolated styrene is 40 mass% or more with respect to the total amount of bound styrene, and the chain styrene structure whose chain | strand of styrene is 8 or more is 5.0 mass% or less. In this case, the vulcanized rubber obtained has excellent performance, which is particularly low hysteresis loss.

The modified conjugated diene-based polymer (A) constituting the modified conjugated diene-based polymer mixture obtained by the method for producing the modified conjugated diene-based polymer mixture of the present embodiment has a Mw of 70 × 10 ⁴ or more and 300 × 10 ⁴ or less as measured by GPC. In the modified conjugated diene polymer (B), Mw is 10 × 10 ⁴ or more and less than 70 × 10 ⁴ .

Thus, as a method of controlling each Mw in continuous superposition | polymerization, the method of adjusting the polymerization temperature, monomer addition amount, and polymerization initiator addition amount in each polymerization process, etc. are mentioned.

<Modification Process>

After the above-described polymerization step, a modified step is performed on the conjugated diene polymer to obtain modified conjugated diene polymers (A) and (B).

In the modification step, a predetermined die having a conjugated diene polymer obtained by the method described above, a linking group reacting with the active terminal of the conjugated diene polymer, and a predetermined functional group having affinity or bond reactivity to the filler. React the denaturant.

Moreover, it is preferable to perform a modification process immediately after a superposition | polymerization process. In that case, there exists a tendency for the modified conjugated diene type polymer with high modification rate to be obtained.

As a modifier, when a compound having a bonding group is monofunctional or bifunctional is used, a linear terminal modified diene polymer is obtained, and when a polyfunctional compound having a bonding group is at least trifunctional, a branched modified diene polymer is obtained. .

As a modifier, Preferably, the monofunctional or polyfunctional compound containing at least 1 sort (s) of element among nitrogen, silicon, tin, phosphorus, oxygen, sulfur, and halogen is used. In addition, an onium structure can be introduced into the modified conjugated diene-based polymer by adding and reacting a terminal denaturant including an onium generator. Moreover, the denaturant containing two or more functional groups containing these elements in a molecule | numerator, or the denaturant containing the functional group containing two or more of these elements can also be used.

As a modifier, it is preferable to have a functional group with few or no active hydrogens, such as a hydroxyl group, a carboxyl group, a primary and a secondary amino group. Active hydrogen tends to deactivate the active end of the conjugated diene polymer.

[Denaturant]

The denaturant will be specifically described below.

Examples of the nitrogen-containing compound include, but are not limited to, isocyanate compounds, isothiocyanate compounds, isocyanuric acid derivatives, nitrogen group-containing carbonyl compounds, nitrogen group-containing vinyl compounds, nitrogen group-containing epoxy compounds, and the like. Can be mentioned.

Examples of the silicon-containing compound include, but are not limited to, a silicon halide compound, an epoxidized silicon compound, a vinylated silicon compound, an alkoxy silicon compound, and an alkoxy silicon compound containing a nitrogen-containing group.

As a tin containing compound, although it is not limited to the following, For example, a halogenated tin compound, an organic tin carboxylate compound, etc. are mentioned.

As a phosphorus containing compound, although it is not limited to the following, For example, a phosphite ester compound, a phosphino compound, etc. are mentioned.

Examples of the oxygen-containing compound include, but are not limited to, epoxy compounds, ether compounds, ester compounds, and the like.

Examples of the sulfur-containing compound include, but are not limited to, mercapto group derivatives, thiocarbonyl compounds, isothiocyanates, and the like.

As a halogen containing compound, although it is not limited to the following, the said silicon halide compound, a halogenated tin compound, etc. are mentioned.

In addition, the onium generating agent is not limited to the following, but for example, a protected amine compound capable of forming a primary or secondary amine (produces ammonium) and a hydrophosphine can be formed. Protected phosphine compounds (which produce phosphonium), hydroxyl groups, and compounds capable of forming thiols (which produce oxonium and sulfonium); and the like. It is preferable to use the terminal denaturing agent which has a functional group for each in a molecule | numerator. As a functional group for couple | bonding the said modified conjugated diene type polymer, carbonyl group (ketone, ester, etc.), unsaturated groups, such as a vinyl group, an epoxy group, a silicon halide group, an alkoxy silicon group, etc. are mentioned.

The denaturant is preferably one having a nitrogen-containing functional group, and the nitrogen-containing functional group is preferably an amine compound having no active hydrogen, and for example, a tertiary amine compound and a protection in which the active hydrogen is substituted with a protecting group. A amine compound and the imine compound represented by general formula -N = C are mentioned.

Examples of the isocyanate compound of the nitrogen-containing compound which is a modifier include, but are not limited to, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, and diphenylmethane of a polymeric type. Diisocyanate (C-MDI), phenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, butyl isocyanate, 1,3,5-benzenetriisocyanate, etc. are mentioned.

Examples of the isocyanuric acid derivative include, but are not limited to, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, 1,3,5-tris (3-tri Ethoxysilylpropyl) isocyanurate, 1,3,5-tri (oxirane-2-yl) -1,3,5-triazinane-2,4,6-trione, 1,3,5- Tris (isocyanatomethyl) -1,3,5-triazinane-2,4,6-trione, 1,3,5-trivinyl-1,3,5-triazinane-2,4,6- Trion etc. are mentioned.

Examples of the nitrogen group-containing carbonyl compound include, but are not limited to, 1,3-dimethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, and 1-methyl. -3- (2-methoxyethyl) -2-imidazolidinone, N-methyl-2-pyrrolidone, N-methyl-2-piperidone, N-methyl-2-quinolone, 4,4'- Bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone, methyl-2-pyridylketone, methyl-4-pyridylketone, propyl-2-pyridylketone, di-4- Pyridylketone, 2-benzoylpyridine, N, N, N ', N'-tetramethylurea, N, N-dimethyl-N', N'-diphenylurea, N, N-diethylcarbamate methyl, N , N-diethylacetamide, N, N-dimethyl-N ', N'-dimethylaminoacetamide, N, N-dimethylpicolinic acid amide, N, N-dimethylisonicotinic acid amide, and the like.

Examples of the nitrogen group-containing vinyl compound include, but are not limited to, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylmaleimide, N-methylphthalimide, N, N-bistrimethylsilylacrylamide, morpholinoacrylamide, 3- (2-dimethylaminoethyl) styrene, (dimethylamino) dimethyl-4-vinylphenylsilane, 4,4'-vinylidenebis (N, N- Dimethylaniline), 4,4'-vinylidenebis (N, N-diethylaniline), 1,1-bis (4-morpholinophenyl) ethylene, 1-phenyl-1- (4-N, N- Dimethyl aminophenyl) ethylene etc. are mentioned.

As a nitrogen group containing epoxy compound, although it is not limited to the following, For example, the epoxy group containing hydrocarbon compound couple | bonded with the amino group is mentioned, You may have an epoxy group couple | bonded with the ether group. For example, the compound represented by General formula (4) is mentioned.

In said formula (4), R is nitrogen, such as a bivalent or more hydrocarbon group or polar groups which have oxygen, such as ether, epoxy, and ketone, polar groups which have sulfur, such as thioether, and thioketone, tertiary amino group, and imino group. It is a divalent or more organic group which has at least 1 sort (s) of polar group chosen from the polar group which has.

The divalent or higher hydrocarbon group is a saturated or unsaturated linear, branched or cyclic hydrocarbon group, and includes an alkylene group, an alkenylene group, a phenylene group and the like. Preferably, it is a hydrocarbon group of 1-20 carbon atoms. For example, methylene, ethylene, butylene, cyclohexylene, 1,3-bis (methylene) -cyclohexane, 1,3-bis (ethylene) -cyclohexane, o-, m-, p-phenylene, m-, p-xylene, bis (phenylene) -methane, etc. are mentioned.

In said formula (4), R <^1> , R <^4> is a C1-C10 hydrocarbon group, R <^1> , R <^4> may mutually be same or different.

R <^2> , R <^5> is hydrogen or a C1-C10 hydrocarbon group, R <^2> , R <^5> may mutually be same or different.

R <^3> is a C1-C10 hydrocarbon group or the structure of following formula (5).

R ¹ , R ² and R ³ may have a cyclic structure bonded to each other.

Moreover, when R <^3> is a hydrocarbon group, the cyclic structure couple | bonded with R may be sufficient. In the case of the said cyclic structure, the form which N and R couple | bonded with R <^3> directly bond may be sufficient.

In said formula (4), n is an integer of 1 or more, and m is 0 or an integer of 1 or more.

In said Formula (5), R <^1> , R <^2> is defined like R <^1> , R <^2> of said Formula (4), and R <^1> , R <^2> may mutually be same or different.

As a nitrogen group containing epoxy compound used as a modifier, what has an epoxy group containing hydrocarbon group is preferable, More preferably, it has a glycidyl group containing hydrocarbon group.

As an epoxy-group containing hydrocarbon group couple | bonded with an amino group or an ether group, glycidyl amino group, diglycidyl amino group, or glycidoxy group is mentioned, for example. Further preferred molecular structures are epoxy group-containing compounds each having a glycidylamino group or a diglycidylamino group and a glycidoxy group, and the compounds represented by the following general formula (6) may be mentioned.

In said Formula (6), R is defined similarly to R of said Formula (4), and R <^6> is a C1-C10 hydrocarbon group or the structure of following formula (7).

When R <^6> is a hydrocarbon group, it may combine with R and may have a cyclic structure, and in that case, the form which N and R couple | bonded with R <^6> directly bond may be sufficient.

In formula (6), n is an integer of 1 or more, and m is 0 or an integer of 1 or more.

As a nitrogen group containing epoxy compound used as a modifier, the compound which has one or more diglycidyl amino group and one or more glycidoxy group in a molecule | numerator is more preferable.

As a nitrogen-group containing epoxy compound used as a modifier, it is not limited to the following, For example, N, N- diglycidyl-4- glycidoxy cyanine, 1-N, N- diglycidylamino Methyl-4-glycidoxy-cyclohexane, 4- (4-glycidoxyphenyl)-(N, N-diglycidyl) aniline, 4- (4-glycidoxyphenoxy)-(N, N -Diglycidyl) aniline, 4- (4-glycidoxybenzyl)-(N, N-diglycidyl) aniline, 4- (N, N'-diglycidyl-2-piperazinyl) -Glycidoxybenzene, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 4,4- Methylene-bis (N, N-diglycidylaniline), 1,4-bis (N, N-diglycidylamino) cyclohexane, N, N, N ', N'-tetraglycidyl-p -Phenylenediamine, 4,4'-bis (diglycidylamino) benzophenone, 4- (4-glycidylpiperazinyl)-(N, N-diglycidyl) aniline, 2- [2- (N, N-diglycidylamino) ethyl] -1-glycidylpyrrolidine, N, N-diglycidyl Nilin, 4,4'- diglycidyl-dibenzylmethylamine, N, N- diglycidylaniline, N, N- diglycidyl ortho toluidine, N, N- diglycidylaminomethylcyclohexane Etc. can be mentioned. Among these, N, N- diglycidyl-4-glycidoxycyanine and 1,3-bis (N, N- diglycidylaminomethyl) cyclohexane are particularly preferable.

Examples of the halogenated silicon compound that is a modifier include, but are not limited to, dibutyl dichlorosilane, methyltrichlorosilane, dimethyldichlorosilane, methyldichlorosilane, trimethylchlorosilane, tetrachlorosilane, and tris (trimethylsiloxy). Chlorosilane, tris (dimethylamino) chlorosilane, hexachlorodisilane, bis (trichlorosilyl) methane, 1,2-bis (trichlorosilyl) ethane, 1,2-bis (methyldichlorosilyl) ethane, 1, 4-bis (trichlorosilyl) butane, 1, 4-bis (methyldichlorosilyl) butane, etc. are mentioned.

Although it is not limited to the following as an epoxidation silicon compound which is a modifier, For example, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane, 3-glycidoxy propylmethyl diethoxy Silane, epoxy modified silicone, and the like.

Examples of the alkoxysilicon compound as the modifier include, but are not limited to, tetramethoxysilane, tetraethoxysilane, triphenoxymethylsilane, methoxy substituted polyorganosiloxane, and the like.

As an alkoxy silicon compound containing the nitrogen containing group which is a modifier, although it is not limited to the following, For example, 3-dimethylaminopropyl trimethoxysilane, 3-dimethylaminopropylmethyldimethoxysilane, 3-diethylaminopropyl tri Ethoxysilane, 3-morpholinopropyltrimethoxysilane, 3-piperidinopropyltriethoxysilane, 3-hexamethyleneiminopropylmethyldiethoxysilane, 3- (4-methyl-1-piperazino ) Propyltriethoxysilane, 1- [3- (triethoxysilyl) -propyl] -3-methylhexahydropyrimidine, 3- (4-trimethylsilyl-1-piperazino) propyltriethoxysilane, 3- (3-triethylsilyl-1-imidazolidinyl) propylmethyldiethoxysilane, 3- (3-trimethylsilyl-1-hexahydropyrimidinyl) propyltrimethoxysilane, 3-dimethylamino-2 -(Dimethylaminomethyl) propyltrimethoxysilane, bis (3-dimethoxymethylsilylpropyl) -N-methylamine, bis (3-tri Methoxysilylpropyl) -N-methylamine, bis (3-triethoxysilylpropyl) methylamine, tris (trimethoxysilyl) amine, tris (3-trimethoxysilylpropyl) amine, N, N, N ', N'-tetra (3-trimethoxysilylpropyl) ethylenediamine, 3-isocyanatopropyltrimethoxysilane, 3-cyanopropyltrimethoxysilane, 2,2-dimethoxy-1- (3 -Trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2 -Dimethoxy-1- (4-trimethoxysilylbutyl) -1-aza-2-silacyclohexane, 2,2-dimethoxy-1- (3-dimethoxymethylsilylpropyl) -1-aza-2 -Silacyclopentane, 2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-butyl-1-aza-2-silacyclopentane, 2,2 -Dimethoxy-1-methyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-8- (4-methylpiperazinyl) methyl-1,6-dioxa-2-silacyclooctane, 2,2-dimethoxy-8- (N, N -Diethylamino) methyl-1,6-dioxa-2-silacyclooctane etc. are mentioned.

As a protected amine compound which can form the primary or secondary amine which is a modifier, As a compound which has an unsaturated bond and a protected amine in a molecule | numerator, although it is not limited to the following, For example, 4,4'-vinyl Lidenebis [N, N-bis (trimethylsilyl) aniline], 4,4'-vinylidenebis [N, N-bis (triethylsilyl) aniline], 4,4'-vinylidenebis [N, N- Bis (t-butyldimethylsilyl) aniline], 4,4'-vinylidenebis [N-methyl-N- (trimethylsilyl) aniline], 4,4'-vinylidenebis [N-ethyl-N- (trimethyl Silyl) aniline], 4,4'-vinylidenebis [N-methyl-N- (triethylsilyl) aniline], 4,4'-vinylidenebis [N-ethyl-N- (triethylsilyl) aniline] , 4,4'-vinylidenebis [N-methyl-N- (t-butyldimethylsilyl) aniline], 4,4'-vinylidenebis [N-ethyl-N- (t-butyldimethylsilyl) aniline] , 1- [4-N, N-bis (trimethylsilyl) aminophenyl] -1- [4-N-methyl-N- (trimethylsilyl) aminophenyl] ethylene, 1- [4-N, N-bis ( Trimethylsil ) Amino-phenyl] -1- [4-N, N- dimethylaminophenyl] it is ethylene and the like.

As a compound which has an alkoxysilane and a protected amine in a molecule | numerator as a protected amine compound which can form a primary or secondary amine which is a modifier, Although it is not limited to the following, For example, N, N-bis ( Trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl ) Aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, N, N-bis (triethylsilyl) Aminopropylmethyldiethoxysilane, 3- (4-trimethylsilyl-1-piperazino) propyltriethoxysilane, 3- (3-triethylsilyl-1-imidazolidinyl) propylmethyldiethoxysilane, 3 -(3-trimethylsilyl-1-hexahydropyrimidinyl) propyltrimethoxysilane, 2,2-dimethok -1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclo Pentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) -1-aza-2-silacyclohexane, 2,2-dimethoxy-1- (3-dimethoxymethylsilylpropyl)- 1-aza-2-silacyclopentane, 2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-butyl-1-aza-2-silacyclo Pentane, 2,2-dimethoxy-1-methyl-1-aza-2-silacyclopentane, and the like.

Examples of the halogenated tin compound as the modifier include, but are not limited to, tetrachlorotin, tetrabromine tin, trichlorobutyltin, trichlorooctyltin, dibromdimethyltin, dichlorodibutyltin, chlorotributyltin and chlorotrioctyl Tin, chlorotriphenyltin, 1,2-bis (trichlorostannyl) ethane, 1,2-bis (methyldichlorostannyl) ethane, 1,4-bis (trichlorostannyl) butane, 1,4- Bis (methyldichlorostannyl) butane etc. are mentioned.

Examples of the organic tin carboxylate compound which is a modifier include, but are not limited to, ethyl tin tristearate, butyl tin trioctanoate, butyl tin tristearate, butyl tin trilaurate, and dibutyl tin bis. Octanoate etc. are mentioned.

Although it does not restrict | limit to the following as a phosphite ester compound which is a modifier, For example, trimethyl phosphite, a tributyl phosphite, a phosphite triphenoxide, etc. are mentioned.

Examples of the phosphino compound that is a modifier include, but are not limited to, P, P-bis (trimethylsilyl) phosphinopropyltrimethoxysilane and P, P-bis (triethylsilyl) phosphinopropylmethyl. Protected phosphino compounds such as oxysilane, 3-dimethylphosphinopropyltrimethoxysilane, 3-diphenylphosphinopropyltrimethoxysilane, and the like.

Examples of the oxygen-containing compound which is a modifier include, but are not limited to, polyglycidyl ethers such as ethylene glycol diglycidyl ether and glycerin triglycidyl ether, 1,4-diglycidyl benzene, and the like. Esters such as polyepoxy compounds such as 3,5-triglycidylbenzene, polyepoxidized liquid polybutadiene, epoxidized soybean oil and epoxidized linseed oil, dimethyl adipic acid, diethyl adipic acid, dimethyl terephthalate and diethyl terephthalate Compounds are mentioned, and these produce hydroxyl groups at the polymer ends.

Although it does not restrict | limit as a sulfur containing compound which is a modifier, For example, Protective thiol compounds, such as S-trimethylsilylthiopropyl trimethoxysilane and S-triethylsilylthiopropylmethyldiethylsilane, S-methyl Thiopropyltrimethoxysilane, S-ethylthiopropylmethyldiethoxysilane, ethyl N, N-diethyldithiocarbamate, phenylisothiocyanate, phenyl-1,4-diisothiocyanate, hexamethylene di Isothiocyanate, butyl isothiocyanate, etc. are mentioned.

The modifier is preferably a compound having a silicon-containing functional group, and the silicon-containing functional group preferably has an alkoxysilyl group or silanol group.

The alkoxysilyl group of the modifier, for example, tends to react with the active terminal of the conjugated diene-based polymer to dissociate the alkoxylithium to form a bond between the terminal of the conjugated diene-based polymer chain and the silicon of the modifier residue. The value which subtracted the number of SiOR reduced by reaction from the total number of SiORs which a denaturant 1 molecule has becomes the number of the alkoxysilyl groups which a modifier residue has. In addition, the azasilacycle group of the modifier forms a bond between the> N-Li bond and the conjugated diene polymer terminal and the silicon of the modifier residue. In addition, the> N-Li bond tends to be> NH and LiOH easily by water or the like at the time of finishing. Moreover, in a modifier, the alkoxysilyl group which remained unreacted tends to become a silanol (Si-OH group) easily by the water etc. at the time of finishing.

In the modification step, when using a modifier having three alkoxy groups for one silicon atom, i.e., reacting 3 moles of the active terminal of the conjugated diene-based polymer with respect to 1 mole of the trialkoxysilane group, up to 2 moles of Although reaction with a conjugated diene type polymer occurs, 1 mol of alkoxy groups tend to remain unreacted. This can be confirmed from the fact that 1 mol of the conjugated diene polymer remains as an unreacted polymer without reacting. Moreover, when alkoxy groups are reacted a lot, there exists a tendency which can suppress that a polymer viscosity largely changes at the time of finishing, resulting in a condensation reaction at the time of storage. Preferably, it is preferable to use a modifier having one alkoxysilyl group per one silicon atom.

The modified conjugated diene-based polymer (A) and / or (B) obtained by the modification step described above has a functional group represented by the general formula (1) at the end of polymerization, and is a functional group represented by the general formula (1). It is preferable to have a functional group which has an alkoxysilyl group and an amine at the terminal different from the superposition | polymerization start terminal which has Thereby, the effect of the balance improvement of low hysteresis loss and wet skid resistance is acquired.

Such modified conjugated diene-based polymers (A) and (B) are obtained by appropriately selecting a polymerization initiator and a modifying agent.

Specifically, the aminolithium polymerization initiator randomly polymerizes styrene and butadiene, and adds and reacts a modifier having a functional group having an alkoxysilyl group and an amine therein, thereby having an amino group and a silyl group and an amine at the end of the polymerization. A polymer having a functional group is obtained.

By having a functional group at both ends of a polymer, the affinity and / or reactivity of the both ends of a silica and a polymer mix | blended with the resin composition for tires can be improved, and a dispersibility of a silica can be anticipated.

The reaction temperature in the modification step is preferably the same temperature as the polymerization temperature of the conjugated diene polymer, and particularly preferably a temperature at which heating is not performed after polymerization. It is more preferable that they are 0 degreeC or more and 120 degrees C or less, More preferably, they are 50 degreeC or more and 100 degrees C or less.

The reaction time in the modification step is preferably 10 seconds or more, and more preferably 30 seconds or more.

The mixing of the conjugated diene polymer and the modifier in the modification step may be applied to any of mixing methods such as mechanical stirring and stirring by a static mixer. When a polymerization process is continuous, it is preferable that a modification process is also continuous. As the reactor in the modification step, for example, a tubular or tubular one with a stirrer is used. The modifier may be diluted with an inert solvent and continuously supplied to the reactor.

As a modifier, the compound represented by following General formula (8) is preferable.

In formula (8), R <^12> -R <^14> respectively independently represents a single bond or a C1-C20 alkylene group, R <^15> -R <^18> and R <^20> respectively independently represent C1-C20 An alkyl group is represented, R <^19> and R <^22> represents a C1-C20 alkylene group each independently, and R <^21> represents a C1-C20 alkyl group or a trialkylsilyl group.

m represents the integer of 1-3 and p represents 1 or 2.

R <^12> -R <^22> , m and p in case two or more exist respectively are independent.

i represents the integer of 0-6, j represents the integer of 0-6, k represents the integer of 0-6, (i + j + k) represents the integer of 1-10.

A has an organic group which has a single bond, a C1-C20 hydrocarbon group, or at least 1 atom chosen from the group which consists of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and a phosphorus atom, and does not have active hydrogen. .

Hydrocarbon groups represented by A include saturated, unsaturated, aliphatic and aromatic hydrocarbon groups. The organic group which does not have active hydrogen is an organic group which inactivates the active terminal which a conjugated diene type polymer has. The organic group is an organic group having no functional group having active hydrogens of hydroxyl group (-OH), secondary amino group (> NH), primary amino group (-NH ₂ ), and sulfhydryl group (-SH). In addition, when (i + j + k) is 1, A may not be present.

In said Formula (8), it is preferable that A represents either of following General formula (9)-(12).

In said formula (9), B <^1> represents a single bond or a C1-C20 hydrocarbon group, a represents the integer of 1-10, and when two or more B <^1> exists, they are independent.

Equation (10), B ² is a single bond or a hydrocarbon group having 1 to 20, B ³ is an alkyl group having 1 to 20, a is an integer of 1 to 10, B ² and B ³ is independent, respectively, when two or more exist.

In Formula (11), B ⁴ represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, a represents an integer of 1 to 10, and when a plurality of B ^{4 's} are present, they are each independently.

Equation (12), B ⁵ is a single bond or a hydrocarbon group having 1 to 20, a is an integer of 1 to 10, B ⁵ is, in the case where a plurality is present, is independently.

In Formula (8), when A represents any of Formulas (9) to (12), there is a tendency to obtain a modified conjugated diene polymer having more excellent performance.

As a modifier of the said Formula (8), as (i + j + k) being 1-2, including the thing which overlaps with the modifier mentioned above, and it is not limited to the following, For example, 3-dimethoxy Methylsilylpropyldimethylamine (monofunctional), 3-trimethoxysilylpropyldimethylamine (bifunctional), bis (3-trimethoxysilylpropyl) methylamine (tetra), bis (3-dimethoxymethylsilylpropyl ) Methylamine (bifunctional), (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] ethylamine (tetrafunctional), [3 -(2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) methylamine (4-functional), bis [3- (2,2-dimethoxy- 1-aza-2-silacyclopentane) propyl] methylamine (4-functional), bis (3-triethoxysilylpropyl) ethylamine (4-functional), 1- (3-triethoxysilylpropyl) -2, 2-diethoxy-1-aza-2-silacyclopentane (4-functional), 1- (3-dimethoxymethylsilylpropyl) -2,2-dimethok -1-aza-2-silacyclopentane (trifunctional), [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-(3-diethoxyethylsilylpropyl) methylamine (Trifunctional), bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] methylamine (tetrafunctional), (3-trimethoxysilylpropyl)-[3- ( 1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -methylamine (trifunctional) is mentioned.

Hereinafter, as a polyfunctional compound, (i + j + k) is 3 or more, In the said Formula (8), as a modifier in case A is represented by Formula (9), although it is not limited to the following, Tris (3-trimethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] amine, Bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) amine, tris [3- (2,2-dimethoxy-1- Aza-2-silacyclopentane) propyl] amine, tris (3-ethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2 -Silacyclopentane) propyl] amine, bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-(3-triethoxysilylpropyl) amine, tris [3- ( 2,2-diethoxy-1-aza-2-silacyclopentane) propyl] amine, tetrakis (3-trimethoxysilylpropyl) -1,3-propanedia , Tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, bis (3-trimethoxy Silylpropyl) -bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tris [3- (2,2-dimethoxy-1- Aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) -1,3-propanediamine, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane ) Propyl] -1,3-propanediamine,

Tris (3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, bis (3-tri Methoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2- Azacyclopentane) propyl] -1,3-propanediamine, bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl)-[ 3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, tris [3- (2,2-dimethoxy-1-aza-2 -Silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-triethoxy Silylpropyl) -1,3-propanediamine,

Tris (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, bis (3-triethoxysilyl Propyl) -bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tris [3- (2,2-diethoxy-1-aza -2-silacyclopentane) propyl]-(3-triethoxysilylpropyl) -1,3-propanediamine, tetrakis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) Propyl] -1,3-propanediamine, tris (3-triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1, 3-propanediamine, bis (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2 -Trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-( 3-triethoxysilylpropyl)-[3- (1-ethoxy-2-trime Silyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, tris [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethyl Cyclohexane, tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis ( 3-trimethoxysilylpropyl) -bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tris [3- (2 , 2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, tetrakis [3- (2,2-dimeth Methoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tris (3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila -2- Azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl ]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis [3- (2,2-dimethoxy -1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl)-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl- 1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tetrakis (3-triethoxysilylpropyl) -1,3-propanediamine,

Tris (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis (3-tri Ethoxysilylpropyl) -bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, tris [3- (2,2- Diethoxy-1-aza-2-silacyclopentane) propyl]-(3-triethoxysilylpropyl) -1,3-propanediamine, tetrakis [3- (2,2-diethoxy-1-aza- 2-silacyclopentane) propyl] -1,3-propanediamine, tris (3-triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane ) Propyl] -1,3-bisaminomethylcyclohexane, bis (3-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[ 3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, bis [3- (2,2-diethoxy-1- Aza-2-silacyclopentane) Lofil]-(3-triethoxysilylpropyl)-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -1,3-bisaminomethylcyclohexane, Tris [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl ] -1,3-bisaminomethylcyclohexane, tetrakis (3-trimethoxysilylpropyl) -1,6-hexamethylenediamine, pentakis (3-trimethoxysilylpropyl) -diethylenetriamine Can be.

In Formula (8), the modifier in the case where A is represented by Formula (10) is not limited to the following. For example, tris (3-trimethoxysilylpropyl) -methyl-1,3 -Propanediamine, bis (2-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -methyl-1,3-propanediamine, bis [ 3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) -methyl-1,3-propanediamine, tris (3-triethoxysilyl Propyl) -methyl-1,3-propanediamine, bis (2-triethoxysilylpropyl)-[3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl] -methyl-1 , 3-propanediamine, bis [3- (2,2-diethoxy-1-aza-2-silacyclopentane) propyl]-(3-triethoxysilylpropyl) -methyl-1,3-propanediamine, N ¹ , N ^{1 ′} -(propane-1,3-diyl) bis (N ¹ -methyl-N ³ , N ³ -bis (3- (trimethoxysilyl) propyl) -1,3-propanediamine), N ¹ - (3- (ratio (3- (trimethoxysilyl) propyl) amino) propyl) -N ¹ - methyl -N ³ - (3- (methyl (3- (trimethoxysilyl) propyl) amino) propyl) -N ³ - ⁽³ -(Trimethoxysilyl) propyl) -1,3-propanediamine.

In the formula (8), the modifier in the case where A is represented by formula (11) is not limited to the following. For example, tetrakis [3- (2,2-dimethoxy-1-aza-). 2-silacyclopentane) propyl] silane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) silane, tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-[3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] silane, bis (3-trimethoxysilylpropyl) -bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, (3-trimethoxysilyl)-[3- (1 -Methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) -bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, bis [3- (1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane) -bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, tris ( 3-trimethoxysilyl Phil)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, bis (3-trimethoxysilylpropyl)-[3- (1-methoxy-2- Trimethylsilyl-1-sila-2-azacyclopentane) propyl]-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] silane, bis [3- (1-methoxy -2-trimethylsilyl-1-sila-2-azacyclopentane) propyl] -bis (3-trimethoxysilylpropyl) silane, bis (3-trimethoxysilylpropyl) -bis [3- (1-methoxy Methoxy-2-methyl-1-sila-2-azacyclopentane) propyl] silane.

In the formula (8), the modifier in the case where A is represented by the formula (12) is not limited to the following. For example, 3-tris [2- (2,2-dimethoxy-1-) Aza-2-silacyclopentane) ethoxy] silyl-1- (2,2-dimethoxy-1-aza-2-silacyclopentane) propane, 3-tris [2- (2,2-dimethoxy-1 Aza-2-silacyclopentane) ethoxy] silyl-1-trimethoxysilylpropane.

In the formula (8), the modifier in the case where A represents an organic group having an oxygen atom and no active hydrogen, is not limited to the following. For example, (3-trimethoxysilylpropyl) -[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] ether (4-functional), 3,4,5-tris (3-trimethoxysilylpropyl) -cyclohexyl- [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] ether (8 functional) is mentioned.

In the formula (8), the modifier in the case where A has a phosphorus atom and represents an organic group having no active hydrogen, is not limited to the following. For example, (3-trimethoxysilylpropyl) phosphate , Bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] phosphate, bis [3- (2,2-dimethoxy-1 Aza-2-silacyclopentane) propyl]-(3-trimethoxysilylpropyl) phosphate and tris [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] phosphate Can be.

In the formula (8), A preferably represents the formula (9) or the formula (10), and k represents 0. Thereby, it exists in the tendency to become an easily available modifier, and also when it uses a modified conjugated diene type polymer as a vulcanizate, it exists in the tendency which becomes more excellent in abrasion resistance and low hysteresis loss performance.

Examples of such modifiers include, but are not limited to, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] amine , Tris (3-trimethoxysilylpropyl) amine, tris (3-triethoxysilylpropyl) amine, tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza -2-silacyclopentane) propyl] -1,3-propanediamine, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, Tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, tris (3-trimethoxysilylpropyl ) -Methyl-1,3-propanediamine, bis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl]-(3-trismethoxysilylpropyl) -methyl-1, 3-propanediamine is mentioned.

In the formula (8), A more preferably represents formula (9) or formula (10), k represents 0, and in formula (9) or formula (10), a represents 2 to 10 Represents an integer. By using such a modifier, when vulcanized, the wear resistance and the low hysteresis loss performance tend to be more excellent.

Examples of such modifiers include, but are not limited to, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, N ^1- (3- (bis (3- (trimethoxysilyl) propyl) amino) propyl) -N ¹ - methyl -N ³ - (3- (methyl (3- (trimethoxysilyl) propyl) amino) propyl) -N ³ - (3- (tri Methoxysilyl) propyl) -1,3-propanediamine.

The addition amount of the compound represented by Formula (8) as a modifier can be adjusted so that the number of moles of the polymerization initiator to the number of moles of the modifier can be reacted at a desired stoichiometric ratio, whereby the desired degree of branching is achieved. The number of moles of the specific polymerization initiator is preferably 1.0 times or more, more preferably 2.0 times or more, based on the number of moles of the modifier. In this case, in Formula (8), it is preferable that the functional group number ((m-1) * i + pxj + k) of a modifier is an integer of 1-10, and it is more preferable that it is an integer of 2-10.

Hydrogenation Process

The modified conjugated diene-based polymers (A) and (B) constituting the modified conjugated diene-based polymer mixture obtained by the production method of the present embodiment may each hydrogenate a conjugated diene part.

The method of hydrogenating a conjugated diene part is not specifically limited, A well-known method can be used.

As a preferable method of hydrogenation, the method of hydrogenating by the method of blowing gaseous hydrogen into a polymer solution in presence of a catalyst is mentioned.

As a catalyst, For example, heterogeneous catalysts, such as a catalyst which supported the noble metal on the porous inorganic substance; And homogeneous catalysts such as catalysts made by solubilizing salts such as nickel and cobalt and reacting with organic aluminum and the like, and catalysts using metallocene such as titanocene. Among these, a titanocene catalyst is preferable from a viewpoint which can select mild hydrogenation conditions. In addition, hydrogenation of an aromatic group can be performed by using a supported catalyst of a noble metal.

Examples of the hydrogenation catalyst include, but are not limited to, (1) a supported heterogeneous hydrogenation catalyst in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, and the like (2) So-called Ziegler-type hydrogenation catalysts using transition metal salts such as organic acid salts such as Ni, Co, Fe, Cr, and acetylacetone salts and reducing agents such as organic aluminum, and (3) organic metals such as Ti, Ru, Rh, and Zr. So-called organometallic complexes, such as a compound, etc. are mentioned.

Moreover, as a hydrogenation catalyst, For example, Unexamined-Japanese-Patent No. 42-8704, Unexamined-Japanese-Patent No. 43-6636, Unexamined-Japanese-Patent No. 63-4841, Unexamined-Japanese-Patent No. 1-37970, The well-known hydrogenation catalyst of Unexamined-Japanese-Patent No. 1-53851, Unexamined-Japanese-Patent No. 2-9041, and Unexamined-Japanese-Patent No. 8-109219 is also mentioned. As a preferable hydrogenation catalyst, the reaction mixture of a titanocene compound and a reducing organometallic compound is mentioned.

In the manufacturing process of a modified conjugated diene polymer (A), (B), after a modification process, you may add a deactivator, a neutralizing agent, etc. to a modified conjugated diene polymer solution as needed.

As a deactivator, although it is not limited to the following, For example, Water; Alcohol, such as methanol, ethanol, and isopropanol, etc. are mentioned.

Examples of the neutralizing agent include, but are not limited to, carboxylic acids such as stearic acid, oleic acid and versaic acid (a branched carboxylic acid mixture having 9 to 11 carbon atoms and having a center of 10); The aqueous solution of an inorganic acid and carbonic acid gas are mentioned.

It is preferable to add a stabilizer for rubber | gum to a modified conjugated diene type polymer (A) and (B) from a viewpoint of preventing the gel formation after superposition | polymerization, and a viewpoint of improving the stability at the time of processing.

As a rubber stabilizer, a well-known thing can be used, It is not limited to the following, For example, 2, 6- di-tert- butyl- 4-hydroxytoluene (BHT), n-octadecyl-3- ( Antioxidants such as 4'-hydroxy-3 ', 5'-di-tert-butylphenol) propionate and 2-methyl-4,6-bis [(octylthio) methyl] phenol.

In order to further improve the processability of the modified conjugated diene-based polymer (A) and (B), extender oil may be added to the modified conjugated diene-based copolymer as necessary.

The method of adding the extender oil to the modified conjugated diene-based polymers (A) and (B) is not limited to the following method, but the extender oil is added to the polymer solution, mixed, and the dielectric copolymer solution is removed. The method of solvent is preferable.

The timing for adding the extender oil is not limited to the following time, but may be mentioned after the modification step, before mixing with the polymer solution, or after mixing with both polymer solutions.

From the standpoint of mixing the extender oil, the viscosity of the polymer solution is lowered and the polymer solution is easy to be mixed.

As extender oil, an aromatic oil, a naphthenic oil, a paraffin oil, etc. are mentioned, for example. Among these, aromatic replacement oils having a polycyclic aromatic (PCA) component of 3% by mass or less from the viewpoint of environmental safety and from the viewpoint of oil bleed prevention and wet grip characteristics are preferred. In addition, the oil derived from vegetable oil etc. are mentioned, For example, brand names "Vivamax5000" "Vivamax5100" by H & R company, etc. are mentioned.

Examples of the aromatic substitute oil include Residual Aromatic Extracts (RAE), in addition to TDAE (Treated Distillate Aromatic Extracts), MES (Mild Extraction Solvate), and the like shown in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999).

Although the addition amount of extender oil is not specifically limited, 10 mass parts or more and 60 mass parts or less are preferable with respect to 100 mass parts of modified conjugated diene type polymers, and 20 mass parts or more and 37.5 mass parts or less are more preferable.

<Mixing process>

In the method for producing a modified conjugated diene polymer mixture of the present embodiment, as described above, a polymer solution of a modified conjugated diene polymer (A) and a modified conjugated diene polymer (B) is obtained through a polymerization step and a modification step. Thereafter, these are mixed with a solution and solvent is removed to obtain a modified conjugated diene polymer mixture (C).

It is preferable to provide the storage tank which stores the polymer solution which flowed out from each reaction tank downstream of the reaction tank of a modified conjugated diene type polymer (A), and the reaction tank of a modified conjugated diene type polymer (B) about a mixing process. . By providing the storage tanks for each polymer, the flow rate can be adjusted before the mixing step after the modification step, it is easy to finely adjust the mixing ratio of the polymer solution, and can be stored in a different tank from the reaction tank.

As for the capacity of a storage tank, it is more preferable that it is larger than a reaction tank.

Although not limited to the following as a mixing means of this embodiment, the thing using the tank provided with a rotary stirrer, or the pipe provided with a rotary stirrer or a static mixer is mentioned. It is preferable to use the tank provided with a rotary stirrer from a viewpoint of stirring ability, and it is preferable to use the tube provided with a rotary stirrer or a static mixer from a viewpoint of manufacturing efficiency.

Although the temperature in a mixing process is not specifically limited, It is preferable that they are 0 degreeC or more and 120 degrees C or less, and it is more preferable that they are 50 degreeC or more and 100 degrees C or less. This is because the higher the temperature, the lower the viscosity of the polymer solution and the easier it is to mix. In a preferred embodiment, the solution flowing out of the head of the polymerization reaction tank is temporarily stored, and then mixed thereafter, if the storage time is short and the temperature of the solution is maintained even after outflow from the polymerization tank. Although the storage time is long, the temperature is low, such as when the temperature of the solution tends to be lowered, the storage tank, the mixing tank, piping and the like may be kept warm or heated.

The mixed mass ratio of the modified conjugated diene-based polymer (A) and the modified conjugated diene-based polymer (B) in the mixing step is preferably ((A) / (B)) = 90/10 to 40/60, more preferably Preferably it is 85 / 15-50 / 50, More preferably, it is 80 / 20-55 / 45, More preferably, it is 75 / 25-60 / 40.

When it exists in this range, there exists a tendency for the balance of the wear resistance at the time of using a vulcanized material and the workability balance at the time of using a vulcanized material.

In addition, the above-mentioned ratio is the mass ratio of a modified conjugated diene type polymer, and when the density | concentration of the polymer solution of a modified conjugated diene type polymer (A) and the polymer solution of a modified conjugated diene type polymer (B) is the same, it is as mass ratio of a solution as it is. Although it is good to employ | adopt, these solution concentrations may differ. This is because, in the case of producing a polymer having a low molecular weight, the heat of reaction tends to be increased by increasing the amount of the polymerization initiator added, so that the concentration of the solution may be lowered in order to maintain the polymerization temperature. In this case, after considering the solution concentration, it is preferable to adjust the ratio of mixing so as to be a mass ratio of the preferred polymer.

The solvent removal process can use well-known methods, such as drying and devolatilization. As the method, for example, the solvent is separated by steam stripping or the like, and then the polymer is separated by filtration and further dewatered and dried to obtain the polymer, concentrated in a flushing tank, and further devolatilized by a vent extruder or the like. The method of devolatilizing directly with a method, a drum dryer, etc. is mentioned.

〔Properties〕

(Molecular Weight)

The weight average molecular weight (Mw) of the modified conjugated diene polymer (A) is 70 × 10 ⁴ or more and 300 × 10 ⁴ or less, preferably 70 × 10 ⁴ or more and 200 × 10 ⁴ or less, more preferably 100 × 10 ⁴ or more and 180 x 10 ⁴ or less. It is 70 * 10 <^4> or more from a viewpoint of the abrasion resistance in the case of using a vulcanizate, It is 300 * 10 <^4> or less from a viewpoint of the balance of the wear resistance in the case of using a vulcanizate, and the vulcanizate, and it is 180 * 10 <^4> or less It is preferable.

The weight average molecular weight (Mw) of the modified conjugated diene polymer (B) is 10 × 10 ⁴ or more and less than 70 × 10 ⁴ , preferably 15 × 10 ⁴ or more and 60 × 10 ⁴ or less, and more preferably 30 × 10 ⁴ or more and 55 x 10 ⁴ or less. It is 10x10 <^4> or more from a viewpoint of the abrasion resistance in the case of using a vulcanizate, and it is less than 70x10 <^4> and 55 * 10 <^4> or less from a viewpoint of the balance of abrasion resistance in the case of using a vulcanized material and workability when it is made into a vulcanized material desirable.

In general, when the molecular weight is large, the wear resistance is excellent, but the workability is inferior. On the other hand, when molecular weight is small, it is excellent in workability, but wear resistance is inferior.

The modified conjugated diene polymer (A) having 70 × 10 ⁴ or more and 300 × 10 ⁴ or less has a large molecular weight and is excellent in wear resistance, but tends to be inferior in workability. On the other hand, the modified conjugated diene type polymer (B) of 10x10 <^4> or more and less than 70x10 <^4> has a small molecular weight, and there exists a tendency for abrasion resistance to be inferior. However, by mixing both, there exists a tendency for the modified conjugated diene type polymer mixture (C) which has each advantage, ie excellent in the balance of abrasion resistance and workability, to be obtained.

The weight average molecular weight of the modified conjugated diene polymer mixture (C) is 70 × 10 ⁴ or more and 300 × 10 ⁴ or less, preferably 85 × 10 ⁴ or more and 200 × 10 ⁴ or less, and more preferably 100 × 10 ⁴ It is more than 180 * 10 <^4> . It is preferable that it is 70 * 10 <^4> or more from a viewpoint of abrasion resistance in the case of using a vulcanized material, and 180 * 10 <^4> or less from a viewpoint of the balance of the wear resistance in the case of using a vulcanized material, and the workability at the time of making it a vulcanized material.

ΔMw a difference between the weight average molecular weight of the present embodiment of the modified conjugated diene-based polymer (A) and the modified conjugated diene-based polymer (B) is preferably at least, 50 × 10 ^4, and more preferably at least 60 × 10 ^4, More preferably, it is 70x10 <^4> or more, More preferably, it is 80x10 <^4> or more.

When it exists in this range, there exists a tendency which is excellent in the balance of the wear resistance at the time of using a vulcanized material, and the workability at the time of using a vulcanized material.

Abrasion resistance tends to be excellent as the molecular weight is large, and workability tends to be excellent as the molecular weight is small.

The larger the difference in the weight average molecular weight of the modified conjugated diene-based polymer (A) and the modified conjugated diene-based polymer (B) is a modified conjugated diene-based polymer (A), which results in a modified conjugated diene-based polymer that is more specialized in wear resistance. If it is a conjugated diene type polymer (B), it means that it becomes a modified conjugated diene type polymer more specialized in workability.

Therefore, there exists a tendency for the complementary effect at the time of mixing both.

The weight average molecular weight (Mw) of a modified conjugated diene type polymer (A) and (B) can be controlled by the method of adjusting the polymerization temperature, monomer addition amount, and polymerization initiator addition amount in each polymerization process.

When the polymerization temperature in the polymerization step is increased, the polymerization reaction rate is increased, and a polymer having a large weight average molecular weight tends to be obtained. However, if the polymerization temperature is made too high, the modification reaction does not proceed due to deactivation of the polymer terminal due to heat, and the weight average molecular weight of the modified conjugated diene polymer tends to be difficult to increase.

When the amount of monomer added in the polymerization step is increased, the amount of monomer to be polymerized with respect to one molecule of the polymerization initiator increases, so that the weight average molecular weight tends to increase.

When the amount of the polymerization initiator added in the polymerization step is increased, the amount of monomer to be polymerized with respect to one molecule of the polymerization initiator decreases, so that the weight average molecular weight tends to decrease.

From this, the weight average molecular weight difference (ΔMw) of the modified conjugated diene-based polymer (A) and (B) is based on the conditions in the polymerization step of the modified conjugated diene-based polymer (A) and / or the modified conjugated diene-based polymer (B). By adjusting suitably, it can control to the said numerical range.

(Molecular weight distribution)

The molecular weight distribution (Mw / Mn) of the modified conjugated diene polymer mixture (C) is from 1.8 to 4.5. Preferably they are 1.85 or more and 4.0 or less, More preferably, they are 1.90 or more and 3.50 or less.

When it exists in this range, there exists a tendency which is excellent in the balance of the wear resistance at the time of using a vulcanized material, and the workability at the time of using a vulcanized material.

The molecular weight distribution of the modified conjugated diene polymer mixture (C) can be controlled in the above numerical range by adjusting the molecular weight difference, molecular weight distribution, and composition ratio of the modified conjugated diene polymer (A) and the modified conjugated diene polymer (B). .

(Denaturation rate)

It is preferable that the modification rate of a modified conjugated diene type polymer mixture (C) is 50 mass% or more with respect to the total amount of a conjugated diene type polymer, More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more. When the modification rate is in the above range, there is a tendency to be excellent in workability when forming a vulcanized product and excellent in balance between low hysteresis loss and wet skid resistance when vulcanized.

It is preferable that the modification rate of a modified conjugated diene type polymer (A) and a modified conjugated diene type polymer (B) is 50 mass% with respect to the conjugated diene type polymer total amount, It is more preferable that it is 65 mass% or more, It is 80 mass% or more Even more preferred.

When it exists in this range, it exists in the tendency for the workability at the time of making a vulcanized material and the balance of the low hysteresis loss and the wet skid resistance at the time of making it vulcanized. It is preferable that both a modified conjugated diene type polymer (A) and a modified conjugated diene type polymer (B) have a high modification rate.

When comparing the modified conjugated diene polymer with a large molecular weight and the modified conjugated diene polymer with a small molecular weight, the modified conjugated diene polymer having a lower molecular weight tends to have an excellent balance between low hysteresis loss and wet skid resistance when vulcanized. There is this. Therefore, when either of the modified conjugated diene polymer (A) and the modified conjugated diene polymer (B) has a high modification rate, the higher the modification rate of the modified conjugated diene polymer (B) is preferable.

The modification rates of the modified conjugated diene-based polymer mixture (C), the modified conjugated diene-based polymer (A) and (B) are, for example, the purity of the monomer or solvent used for the polymerization, the amount of the modifier added, and the temperature in the modification step. Etc., it is possible to control the above-described numerical range.

(Shrinkage factor)

The shrinkage factor (g ') measured by the GPC-light scattering method measurement with a viscosity detector (hereinafter also referred to simply as "GPC-light scattering method measurement with viscosity detector" or "3D-GPC measurement") is the modified conjugated diene-based polymer. It is an index of the index of. For example, as the shrinkage factor g 'decreases, the number of branches of the modified conjugated diene-based polymer (for example, the number of branches of the molded polymer (also referred to as the "number of molded polymers")) tends to increase. have.

When comparing modified conjugated diene-based polymers having the same molecular weight, the more the branching of the modified conjugated diene-based polymer is, the smaller the shrinkage factor (g ') is. Therefore, the shrinkage factor (g') in this case can be used as an index of branching. Can be.

Shrinkage factor (g ') is measured using 3D-GPC measurement.

The constants (K, α) in the relationship of intrinsic viscosity and molecular weight ([η] = KMα ([η]: intrinsic viscosity, M: molecular weight)) were set to logK = -3.883 and α = 0.771, and the standard intrinsic viscosity [η ] Create a graph of the relationship between ₀ and molecular weight M.

As a relation of the normal intrinsic viscosity [η] intrinsic in each molecular weight M of the sample obtained by the 3D-GPC measuring the viscosity with respect to ₀ to [η] standard intrinsic viscosity [η] intrinsic to the ₀ viscosity [η] [η] / [eta] ₀ is computed by each molecular weight M, and its average value is made into shrinkage factor (g ').

More specifically, it can measure by the method as described in the Example mentioned later.

In the modified conjugated diene-based polymer (A) and / or the modified conjugated diene-based polymer (B), a shrinkage factor (g ') measured using 3D-GPC is 0.70 or more and 1.0 or less as a preferred form.

When the shrinkage factor (g ') of the modified conjugated diene-based polymer (A) and / or (B) is in the above range, there is a tendency that the strength at high temperature is excellent.

Shrinkage factor (g ') becomes an index of the branched structure of a modified conjugated diene type copolymer, The modified conjugated diene type polymer whose shrinkage factor (g') is 0.70 or more and 1.0 or less is a branch in 1 molecule of a modified diene type polymer. There exists a tendency for the number of to be a modified conjugated diene type polymer of four branches or less. In this case, the shrinkage factor g 'is more preferably 0.73 or more and 0.99 or less, and still more preferably 0.75 or more and 0.98 or less.

In order for the shrinkage factor (g ') to obtain the modified conjugated diene-based copolymer in the above range, for example, a modifier having four or less reaction points with the living active terminal is one-fourth of the total moles of the polymerization initiator. It is effective to add it with the above-mentioned number of moles, and to obtain the modified conjugated diene type copolymer of four branches or less.

Since the intensity | strength in high temperature has the same branched structure, since the one where molecular weight is larger tends to be excellent, it is preferable that the modified conjugated diene type polymer (A) with a large molecular weight has a shrinkage factor (g ') of 0.70 or more and 1.0 or less.

The modified conjugated diene-based polymer (A) and / or (B) more preferably has a shrinkage factor (g ') of 0.30 or more and less than 0.70 measured using 3D-GPC.

Such a modified conjugated diene-based polymer has a lower viscosity of the composition to which the filler is added, resulting in more excellent workability.

Shrinkage factor (g ') becomes an index of the branched structure of the said modified conjugated diene type copolymer, As a modified conjugated diene type polymer whose shrinkage factor (g') is 0.30 or more and less than 0.70, in one molecule of a modified diene type polymer The number of branches tends to be modified conjugated diene polymers having five or more branches.

In order for the shrinkage factor (g ') to obtain the modified conjugated diene-based copolymer in the above-mentioned range, for example, a modifier having five or more reaction points with living active terminals is a fifth of the total moles of the polymerization initiator. It is effective to add in the following number of moles to obtain a modified conjugated diene copolymer of five or more branches.

The modified conjugated diene polymer having a shrinkage factor (g ') of 0.30 or more and less than 0.64 is 6 branches or more, and the modified conjugated diene polymer having 0.30 or more and less than 0.59 tends to be 8 branches or more. Such a modified conjugated diene-based polymer has a lower viscosity of the composition to which the filler is added, and is more excellent in workability.

Since the workability is the same branched structure, the smaller the molecular weight tends to be, the modified conjugated diene polymer (B) having a lower molecular weight preferably has a shrinkage factor (g ') of 0.30 or more and less than 0.70, and 0.30 or more and less than 0.64. More preferably, it is more preferable that it is 0.30 or more and less than 0.59.

Shrinkage factor (g ') measured using 3D-GPC of modified conjugated diene-based polymer (A) is 0.70 or more and 1.0 or less, shrinkage factor (g) measured using 3D-GPC of modified conjugated diene-based polymer (B) It is preferable that ') is 0.30 or more and less than 0.70. When it exists in such a range, there exists a tendency for the modified conjugated diene type polymer mixture which is excellent in the balance of high temperature strength and workability to be obtained.

(Nitrogen content)

In the manufacturing method of this embodiment, it is preferable that content of nitrogen of a modified conjugated diene type polymer (B) is 3 mass ppm or more and 70 mass ppm or less.

When it is 3 mass ppm or more, the effect of improving the balance of low hysteresis loss and wet skid resistance when a vulcanizate is obtained is obtained, and when it is 70 mass ppm or less, the suppression of stiffness fall by silica being disperse | distributed too much Effect is obtained.

More preferably, they are 6 mass ppm or more and 60 mass ppm or less, More preferably, they are 10 mass ppm-50 mass ppm.

Nitrogen content can be controlled in the said numerical range by adjusting suitably the ratio of nitrogen contained in a modifier, the addition amount of a nitrogen containing modifier, and the bond amount of the modifier to a superposition | polymerization terminal.

POLYMER COMPOSITION

The modified conjugated diene polymer mixture obtained by the method for producing the modified conjugated diene polymer mixture of the present embodiment can be made into a polymer composition by combining with other materials.

It is preferable that a polymer composition contains 10 mass% or more of modified conjugated diene type polymer mixtures (C).

The polymer composition may contain polymers other than the modified conjugated diene polymer mixture (C).

As polymers other than the modified conjugated diene-based polymer mixture (C), rubbery polymers having a structure other than the structures of the modified conjugated diene-based polymer (A) and (B) (hereinafter referred to as "other rubbery polymers"), Or dendritic polymers.

Examples of the other rubbery polymer include, but are not limited to, the following: a conjugated diene polymer or a hydrogenated product thereof, a random copolymer of a conjugated diene compound and a vinyl aromatic compound, or a hydrogenated product thereof, a conjugated diene compound and a vinyl. The block copolymer of an aromatic compound, its hydrogenated substance, a diene type polymer, a natural rubber is mentioned. Specific other rubbery polymers include, but are not limited to, butadiene rubber or its hydrogenated substance, isoprene rubber or its hydrogenated substance, styrene-butadiene rubber or its hydrogenated substance, styrene-butadiene block copolymer or its Styrene-type elastomers, such as a hydrogenated substance, a styrene- isoprene block copolymer, or its hydrogenated substance, an acrylonitrile- butadiene rubber, or its hydrogenated substance.

Although it is not limited to the following as the said diene type polymer, For example, ethylene propylene rubber, ethylene propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene- Olefin elastomers such as octene rubber, butyl rubber, butyl bromide rubber, acrylic rubber, fluorine rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, urethane Rubber and polysulfide rubber.

As said natural rubber, although it is not limited to the following, For example, RSS3-5 which is a smoke sheet, SMR, and epoxidized natural rubber are mentioned.

As a method of mixing the modified conjugated diene-based polymer mixture (C) with a polymer other than the modified conjugated diene-based polymer (A) and (B) (called another polymer), it is different from the solution of the modified conjugated diene-based polymer mixture (C). Various methods, such as the method of mixing the solution of a polymer, the method of mechanically mixing a modified conjugated diene type polymer mixture (C), and another polymer, are mentioned.

The other polymer mentioned above may be a modified rubber to which functional groups which have polarity, such as a hydroxyl group and an amino group, are provided. When used for tires, butadiene rubber, isoprene rubber, styrene-butadiene rubber, natural rubber and butyl rubber are preferably used.

When another polymer is said "other rubbery polymer", it is preferable that it is 2,000 or more and 2,000,000 or less, and, as for the weight average molecular weight from a viewpoint of the balance of a performance and a processing characteristic, it is more preferable that it is 5,000 or more and 1,500,000 or less. Moreover, a low molecular weight rubbery polymer and what is called liquid rubber can also be used. These other rubbery polymers may be used individually by 1 type, and may use 2 or more types together.

When the polymer composition containing the modified conjugated diene-based polymer mixture (C) contains another rubbery polymer, the content ratio (mass ratio) of the modified conjugated diene-based polymer mixture (C) to the other rubbery polymer is As (modified conjugated diene polymer mixture (C) / other rubbery polymer), 10/90 or more and 100/0 or less are preferable, 20/80 or more and 90/10 or less are more preferable, 50/50 or more and 80/20 The following is more preferable.

Therefore, the polymer composition preferably contains 10 parts by mass or more and 100 parts by mass or less of the modified conjugated diene polymer mixture (C) with respect to the total amount (100 parts by mass) of the polymer composition, more preferably 20 parts by mass. 90 mass parts or less are included, More preferably, 50 mass parts or more and 80 mass parts or less are included.

When the content ratio of (modified conjugated diene-based polymer mixture (C) / other rubbery polymer) is within the above range, when a vulcanized product is used, the balance between low hysteresis loss and wet skid resistance is excellent, and abrasion resistance and breaking strength are also satisfied. .

The modified conjugated diene polymer mixture (C) is suitably used as a vulcanizate. Examples of the vulcanizate include tires, hoses, soles, anti-vibration rubbers, automobile parts, and anti-vibration rubbers, and also rubbers for resin reinforcement such as impact-resistant polystyrene and ABS resins. In particular, the modified conjugated diene polymer is suitably used for the composition of tread rubber for tires. The vulcanizate is, for example, a modified conjugated diene-based polymer mixture (C), if necessary, inorganic fillers such as silica-based inorganic fillers, carbon black, rubber-like polymers other than the modified conjugated diene-based polymer mixture (C), and silanes. It can be obtained by kneading a coupling agent, a softening agent for rubber, a vulcanizing agent, a vulcanizing accelerator, a vulcanizing aid, or the like to form a rubber composition, followed by heating and vulcanization.

[Rubber composition]

The modified conjugated diene polymer mixture obtained by the production method of the present embodiment can be used in a rubber composition.

It is preferable that the said rubber composition contains 100 mass parts of rubbery polymers containing 10 mass% or more of modified conjugated diene copolymer mixtures (C), and 5-150 mass parts of fillers.

Moreover, it is preferable that the said filler contains a silica type inorganic filler.

The rubber composition tends to be more excellent in workability when forming a vulcanizate by dispersing a silica-based inorganic filler, and when the vulcanizate is used, a balance between low hysteresis loss and wet skid resistance, and breaking strength and wear resistance Tends to be excellent.

When the said rubber composition is used for vulcanized rubber applications, such as an automobile component, such as a tire and dustproof rubber, and shoes, it is preferable to contain a silica type inorganic filler.

Although it is not limited to the following as a filler, For example, a silica type inorganic filler, carbon black, a metal oxide, and a metal hydroxide are mentioned. Among these, silica type inorganic fillers are preferable. These may be used individually by 1 type and may use 2 or more types together.

It is preferable that it is 5.0 mass part or more and 150 mass parts or less with respect to 100 mass parts of rubbery polymers containing a modified conjugated diene type polymer mixture (C), and, as for filler content in the said rubber composition, it is more than 10 mass parts and 120 mass parts or less It is more preferable that it is 20 mass parts or more and 100 mass parts or less.

It is preferable that content of a filler is 5.0 mass parts or more from a viewpoint of the addition effect of a filler, and it is preferable that it is 150 mass parts or less from a viewpoint which disperse | distributes a filler sufficiently and makes processability and mechanical strength of a rubber composition practically sufficient. Do.

The silica-based inorganic filler is not particularly limited and known ones can be used, but solid particles containing SiO ₂ or Si ₃ Al as a structural unit are preferred, and solids containing SiO ₂ or Si ₃ Al as a main component of the structural unit. Particles are more preferred. Here, a main component means the component contained 50 mass% or more, Preferably it is 70 mass% or more, More preferably, 80 mass% or more in a silica type inorganic filler.

Examples of the silica-based inorganic filler include, but are not limited to, inorganic fibrous materials such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber. Moreover, the mixture of the inorganic filler other than a silica type, the silica type inorganic filler, the silica type inorganic filler which hydrophobized the surface, is also mentioned. Among these, silica and glass fiber are preferable from a viewpoint of strength, abrasion resistance, etc., and a silica is more preferable. As silica, dry silica, wet silica, synthetic silicate silica is mentioned, for example. Among these silicas, wet silica is preferable from the viewpoint of excellent balance between the improvement effect of the fracture characteristics and the wet skid resistance.

In the rubber composition, from the viewpoint of obtaining practically good wear resistance and fracture characteristics, the nitrogen adsorption specific surface area determined by the BET adsorption method of the silica-based inorganic filler is preferably 100 m 2 / g or more and 300 m 2 / g or less, and 170 m 2 It is more preferable that it is / g or more and 250 m <2> / g or less.

In addition, if necessary, a silica-based inorganic filler having a relatively small specific surface area (eg, a specific surface area of less than 200 m 2 / g) and a silica-based inorganic filler having a relatively large specific surface area (eg, 200 m 2 / g or more) Can be used in combination.

In particular, in the case of using a silica-based inorganic filler having a relatively large specific surface area (for example, 200 m 2 / g or more), the modified conjugated diene-based polymer improves dispersibility of silica, and is particularly effective in improving wear resistance. It tends to be able to highly balance good fracture characteristics and low hysteresis losses.

It is preferable that content of the silica-type inorganic filler in a rubber composition is 5.0 mass part or more and 150 mass parts with respect to 100 mass parts of rubbery polymers containing a modified conjugated diene type polymer mixture (C), and they are 20 mass parts or more and 100 mass parts or less It is more preferable. The content of the silica-based inorganic filler is preferably 5.0 parts by mass or more from the viewpoint of the addition effect of the inorganic filler, from the viewpoint of sufficiently dispersing the inorganic filler and making the workability and mechanical strength of the rubber composition practically sufficient. It is preferable that it is 150 mass parts or less.

Although carbon black is not limited to the following, Carbon black of each class, such as SRF, FEF, HAF, ISAF, SAF, is mentioned, for example. Among these, carbon black whose nitrogen adsorption specific surface area is 50 m <2> / g or more and dibutyl phthalate (DBP) oil absorption amount is 80 mL / 100 g or less is preferable.

0.5 mass part or more and 100 mass parts or less are preferable with respect to 100 mass parts of rubbery polymers containing a modified conjugated diene type polymer mixture (C), and, as for content of carbon black, 3.0 mass parts or more and 100 mass parts or less are more preferable. , 5.0 parts by mass or more and 50 parts by mass or less are more preferable. It is preferable to make content of carbon black into 0.5 mass part or more from a viewpoint of expressing the performance calculated | required for the use of tires, such as dry grip performance and electroconductivity, and to make it 100 mass parts or less from a dispersible viewpoint. Do.

A metal oxide means the solid particle which has chemical formula MxOy (M represents a metal atom and x and y respectively independently represent the integer of 1-6.) As a main component of a structural unit. Although it is not limited to the following as a metal oxide, For example, alumina, titanium oxide, magnesium oxide, and zinc oxide are mentioned.

Although it is not limited to the following as a metal hydroxide, For example, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide is mentioned.

The said rubber composition may also contain a silane coupling agent.

The silane coupling agent has a function of intimately interacting the rubbery polymer with the inorganic filler, has affinity or bonding groups for the rubbery polymer and the silica-based inorganic filler, respectively, and has a sulfur-bonding portion and an alkoxysilyl group. Or the compound which has a silanol group part in 1 molecule is preferable. As such a compound, for example, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2- (Triethoxysilyl) -ethyl]-tetrasulfide is mentioned.

0.1 mass part or more and 30 mass parts or less are preferable with respect to 100 mass parts of inorganic fillers mentioned above, as for content of a silane coupling agent, 0.5 mass part or more and 20 mass parts or less are more preferable, 1.0 mass part or more and 15 mass parts or less are More preferred. When content of a silane coupling agent is the said range, there exists a tendency which can make the addition effect of a silane coupling agent more remarkable.

The said rubber composition may also contain the rubber softener from a viewpoint of improving the workability.

As the rubber softener, mineral oil or a liquid or low molecular weight synthetic softener is preferable. The softening agent for mineral oil type rubber called process oil or extender oil which is used in order to soften rubber, increase volume, and improve workability is a mixture of aromatic ring, naphthenic ring, and paraffin chain, It is called paraffin type that occupies 50 mass% or more in carbon, and naphthenic system occupies 30 mass% or more and 45 mass% or less among all carbons, naphthenic system, and aromatic carbon number occupies more than 30 mass% of all carbon by aromatic It is called the system.

When the modified conjugated diene polymer (A) and the modified conjugated diene polymer (B) contained in the modified conjugated diene polymer mixture (C) are copolymers of a conjugated diene compound and a vinyl aromatic compound, it is suitable as a softener for rubber to be used. Having an aromatic compound content is preferable because affinity with the copolymer tends to be good.

0 mass part or more and 100 mass parts or less are preferable with respect to 100 mass parts of rubbery polymers containing a modified conjugated diene type polymer mixture (C), and, as for content of a rubber softener, 10 mass parts or more and 90 mass parts or less are more preferable. And 30 mass parts or more and 90 mass parts or less are more preferable. When content of the softener for rubber is 100 mass parts or less with respect to 100 mass parts of rubbery polymers, there exists a tendency to suppress bleed out and to suppress stickiness of the rubber composition surface.

The method for mixing the modified conjugated diene-based polymer mixture (C) with other rubbery polymers, silica-based inorganic fillers, carbon black or other fillers, silane coupling agents, rubber softeners, and the like is limited below. However, for example, melt kneading method using a general admixture such as an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multi-screw screw extruder, and a method of heating and removing a solvent after dissolving and mixing each component Can be mentioned.

Among these, the melt kneading method using a roll, a Banbury mixer, a kneader, and an extruder is preferable from a viewpoint of productivity and favorable kneading | mixing property. Moreover, the method of kneading a rubbery polymer and other fillers, a silane coupling agent, and an additive at once, and the method of dividing and mixing into several times are applicable.

The rubber composition may be a vulcanized composition which has been vulcanized by a vulcanizing agent. Examples of the vulcanizing agent include, but are not limited to, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur and sulfur compounds.

The sulfur compound includes sulfur monochloride, sulfur dichloride, disulfide compound, high molecular weight sulfur compound and the like. 0.01 mass part or more and 20 mass parts or less are preferable with respect to 100 mass parts of rubbery polymers, and, as for content of a vulcanizing agent, 0.1 mass part or more and 15 mass parts or less are more preferable. As a vulcanization method, a conventionally well-known method can be applied, As for vulcanization temperature, 120 degreeC or more and 200 degrees C or less are preferable, More preferably, they are 140 degreeC or more and 180 degrees C or less.

At the time of vulcanization, you may use a vulcanization accelerator as needed. As a vulcanization accelerator, a conventionally well-known material can be used, It is not limited to the following, For example, sulfenamide type, guanidine type, thiuram type, aldehyde-amine type, aldehyde-ammonia type, thiazole type, thio Vulcanization accelerators of urea and dithiocarbamate. In addition, as a vulcanization adjuvant, although not limited to the following, For example, zincation and a stearic acid are mentioned. 0.01 mass part or more and 20 mass parts or less are preferable with respect to 100 mass parts of rubber components, and, as for content of a vulcanization accelerator, 0.1 mass part or more and 15 mass parts or less are more preferable.

In the rubber composition, various additives such as other softeners and fillers, heat stabilizers, antistatic agents, weathering stabilizers, anti-aging agents, colorants, lubricants and the like other than those described above are used within the scope of not impairing the object of the present embodiment. You may also As other softeners, well-known softeners can be used. As other filler, calcium carbonate, magnesium carbonate, aluminum sulfate, barium sulfate is mentioned, for example. As said heat stabilizer, antistatic agent, weathering stabilizer, anti-aging agent, coloring agent, lubricant, a well-known material can be used, respectively.

〔tire〕

The said rubber composition is used suitably as a rubber composition for tires.

Although the said rubber composition is not limited to the following, For example, various tires, such as a fuel economy tire, a four season tire, a high performance tire, and a studless tire: each part of a tire, such as a tread, a carcass, a side wall, a bead part, etc. It is available to. In particular, the rubber composition for tires containing the modified conjugated diene-based polymer mixture (C) is excellent in the balance and wear resistance of low hysteresis loss and wet skid resistance when used as a vulcanizate, and therefore, for treads of fuel economy-saving tires and high-performance tires. As it is, it is used more suitably.

EXAMPLE

Hereinafter, although a specific Example and a comparative example are given and this embodiment is demonstrated in detail, this embodiment is not limited at all by the following example.

The material used by the Example and the comparative example and the evaluation method of various characteristics are shown below.

[Purification of 1,3-butadiene]

The 1, 3- butadiene used for superposition | polymerization of a modified conjugated diene type polymer was refine | purified by the following process.

(Washing process)

It operated under the conditions of circulating water quantity 1m <3> / hr, and renewed (makeup) quantity 0.1m <3> / hr.

The 1,3-butadiene and the wash water are mixed using a static mixer (Static mixer N60 series, manufactured by Noritake Co., Ltd.), and then transferred to a decanter, and the 1,3-butadiene phase with the decanter. The aqueous phase was separated.

Moreover, it operated on the conditions of 30 degreeC of liquid temperature, and 1.0 MPaG of decanter pressures.

The residence time of the 1,3-butadiene phase in the decanter was 30 minutes.

The water phase separated by the decanter was introduced into a de1,3-butadiene bath, mixed with steam and heated to 89 ° C, at the same time, the voltage was set to 0.01 MPaG, and 1,3-butadiene was separated from the water phase.

(Oxygen removal step by deoxidizer)

Subsequently, 1,3-butadiene after the said (washing process) and the said deoxidizer were used at the circulation flow rate of 1m <3> / hr using the 10% aqueous solution of DiClean F-504 (Kurita Co., Ltd.) as a deoxidizer. The aqueous solution of was mixed using the static mixer and liquid solution extraction was performed.

Then, it moved to the decanter and separated the 1, 3- butadiene phase and the water phase with the said decanter.

The residence time of the 1,3-butadiene phase in the decanter was 30 minutes. Moreover, it operated on the conditions of 30 degreeC of liquid temperature, and 1.0 MPaG of decanter pressures.

(Polymerization inhibitor removal process)

Subsequently, a 10% caustic soda water solution was mixed with 1,3-butadiene after the above (oxygen removal step by deoxidant) using a packed column containing polling at a circulation flow rate of 1 m 3 / hr, to extract liquid solution. The decanter was further transferred to another decanter, and the 1,3-butadiene phase and the aqueous phase were separated by the other decanter.

The residence time of the 1,3-butadiene phase in this other decanter was 60 minutes. In addition, in the polymerization inhibitor removal process, it operated on the conditions of 30 degreeC of liquid temperature, and 1.0 MPaG of decanter pressures.

(Dewatering Tower Process)

In the above (polymerization inhibitor removal step), mixed hexane was added to 1,3-butadiene separated by another decanter, and the concentration was 1,3-butadiene: 50% by mass and supplied to the dehydration tower.

In the dehydration tower, the azeotropic mixture of 1,3-butadiene and water which flowed out from the top (top) was cooled and condensed, and then transferred to a decanter, and the 1,3-butadiene phase and the water phase were separated by the decanter.

The water phase was removed, and the 1,3-butadiene phase was returned to the tower entrance of the dehydration tower, and the dehydration tower process was performed continuously.

The mixed solution of 1,3-butadiene and hexane dehydrated was taken out from the bottom (top) of the dehydration column.

(Adsorption step)

After the above (dehydration step), the mixed solution of 1,3-butadiene and hexane is passed through a 500L desiccant dryer (vertical cylindrical bath manufactured by HITACHI Seisakusho Co., Ltd.) containing activated alumina, and 1,3-butadiene Trace residual impurities in the mixture were adsorbed and removed to obtain purified 1,3-butadiene.

[Purification of styrene]

The styrene used for superposition | polymerization of a modified conjugated diene type polymer was refine | purified by the following process.

(Gamma) -alumina shape | molded to the column shape of 3 mm (phi) x3mm was impregnated in the palladium chloride aqueous solution of 0.6% of density | concentration, and it dried at 100 degreeC overnight. Subsequently, the dried product was reduced for 16 hours at a temperature of 400 ° C. under a hydrogen stream to obtain a hydrogenation catalyst having a composition of Pd (0.3%) / γ-Al ₂ O ₃ . Purified styrene was obtained by charging 2000 g of the obtained hydrogenation catalyst to a tubular reactor and circulating for 8 hours, keeping the temperature of this catalyst at 80 degreeC.

[Purification of normal hexane]

The normal hexane used for superposition | polymerization of a modified conjugated diene type polymer was refine | purified by the following process.

2000 g of molecular 13-X (Union Showa) was charged to a tubular reactor and circulated at room temperature for 24 hours to obtain purified normal hexane.

[Purity analysis (calculation of impurity total) of raw materials]

As impurities in the raw materials, quantitative analysis of allenes, acetylenes, and amines was performed.

Allens and acetylenes were qualitatively determined by gas chromatography.

In addition, the column used Rt-Alumina BOND / MAPD (Shimadzu Seisakusho).

In addition, amines were extracted using boric acid, quantified by a titration method, and the total amount of impurities (ppm) was calculated.

((Physical Property 1) Amount of Bonded Styrene)

Using the modified conjugated diene-based polymer as a sample, 100 mg of the sample was dissolved in chloroform with a total volume of 100 mL, and used as a measurement sample.

The amount of binding styrene (mass%) with respect to 100 mass% of the modified conjugated diene polymer which is a sample was measured by the absorption amount of the ultraviolet absorption wavelength (near 254 nm) by the phenyl group of styrene (the spectrophotometer "UV made from Shimadzu Corporation) -2450 ").

[(Physical property 2) microstructure (butadiene bond amount) of butadiene part]

Using the modified conjugated diene polymer as a sample, 50 mg of the sample was dissolved in 10 mL of carbon disulfide to obtain a measurement sample.

Using a solution cell, the infrared spectrum was measured in the range of 600 to 1000cm ^-1, the formula of Hampton method (RRHampton, the method described in Analytical Chemistry 21, 923 (1949) ) by absorption of the predetermined wave number According to this, the microstructure of the butadiene portion, that is, the 1,2-vinyl bond amount (mol%) was obtained (Fourier transform infrared spectrophotometer "FT-IR230" manufactured by Nippon Bunko Co., Ltd.).

[(Physical property 3) molecular weight]

RI detector (trade name "HLC8020 made by Tosoh Corporation" using a GPC measuring device (trade name "HLC-8320GPC" manufactured by Tosoh Corporation) in which three modified conjugated diene-based polymers were used as samples and three columns containing polystyrene gels as fillers were used. The weight average molecular weight (Mw ₁ ), the number average molecular weight (Mn ₁ ), and the molecular weight distribution (Mw ₁ / Mn ₁ ) are determined based on the calibration curve obtained using standard polystyrene. It was.

Eluent was used as THF (tetrahydrofuran).

The column connected three brand names "TSKgel SuperMultiporeHZ-H" made by Tosoh Corporation, and used the brand name "TSKguardcolumn SuperMP (HZ) -H" made by Tosoh Corporation as its guard column.

10 mg of the sample for measurement was dissolved in 20 mL of THF to make a measurement solution. 10 μL of the measurement solution was injected into a GPC measuring device, and the measurement was performed under an oven temperature of 40 ° C. and a THF flow rate of 0.35 mL / min.

(Physical property 4) Modification rate with respect to total amount of conjugated diene type polymer]

The chromatogram was measured by applying the characteristic which the modified basic polymer component adsorb | sucked to the GPC column which used the modified conjugated diene type polymer as a sample for measurement, and a silica gel as a filler.

The adsorption amount to the silica column was measured from the difference between the chromatogram measured by the polystyrene column and the chromatogram measured by the silica column in the measurement sample solution containing the measurement sample and the low molecular weight internal standard polystyrene. , The denaturation rate was calculated.

Specifically, it is as showing below.

Preparation of Sample Solution for Measurement:

10 mg of the measurement sample and 5 mg of the standard polystyrene were dissolved in 20 mL of THF (tetrahydrofuran) to obtain a sample solution for measurement.

GPC measurement conditions using polystyrene column:

Using the brand name "HLC-8320GPC" manufactured by Tosoh Corporation, THF was used as the eluent, 10 μL of the sample solution for measurement was injected into the apparatus, and the RI detector was placed under conditions of a column oven temperature of 40 ° C and a THF flow rate of 0.35 mL / min. To obtain a chromatogram. The column connected three brand names "TSKgel SuperMultiporeHZ-H" made by Tosoh Corporation, and used the brand name "TSKguardcolumn SuperMP (HZ) -H" made by Tosoh Corporation as its guard column.

GPC measurement conditions using silica column:

Using the brand name "HLC-8320GPC" manufactured by Tosoh Corporation, THF was used as the eluent, 50 μL of the sample solution for measurement was injected into the apparatus, and the RI detector was placed under conditions of a column oven temperature of 40 ° C and a THF flow rate of 0.5 mL / min. To obtain a chromatogram. The column was connected by using brand names "Zorbax PSM-1000S", "PSM-300S", and "PSM-60S", and was used by connecting a brand name "DIOL 4.6 x 12.5mm 5micron" as a guard column to the front end thereof.

How to calculate denaturation rate:

The total peak area of the chromatogram using the polystyrene column was 100, the peak area of the sample was P1, the peak area of the standard polystyrene was P2, and the total peak area of the chromatogram using the silica column was 100. The peak area of P3 was set to P4 and the peak area of standard polystyrene was P4, and the modification ratio (mass%) was obtained from the following equation.

Modification rate (mass%) = [1- (P2 × P3) / (P1 × P4)] × 100

(In the above formula, P1 + P2 = P3 + P4 = 100.)

[(Physical Property 5) Modification Rate of Low Molecular Weight Component]

According to the measurement of said (physical property 3), RI detector (brand name "HLC8020 made by Tosoh Corporation) was used using the GPC measuring apparatus (brand name" HLC-8320GPC "by Tosoh Corporation) which connected three columns which made polystyrene gel fillers. The chromatogram is measured using a quot;) and based on the calibration curve obtained using standard polystyrene, the weight average molecular weight (Mw ₂ ), number average molecular weight (Mn ₂ ) and molecular weight distribution (Mw ₂ / of the modified conjugated diene-based polymer Mn ₂ ) and the peak top molecular weight (Mp ₂ ) of the modified conjugated diene polymer were measured.

In addition, the peak top molecular weight (Mp ₂₎ when the peak top, or peak top the plurality present in the molecular weight curve, and to be the peak top molecular weight of a minimum molecular weight of the peak top molecular weight 1 (Mp ₂₎ The height of the chart in the molecular weight which is / 2 was made into L1.

Using a silica column in accordance with the measurement of the (property 3) the height of the chart of the measurement, peak top molecular weight of 1/2 the molecular weight (Mp ₂₎ to the L2.

The molecular weight component which is 1/2 of the molecular weight of this peak top is made into the low molecular weight component.

The modification rate of the low molecular weight component was calculated by 1-L1 / L2.

[Modification of Low Molecular Weight Components]

The modification degree of the low molecular weight component was calculated by dividing the modification rate (FL) of the (physical property 5) low molecular weight component by the modification rate (FT) of the total amount of the (physical property 4) conjugated diene polymer.

Denaturity of low molecular weight component = (FL / FT) × 100

((Physical Property 6) Shrinkage Factor (g ')]

Using a modified conjugated diene polymer as a sample, a chromatogram was measured using a GPC-scattering measuring device equipped with a viscosity detector having three columns of polystyrene gel-filled fillers, and based on the solution viscosity and the light scattering method. Was obtained.

As the eluent, a mixed solution of tetrahydrofuran and triethylamine (THF in TEA: triethylamine 5 mL was mixed and adjusted to 1 L of tetrahydrofuran) was used.

The column was used by connecting guard column: brand name "TSKguardcolumn HHR-H" manufactured by Tosoh Corporation, and column name: "TSKgel G6000HHR", "TSKgel G5000HHR" and "TSKgel G4000HHR" manufactured by Tosoh Corporation.

The GPC-light scattering measuring apparatus (the brand name "Viscotek TDAmax" by Malvern) was used with the viscosity detector on the conditions of oven temperature of 40 degreeC, and THF flow rate of 1.0 mL / min.

10 mg of the sample for measurement was dissolved in 20 mL of THF to prepare a sample solution for measurement, and 200 μL of the sample solution for measurement was injected into a GPC measuring device and measured.

The intrinsic viscosity and molecular weight of the obtained sample solution for measurement, and the constant (K, alpha) in the relationship of intrinsic viscosity and molecular weight ([η] = KMα ([η]: intrinsic viscosity, M: molecular weight) logK = -3.883) , intrinsic viscosity [η] at each molecular weight M for the relationship between the standard intrinsic viscosity [η] ₀ and the molecular weight M created by setting α = 0.771 and inputting the range of the molecular weight M to 1000 to 20000000. the intrinsic viscosity of the ₀ as the relationship [η] calculating a [η] / [η] ₀ in each molecular weight M, which was the average value to its shrinkage factor (g ').

In addition, g 'is the value which M averaged in 1 million or more and 2 million or less.

[Production of Modified Conjugated Diene-Based Polymer]

(Modified conjugated diene polymer A1)

Its inner volume is 10L, the ratio (L / D) of the inner height L and the diameter D is 4.0, and has an inlet at the bottom and an outlet at the top, and a stirrer which is a model reactor with a stirrer and a jacket for temperature control. Two molding pressure vessels were connected to each other to form a polymerization reactor.

12.2 g / min of 1,3-butadiene, which had been previously removed from water, was mixed with styrene (12.0 g / min) and n-hexane under the conditions of 210 g / min. The allenes contained in this mixture were 9 ppm, the acetylenes were 15 ppm, and the amines were 2 ppm. The impurity total was 26 ppm.

In the static mixer provided in the middle of the piping for supplying the mixed solution to the inlet of the first reactor, n-butyllithium for residual impurity inert treatment is added at 0.0800 mmol / min and mixed, followed by mixing at the bottom of the first reactor. It was fed continuously.

In addition, piperidinolithium prepared in advance as a polymerization initiator with 2, 2-bis (2-oxolanyl) propane as a polar substance at a rate of 0.0120 g / min (it abbreviates as "LA-1" in a table | surface).) And n-butyllithium (obtained by preparing molar ratio piperidinolithium: n-butyllithium = 0.75: 0.25, piperidine and n-butyllithium at molar ratio piperidine: n-butyllithium = 0.75: 1.00) The mixed solution was fed to the bottom of the first polymerization reactor in which the mixed solution was vigorously mixed with a stirrer at a rate of 0.0800 mmol (lithium molar ratio) / minute, and the polymerization reaction was continued continuously.

The temperature was controlled such that the temperature of the polymer solution at the first reactor top outlet was 65 ° C. By connecting the top of the first reactor and the bottom of the second reactor, the polymer solution was continuously fed from the top of the first reactor to the bottom of the second reactor. The temperature was controlled such that the temperature of the polymer at the second reactor top outlet was 70 ° C.

Subsequently, when the polymerization was sufficiently stable, an antioxidant (BHT) was continuously added at 0.055 g / min (n-hexane solution) so as to be 0.2 g per 100 g of polymer to the polymer solution flowing out of the outlet of the second reactor, and polymerization was performed. The reaction was terminated.

At the same time as the antioxidant, 100 g of the polymer was added continuously so that the extender oil (Jomo process NC140 manufactured by JX Nikko-Niseki Energy Co., Ltd.) was 37.5 g, and mixed with a static mixer.

The solvent was removed by steam stripping the modified conjugated diene polymer solution after extension oil mixing, and the modified conjugated diene polymer A1 was obtained. Various measurements were made and the results are shown in Table 1.

In addition, the obtained polymer solution was sent to the molding pressure vessel whose inner volume was 100L.

(Modified conjugated diene polymer A2)

Its inner volume is 10L, the ratio (L / D) of the inner height L and the diameter D is 4.0, and has an inlet at the bottom and an outlet at the top, and a stirrer which is a model reactor with a stirrer and a jacket for temperature control. Two molding pressure vessels were connected to each other to form a polymerization reactor.

12.2 g / min of 1,3-butadiene, which had been previously removed from water, was mixed with styrene (12.0 g / min) and n-hexane under the conditions of 210 g / min. The allenes contained in this mixture were 9 ppm, the acetylenes were 15 ppm, and the amines were 2 ppm. The impurity total was 26 ppm.

In the static mixer provided in the middle of the piping for supplying the mixed solution to the inlet of the first reactor, n-butyllithium for residual impurity inert treatment is added at 0.0800 mmol / min and mixed, followed by mixing at the bottom of the first reactor. It was fed continuously.

In addition, piperidino lithium prepared in advance as a polymerization initiator at a rate of 0.0157 g / min as a polar substance at a rate of 0.0157 g / min (abbreviated as "LA-1" in the table.) And n-butyllithium (obtained by preparing molar ratio piperidinolithium: n-butyllithium = 0.75: 0.25, piperidine and n-butyllithium at molar ratio piperidine: n-butyllithium = 0.75: 1.00) The mixed solution was supplied to the bottom of the first polymerization reactor in which the mixed solution was vigorously mixed with a stirrer at a rate of 0.144 mmol (lithium molar ratio) / minute, and the polymerization reaction was continued continuously.

The temperature was controlled such that the temperature of the polymer solution at the first reactor top outlet was 65 ° C. By connecting the top of the first reactor and the bottom of the second reactor, the polymer solution was continuously fed from the top of the first reactor to the bottom of the second reactor. The temperature was controlled such that the temperature of the polymer at the second reactor top outlet was 70 ° C.

Subsequently, when the polymerization is sufficiently stable, bis (3-trimethoxysilylpropyl) methylamine (abbreviated as "A" in the table) is 0.0360 mmol / in the polymer solution flowing out from the outlet of the second reactor as a modifier. The polymer solution added continuously at the rate of minutes and the modifier added were mixed and modified by passing through a static mixer.

To the modified polymer solution, antioxidant (BHT) was continuously added at 0.055 g / min (n-hexane solution) so as to be 0.2 g per 100 g of polymer, and the modification reaction was completed.

At the same time as the antioxidant, 100 g of the polymer was added continuously so that the extender oil (Jomo process NC140 manufactured by JX Nikko-Niseki Energy Co., Ltd.) was 37.5 g, and mixed with a static mixer.

The solvent was removed by steam stripping the modified conjugated diene polymer solution after extension oil mixing, and the modified conjugated diene polymer A2 was obtained. Various measurements were made and the results are shown in Table 1.

Moreover, the obtained modified conjugated diene type polymer solution was sent to the molding pressure vessel whose inner volume was 100L.

(Modified conjugated diene polymer A3, modified conjugated diene polymer B1 to B3)

The production method is similar to the modified conjugated diene polymer A2, and the amount of the polymerization initiator, the amount of the polar substance, the type of the modifier, and the amount of the modifier are adjusted as shown in Tables 1 to 2 below, and the modified conjugated diene polymer A3 and modified conjugated diene polymers B1 to B3 were obtained.

In Tables 1 and 2, the modifier "B" is N, N, N'-tris (3-trimethoxysilylpropyl) -N '-[3- (2,2-dimethoxy-1-aza-2- Silacyclopentane) propyl] -1,3-propanediamine.

(Modified conjugated diene polymer A4)

Its inner volume is 10L, the ratio (L / D) of the inner height L and the diameter D is 4.0, and has an inlet at the bottom and an outlet at the top, and a stirrer which is a model reactor with a stirrer and a jacket for temperature control. Two molding pressure vessels were connected to each other to form a polymerization reactor.

18.0 g / min of 1, 3- butadiene removed by water previously, 9.7 g / min of styrene, and n-hexane were mixed on the conditions of 145 g / min. The allenes contained in this mixture were 9 ppm, the acetylenes were 15 ppm, and the amines were 2 ppm. The impurity total was 26 ppm.

In the static mixer provided in the middle of the piping for supplying the mixed solution to the inlet of the reactor, n-butyllithium for residual impurity inert treatment was added at 0.0648 mmol / min, mixed, and then continuously supplied to the bottom of the reactor. .

Further, at a rate of 0.0216 g / min for 2,2-bis (2-oxolanyl) propane as the polar substance, n-butyllithium (abbreviated as "NBL" in the table) as the polymerization initiator is 0.0864 mmol / At the rate of minutes, it was supplied to the bottom of the polymerization reactor mixed vigorously with a stirrer and the polymerization reaction was continued continuously. The temperature was controlled such that the temperature of the polymer solution at the reactor top outlet was 75 ° C.

When the polymerization is sufficiently stable, 0.0432 of 3- (4-methyl-1-piperazino) propyltriethoxysilane (abbreviated as "C" in the table) is used as a modifier in the polymer solution flowing out from the outlet of the reactor. The polymer solution added continuously at a rate of mmol / min and the denaturant added were mixed and modified by passing through a static mixer.

To the polymer solution subjected to the modification reaction, an antioxidant (BHT) was continuously added at 0.055 g / min (n-hexane solution) so as to be 0.2 g per 100 g of the polymer, and the coupling reaction was completed. Simultaneously with the antioxidant, oil was continuously added to 100 g of the polymer (Jomo process NC140 manufactured by JX Nikko Nesseki Energy Co., Ltd.) to 37.5 g, and mixed with a static mixer.

The solvent was removed by steam stripping the modified conjugated diene polymer solution after extension oil mixing, and the modified conjugated diene polymer A4 was obtained. Various measurements were made and the results are shown in Table 1.

Moreover, the obtained modified conjugated diene type polymer solution was sent to the molding pressure vessel whose inner volume was 100L.

(Modified conjugated diene polymer A5 to A11, modified conjugated diene polymer B4 to B10)

In the same manner as in the modified conjugated diene-based polymer A4, the addition amount of the polymerization initiator, the addition amount of the polar substance, the type of the modifying agent, and the addition amount of the modifying agent are adjusted as shown in Tables 1 and 2 below to modify the modified conjugated diene-based polymer A5. To A11 and modified conjugated diene-based polymers B4 to B10 were obtained.

Various measurements were performed and the results are shown in Tables 1 and 2.

In addition, the obtained modified conjugated diene-based polymer solution was fed to a molding pressure vessel having a volume of 100 L, respectively.

In Tables 1 and 2, the modifier "D" is tetraglycidyl-1,3-bisaminomethylcyclohexane.

Modifier "E" is tris (3-trimethoxysilylpropyl) amine.

When two numerical values are described in polymerization temperature in a table | surface, it shows that the former is the 1st group and the latter is the 2nd group.

Hereinafter, it shows about a modifier.

A: bis (3-trimethoxysilylpropyl) methylamine

B: N, N, N'-tris (3-trimethoxysilylpropyl) -N '-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3 Propanediamine

C: 3- (4-methyl-1-piperazino) propyltriethoxysilane

D: tetraglycidyl-1,3-bisaminomethylcyclohexane

E: tris (3-trimethoxysilylpropyl) amine

Example 1: Modified Conjugated Diene-based Polymer Mixture C1)

The polymer solution of the modified conjugated diene-based polymer A6 and the polymer solution of the modified conjugated diene-based polymer B1 prepared by the above-described method and delivered to a molding pressure vessel has a mass ratio of the modified conjugated diene-based polymer A6 and the modified conjugated diene-based polymer B1. , (A6) :( B1) = 70:30 The liquid was sent so that it might be joined in piping. After confluence, the mixture was stirred and mixed with a rotary stirrer.

Subsequently, the solvent was removed by steam stripping to obtain a modified conjugated diene polymer mixture C1.

Various measurements were made and the results are shown in Table 3.

(Examples 2 to 21: modified conjugated diene polymer mixture C2 to C21)

The production method is performed in the same manner as the modified conjugated diene-based polymer mixture C1, and the combination of the modified conjugated diene-based polymer A and the modified conjugated diene-based polymer B is used to change the conjugated diene-based polymer A in the modified conjugated diene-based polymer mixture C. The contents were changed as shown in Tables 3 and 4 to obtain modified conjugated diene polymer mixtures C2 to C21.

Various measurements were performed and the results are shown in Tables 3 and 4.

[Examples 22 to 42 and Comparative Examples 1 to 21]

According to the formulation shown below using the sample (modified conjugated diene-type polymer mixture C1-C21, modified conjugated diene type polymer A1-A11, modified conjugated diene type polymer B1-B10) shown in the said Tables 1-4 as a raw material rubber, The modified conjugated diene polymer composition containing each raw material rubber was obtained.

Sample: 100 parts by mass

Silica (manufactured by Evonik Degussa Co., Ltd., trade name "Ultrasil7000GR", nitrogen adsorption specific surface area: 175 m 2 / g): 75 parts by mass

Silane coupling agent (Evonik Degussa make, brand name "Si75" (tetraethoxysilylpropyl disulfide): 6 parts by mass

Process oil (manufactured by JX Nikko-Niseki Energy, trade name `` NC140 ''): 42 parts by mass

Carbon black (trade name: "Shith KH (N339)", iodine adsorption amount 90 g / kg, CTAB specific surface area 95 m <2> / g) by Toka Carbon Co., Ltd .: 5 parts by mass

Zinc (Mitsui Kinzoku Kogyo Kogyo Co., Ltd., brand name "Zinc 1"): 2.5 parts by mass

Stearic acid: 1.0 parts by mass

Wax: (manufactured by Ouchi Shinko Chemical Co., Ltd., trade name "Sun Rust", rhubarb white granules, freezing point 65 ° C or higher, specific gravity 0.93, 1.5 parts by mass

Anti-aging agent (N-isopropyl-N'-phenyl-p-phenylenediamine): 2.0 parts by mass

Sulfur: 2.2 parts by mass

Vulcanization accelerator (N-cyclohexyl-2-benzothiazyl sulfinamide): 1.7 parts by mass

Vulcanization accelerator (diphenylguanidine): 2.0 parts by mass

The above materials were kneaded by the following method to obtain an unvulcanized rubber composition and a vulcanized rubber sheet.

Using a kneader equipped with a temperature control device (0.5L capacity), as a kneading in the first stage, a modified conjugated diene-based polymer (modified SBR1) and a silica-based inorganic filler (with a filling rate of 65% and a rotor rotational speed of 50 rpm) Silica), silane coupling agent, and process oil were kneaded for 4 minutes. At this time, the temperature of the kneader was controlled and the discharge temperature (compound) obtained the modified conjugated diene polymer composition at 155-160 degreeC.

Subsequently, as a kneading | mixing of the 2nd stage, after cooling the compound obtained above to room temperature, carbon black, zincation, a stearic acid, a wax, and an antioxidant were added, and it knead | mixed for 3 minutes with the said kneader. Also in this case, discharge temperature (blend) was adjusted to 155-160 degreeC by the temperature control of the mixer. Then, after discharging the compound from the kneader, the compound was passed through the 10-inch φ open roll six times to produce a sheet-like unvulcanized rubber composition, and after cooling, the workability was evaluated.

In addition, after the unvulcanized composition was heated to 70 ° C. for 30 minutes using an oven, sulfur and a vulcanization accelerator were added and kneaded with a 10 inch phi open roll set at 70 ° C. as a kneading in the third stage. . Then, the remainder of the composition was vulcanized and molded in a vulcanization press at 160 ° C. for 20 minutes to obtain a vulcanizate. After vulcanization, the physical properties of the rubber composition were measured. Physical property measurement results are shown in Tables 5 to 10 below.

[Physical measurement method]

(Compound Mooney Viscosity)

After kneading of the second stage, the Mooney viscosity was measured using an L-type rotor in accordance with JIS K6300, using a Mooney viscometer (trade name "VR1132" manufactured by Uejima Seisakusho Co., Ltd.) as a sample. .

Measurement temperature was 100 degreeC.

First, the sample was preheated at the test temperature for 1 minute, the rotor was rotated at 2 rpm, the torque after 4 minutes was measured, and it was set as Mooney viscosity (ML _{(1 + 4)} ).

The result of the comparative example 6 was made into 100 and indexed, and it was set as the index of workability. The larger the index, the better the workability.

(Viscoelastic parameters)

About the rubber composition after vulcanization, the viscoelasticity parameter was measured in the torsion mode using the viscoelasticity tester "ARES" made from Leometrics Scientific. Each measured value was indexed by making the result with respect to the rubber composition of the comparative example 6 100.

Tanδ measured at a frequency of 10 Hz and a strain of 1% at 0 ° C was used as an index of wet grip property. Larger value indicates better wet grip property. In addition, the inverse of tan-delta measured by the frequency of 10 Hz and 3% of deformation at 50 degreeC was made into the index of fuel economy saving. Larger values indicate better fuel economy.

(Tensile breaking strength)

About the rubber composition after vulcanization, tensile breaking strength was measured based on the tensile test method of JISK6251, and the result of Comparative Example 6 was made into 100, and it indexed.

(Wear resistance)

About the rubber composition after vulcanization, the load amount of 44.4 N and 1000 revolutions is measured based on JISK6264-2 using the Akron abrasion tester (made by Yasuda Seiki Seisakusho Co., Ltd.), and the result of the comparative example 6 is made into 100 Exponentially. The larger the index, the better the wear resistance.

Mass fraction of the modified conjugated diene-based polymer A and the modified conjugated diene-based polymer B from the evaluation results of the compositions of Comparative Examples 1 to 21 using only the modified conjugated diene-based polymers A1 to A11 and the modified conjugated diene-based polymers B1 to B10 alone. By considering, the expected value of the evaluation result of the composition of Examples 22-32 using the modified conjugated diene type polymer mixture C1-C21 of Examples 1-21 was computed.

For example, in the case of the modified conjugated diene-based polymer mixture C1, since the mass ratio of the modified conjugated diene-based polymer A and the modified conjugated diene-based polymer B is 70:30, (expected value of the evaluation result of the modified conjugated diene-based polymer C1) = ( The evaluation result of the modified conjugated diene polymer A) x (70/100) + (the evaluation result of the modified conjugated diene polymer B) x (30/100).

In the same manner, the expected values calculated from each were compared with the actual results.

The expected values and the measurement results are shown in Tables 5 to 8 below.

In Tables 5-8, the numerical value on the left side of each Example column is an actual measured value, and the numerical value on the right side is an estimated value calculated from the mass fraction.

The measured value of the comparative example 1-the comparative example 21 is shown in following Table 9, 10.

As shown in Tables 5 to 10, the compositions using the modified conjugated diene-based polymer mixtures of Examples 1 to 21 are less wear resistant than the compositions using the corresponding modified conjugated diene-based polymers A1 to A11, respectively, but are excellent in workability. I knew.

In addition, the actual measurement result is superior to the estimated value of the composition of the modified conjugated diene-based polymer mixture C in consideration of the mass fraction of the modified conjugated diene-based polymer A and the modified conjugated diene-based polymer B, and has low hysteresis loss and wet skid. It turned out that the balance of resistance, abrasion resistance, and workability is favorable. Similarly, although it was excellent in workability than the composition using the modified conjugated diene type polymers B1-B10 single body, respectively, it turned out that it is excellent in abrasion resistance.

In addition, the actual measurement result is superior to the evaluation expected value of the composition using the modified conjugated diene-based polymer mixture C in consideration of the mass fraction of the modified conjugated diene-based polymer A and the modified conjugated diene-based polymer B, and has low hysteresis loss and wetness. It turned out that the balance of skid resistance, abrasion resistance, and workability is favorable. In addition, it was confirmed to have a sufficient tensile strength for practical use.

In addition, in order to obtain the modified conjugated diene polymer mixture C, the modified conjugated diene polymer A in the solvent-removed state after the polymerization is not mixed with the modified conjugated diene polymer B, but the modified conjugated diene in the solution state before the solvent removal after the polymerization. The polymer A and the modified conjugated diene polymer B were mixed and finished. Thereby, although the finishing process was required twice, it became possible to obtain the modified conjugated diene polymer C by one finishing process, and the manufacturing process became efficient.

The method for producing the modified conjugated diene polymer mixture according to the present invention has industrial applicability in fields such as tire treads, interior / exterior products of automobiles, dustproof rubbers, belts, shoes, foams, and various industrial products.

Claims (10)

A modified conjugated diene polymer (A) having a weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of 70 × 10 ⁴ or more and 300 × 10 ⁴ or less,
The modified conjugated diene polymer (B) having a Mw of 10 × 10 ⁴ or more and less than 70 × 10 ⁴ measured by GPC is continuously polymerized using one or more reactors, respectively.
Solution-mixing the polymer solution containing the said modified conjugated diene type polymer (A), and the polymer solution containing the said modified conjugated diene type polymer (B),
Thereafter, the solvent is removed to obtain a modified conjugated diene polymer mixture (C).
Method of producing a modified conjugated diene-based polymer mixture,
The molecular weight distribution (Mw / Mn) of the said modified conjugated diene type polymer mixture (C) is 1.8 or more and 4.5 or less, The manufacturing method of the modified conjugated diene type polymer mixture. The mixed mass ratio of the modified conjugated diene polymer (A) and the modified conjugated diene polymer (B) in the modified conjugated diene polymer mixture (C) according to claim 1 (A) / (B) ) From 90/10 to 40/60,
Method for producing a modified conjugated diene polymer mixture. The method for producing a modified conjugated diene-based polymer mixture according to claim 1 or 2, wherein Mw of the modified conjugated diene-based polymer (A) is 100 × 10 ⁴ or more and 300 × 10 ⁴ or less. The difference (ΔMw) of the weight average molecular weight of the modified conjugated diene-based polymer (A) and the modified conjugated diene-based polymer (B) is 50 × 10 ⁴ or more,
Method for producing a modified conjugated diene polymer mixture. The modification rate with respect to the total amount of the conjugated diene type polymer of the said modified conjugated diene type polymer mixture (C) is adjusted to 50 mass% or more,
Method for producing a modified conjugated diene polymer mixture. The shrinkage factor (g ') by 3D-GPC of the modified conjugated diene-based polymer (A) and / or the modified conjugated diene-based polymer (B) is 0.70 or more and 1.0 or less.
Method for producing a modified conjugated diene polymer mixture. The shrinkage factor (g ') by 3D-GPC of the modified conjugated diene-based polymer (A) and / or the modified conjugated diene-based polymer (B) is 0.30 or more and less than 0.70.
Method for producing a modified conjugated diene polymer mixture. The said modified conjugated diene type polymer (A) and / or the said modified conjugated diene type polymer (B) has a functional group represented by following General formula (1) in the superposition | polymerization start terminal,
Method for producing a modified conjugated diene polymer mixture.

(In General Formula (1), R ¹ and R ² may be any one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Here, R <^1> and R <^2> may combine and form the cyclic structure with adjacent nitrogen atom, and in that case, R <^1> and R <^2> is a hydrocarbon group of 4-12 carbon atoms in total. R ¹ and R ² may have an unsaturated bond or may have a branched structure.) The said modified conjugated diene type polymer (A) and / or the said modified conjugated diene type polymer (B) has a functional group represented by the said General formula (1) in the superposition | polymerization start terminal, Furthermore, the said General formula Having a functional group containing an alkoxysilyl group and an amine at the terminal different from the said polymerization start terminal which has a functional group represented by (1),
Method for producing a modified conjugated diene polymer mixture. The said modified conjugated diene type polymer (B) has a modification rate with respect to the total amount of a conjugated diene type polymer of 50 mass% or more, The peak top in a molecular weight curve, or the said peak top is a When two or more exist, the modification rate of the component of the molecular weight which is 1/2 of the molecular weight of the peak top with the minimum molecular weight is 1/2 or more of the modification ratio with respect to the total amount of the said modified conjugated diene type polymer, The said modified conjugated diene system Content of nitrogen contained in a polymer (B) is 3 mass ppm or more and 70 mass ppm or less,
Method for producing a modified conjugated diene polymer mixture.